TWI825254B - Film adhesive, laminated sheet, composite sheet, and manufacturing method of laminate - Google Patents

Abstract

A film adhesive of the present embodiment is used for adhering a circuit forming surface of a chip to a light transmissive cover. When one surface of the film adhesive before heating at 260 ℃ is analyzed by X-ray photoelectron spectroscopy and the phosphorus concentration V₁ is measured; and in the film adhesive after measuring the V₁ and heating at 260 ℃ for ten minutes, a surface in which the V₁ is measured is analyzed by X-ray photoelectron spectroscopy and the phosphorus concentration V₂ is measured, the V₁ is 0.1 atomic % or more; and the decrease rate of the phosphorus concentration calculated from the V₁ and V₂ is 25% or less.

Description

Film adhesive, laminated sheet, composite sheet and method for manufacturing laminated body

The present invention relates to a film adhesive, a laminated sheet, a composite sheet and a method for manufacturing a laminated body. This application claims priority based on Japanese Patent Application No. 2018-246838 filed in Japan on December 28, 2018, and the contents of this application are incorporated into this article.

When manufacturing or processing various parts constituting electronic equipment, various film adhesives are used depending on the purpose. For example, when a semiconductor wafer is mounted on a circuit formation surface of a substrate, a film-like adhesive is attached to the inner surface of the semiconductor wafer in advance, and the semiconductor wafer is bonded (die-bonded) to the circuit of the substrate through the film-like adhesive. forming surface. In addition, when protecting the circuit formation surface of a chip such as a sensor, the circuit formation surface is covered with a translucent cover via a translucent film adhesive.

On the other hand, parts with such film-like adhesives are sometimes exposed to high temperatures due to heating steps such as reflow steps. In this case, there may be a problem that the film adhesive is deteriorated due to the influence of heat. For example, if a translucent film adhesive changes color, it will be difficult to read information through the film adhesive. The film-like adhesive contains a resin component to express adhesiveness and, in some cases, a thermosetting component to provide thermosetting properties. However, some of these components are unstable to heat. That is, conventional film adhesives are easily discolored by heating.

As a translucent film-like adhesive, for example, a die-bonding film is disclosed, which is used for die-bonding semiconductor wafers and has a light transmittance of 80% or more at a wavelength of 1065 nm (see Patent Document 1). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 6310748.

[Problem to be solved by the invention]

However, Patent Document 1 does not disclose the physical properties after heating such as the color of the crystal bonding film after heating.

An object of the present invention is to provide a film-like adhesive that is translucent before and after heating and whose coloring after heating is suppressed, a laminated sheet and a composite sheet using the film-like adhesive, and a laminated body using the film-like adhesive manufacturing method. [Means used to solve problems]

The present invention provides a film-like adhesive for bonding the circuit formation surface of a chip and a light-transmitting cover. When the side of the film-like adhesive before heating at 260°C is analyzed by X-ray photoelectron spectroscopy, The phosphorus concentration V ₁ is measured, and the surface of the film-like adhesive in which the V ₁ is measured after the V ₁ is measured and heated at 260° C. for 10 minutes is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus content. When the concentration is V ₂ , the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less. In the film-like adhesive of the present invention, the linear transmittance of the film-like adhesive before heating at 260°C for light with a wavelength of 400 nm to 800 nm is 90% or more, and the film-like adhesive after heating at 260°C for 10 minutes can also be used. The adhesive has a linear transmittance of more than 85% for light with a wavelength of 400 nm to 800 nm, and the thickness of the film-like adhesive is 10 μm to 40 μm. The film adhesive agent of the present invention may contain an aliphatic epoxy compound. The film-like adhesive of the present invention may contain a phenol resin (b2), and the content of the phenol resin (b2) in the film-like adhesive may be 10% by mass or less relative to the total mass of the film-like adhesive.

The film adhesive agent of the present invention may contain aliphatic phosphite as an antioxidant. In the film-shaped adhesive agent of the present invention, the film-shaped adhesive agent may contain an acrylic resin and an aliphatic polyisocyanate-based cross-linking agent, and the acrylic resin may have a functional group capable of bonding to the cross-linking agent. The present invention provides a laminated sheet including the film-like adhesive and a resin film provided on one side of the film-like adhesive. The present invention provides a composite sheet including the film-like adhesive and a cutting sheet provided on one side of the film-like adhesive. The cutting sheet includes a base material and an adhesive layer provided on one side of the base material. The adhesive layer is disposed between the base material and the film-like adhesive. The present invention provides a method for manufacturing a laminated body. The circuit formation surface of the wafer is bonded to one side of the film-like adhesive, and a light-transmitting cover is bonded to the other side of the film-like adhesive, thereby obtaining the aforementioned wafer and the aforementioned film-like adhesive. A laminated body composed of a film-like adhesive and the aforementioned translucent cover are laminated in this order. [Invention effect]

The film-like adhesive of the present invention has translucency before and after heating, and coloring after heating is suppressed. By using the laminated sheet or composite sheet of the present invention provided with the film-shaped adhesive of the present invention, the film-shaped adhesive can be provided on a part to which the film-shaped adhesive is applied. By the method of manufacturing a laminated body of the present invention, a laminated body in which a chip, a film-like adhesive, and a translucent cover are sequentially laminated can be produced.

◇Film-like adhesive The film-like adhesive according to one embodiment of the present invention is used to bond the circuit formation surface of the wafer and the light-transmitting cover, and when the side of the film-like adhesive before heating at 260°C is used, by X-ray photoelectron spectroscopy (in this specification, sometimes referred to as "XPS") was analyzed to measure the phosphorus concentration (in this specification, sometimes referred to as "P concentration") V ₁ , and the aforementioned V ₁ and In the film-like adhesive heated at 260° C. for 10 minutes, the surface of V ₁ was measured and analyzed by X-ray photoelectron spectroscopy (XPS; X-ray photoelectron spectroscopy) to determine the phosphorus concentration (P concentration) V At ₂ , the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ (sometimes referred to as "P concentration reduction rate" in this specification) is 25% or less.

Examples of film adhesives that satisfy the conditions of V ₁ , V ₂ and the aforementioned reduction rate include film adhesives containing a trivalent phosphorus compound. This kind of film adhesive has suppressed turbidity and coloration before and after heating at 260°C, etc., and has a linear transmittance of light with a wavelength of 400nm to 800nm (sometimes referred to as "light (400nm to 800nm)" in this specification). high.

The film adhesive agent of this embodiment can be used for adhesion of target objects when manufacturing or processing various parts constituting electronic equipment. For example, the circuit formation surface of a wafer such as a sensor can be covered with a light-transmitting cover (protective cover) via the film-like adhesive. That is, the aforementioned film-like adhesive can be used to form a film that adheres to the circuit of the chip. In this case, since the film adhesive has high translucency before and after heating and is suppressed from coloring as described above, the circuit formation surface of the wafer can be recognized stably and accurately through the translucent cover and the film adhesive. The visual information of existence.

An example of a sensor to be covered by the translucent cover (protective cover) is a fingerprint sensor. However, this is an example of a sensor.

In this specification, the surface of the substrate and the chip on which the circuit is formed is called the "circuit formation surface". In addition, in this specification, when only "wafer" is described, it does not only refer to semiconductor wafers, but also includes wafers other than semiconductor wafers.

The film-like adhesive agent of this embodiment preferably has thermosetting properties and preferably has pressure-sensitive adhesive properties. For example, a film-like adhesive that has both thermosetting properties and pressure-sensitive adhesive properties can be attached to various adherends by gently pressing it in an uncured state. In addition, the film-like adhesive may be softened by heating and attached to various adherends. The film-like adhesive is cured and eventually becomes a cured product with high impact resistance. The cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The linear transmittance of light (400nm to 800nm) of the film-like adhesive of this embodiment before heating at 260°C (sometimes referred to as "linear transmittance before heating" in this specification) is preferably 90% or more, and more preferably Preferably it is 91.5% or more, further preferably 93% or more, and particularly preferably 94.5% or more. Since the linear transmittance before heating is equal to or higher than the lower limit, the film-like adhesive before heating can correctly identify the nature of the image when the image is observed through the film-like adhesive (in this specification, there are: (referred to as "image recognition") is high.

The upper limit of the linear transmittance of the film adhesive before heating to light (400 nm to 800 nm) is not particularly limited, and may be 100%. For example, it is easier to produce a film-like adhesive with a linear transmittance of 99.8% or less before heating.

The linear transmittance of the film adhesive before heating with light (400 nm to 800 nm) can be appropriately adjusted to a range set by any combination of any of the above lower limit values and upper limit values. For example, in one embodiment, the linear transmittance before heating is preferably 90% to 99.8%, more preferably 91.5% to 99.8%, further preferably 93% to 99.8%, particularly preferably 94.5% to 99.8%. However, these are examples of the linear transmittance before heating.

The linear transmittance of light (400nm to 800nm) of the film-like adhesive according to this embodiment after heating at 260°C for 10 minutes (in this specification, sometimes referred to as "linear transmittance after heating") is preferably 85% or more. , for example, it can be any one of 87.5% or more, 90% or more, and 92% or more. Since the linear transmittance after heating is equal to or higher than the lower limit, the image visibility of the film-like adhesive after heating is high.

The upper limit of the linear transmittance of the film adhesive after the aforementioned heating to light (400 nm to 800 nm) is not particularly limited, and may be 100%. For example, the aforementioned film-like adhesive with a linear transmittance of 99.8% or less after heating is easier to produce.

The linear transmittance of the film adhesive after the above-mentioned heating before light (400 nm to 800 nm) can be appropriately adjusted to a range set by any combination of any of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the linear transmittance after heating is preferably 85% to 99.8%, for example, it may be any one of 87.5% to 99.8%, 90% to 99.8%, and 92% to 99.8%. However, these are examples of the linear transmittance after heating.

The linear transmittance before heating and the linear transmittance after heating of the film-like adhesive to light (400 nm to 800 nm) can be measured by a known method using a spectrophotometer.

The heating conditions of the film-like adhesive at 260° C. and 10 minutes when the linear transmittance after heating is specified are set taking into account the conditions in the heating step such as the reflow step.

The shear strength of the film-like adhesive agent of this embodiment is not particularly limited, but is preferably 20N/2mm□ or more. For example, it can be 50N/2mm□ or more, 60N/2mm□ or more, 70N/2mm□ or more, and 80N/ Any one above 2mm□. When the shear strength of the film-like adhesive is equal to or higher than the aforementioned lower limit, the adhesion force of the film-like adhesive to the object to be adhered becomes stronger. In addition, in this manual, the unit "N/2mm□" is synonymous with "N/(2mm×2mm)".

The upper limit of the shear strength of the film-like adhesive is not particularly limited, either. For example, film adhesives with a shear strength of 300N/2mm□ or less are easier to produce.

The shear strength of the film-like adhesive agent can be appropriately adjusted to be within a range set by any combination of any of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the shear strength is preferably 20N/2mm□ to 300N/2mm□, for example, it can be 50N/2mm□ to 300N/2mm□, 60N/2mm□ to 300N/2mm□, or 70N/2mm Any one of □ to 300N/2mm□, and 80N/2mm□ to 300N/2mm□. However, these are examples of the aforementioned shear strength.

The shear strength of the film-like adhesive in this embodiment is measured by the method shown below. (Measurement method of shear strength of film adhesives) Using a film adhesive with a size of 2 mm × 2 mm and a thickness of 20 μm, a copper plate with a size of 30 mm × 30 mm and a thickness of 300 μm, and a silicon wafer, make one side of the film adhesive and attach it to the surface of the silicon wafer. , the other side is completely attached to the surface of the aforementioned copper plate to form a test piece. On at least one side of the test piece, the film-like adhesive is aligned with the side of the silicon wafer. Under the temperature condition of 23°C, on the side of the test piece where the alignment was performed, the film-like adhesive and the silicon wafer are parallel to the other side of the film-like adhesive. direction, apply force at a speed of 200 μm/s, and use the maximum value of the force applied until the film-like adhesive is destroyed as the shear strength (N/2mm□) of the film-like adhesive.

When the P concentration V ₁ is measured by XPS analysis on one side of the film-like adhesive before heating at 260° C., V ₁ is 0.1 atomic % or more, preferably 0.12 atomic % or more, more preferably 0.14 atomic % or more. For example, it may be 0.2 atomic % or more and 0.3 atomic % or more. When V ₁ is equal to or more than the aforementioned lower limit, the effect of suppressing coloration before heating (for example, heating at 260° C.) of the film adhesive becomes high.

The upper limit of V ₁ is not particularly limited. For example, a film adhesive with _V1 of 0.5 atomic % or less is easier to produce.

V ₁ can be appropriately adjusted to be within a range set by any combination of any of the above lower limit values and upper limit values. For example, in one embodiment, V ₁ is preferably 0.1 atomic % to 0.5 atomic %, more preferably 0.12 atomic % to 0.5 atomic %, further preferably 0.14 atomic % to 0.5 atomic %, for example, it can be 0.2 atomic % to 0.5 atomic %, and any one of 0.3 atomic % to 0.5 atomic %.

When V ₁ is measured and heated at 260° C. for 10 minutes, XPS analysis is performed on the measurement surface of V ₁ to measure P concentration V ₂ , V ₂ is preferably 0.1 atomic % or more, more preferably It is 0.12 atomic % or more, more preferably 0.14 atomic % or more, for example, it can be any one of 0.2 atomic % or more and 0.3 atomic % or more. When V ₂ is equal to or higher than the aforementioned lower limit, the effect of suppressing coloration after heating (for example, heating at 260° C.) of the film adhesive becomes higher.

The upper limit of V ₂ is not particularly limited. For example, film adhesives with a _V2 of 0.5 atomic % or less are easier to produce.

V ₂ can be appropriately adjusted to be within a range set by any combination of any of the above lower limit values and upper limit values. For example, in one embodiment, V ₂ is preferably 0.1 atomic % to 0.5 atomic %, more preferably 0.12 atomic % to 0.5 atomic %, further preferably 0.14 atomic % to 0.5 atomic %, for example, it can be 0.2 atomic % to 0.5 atomic %, and any one of 0.3 atomic % to 0.5 atomic %.

V ₁ and V ₂ can be measured by survey-scanning a 0.1 mm×1 mm area on one side of a 20 μm-thick film adhesive and performing XPS analysis. At this time, the measurement angle was set to 45° and the beam diameter was set to 18 μm. As an X-ray source, aluminum can be used, for example.

The P concentration reduction rate calculated from the aforementioned V ₁ and V ₂ is 25% or less, preferably 20% or less, more preferably 15% or less, for example, it can be any one of 10% or less, 7.5% or less, and 5% or less. By. When the P concentration reduction rate is equal to or less than the aforementioned upper limit, the effect of inhibiting coloration after heating (for example, heating at 260° C.) of the film-like adhesive becomes high.

The lower limit value of the P concentration reduction rate is not particularly limited. For example, a film adhesive with a P concentration reduction rate of 1% or more is easier to produce.

The P concentration reduction rate can be appropriately adjusted within a range set by any combination of the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, the P concentration reduction rate is preferably 1% to 25%, more preferably 1% to 20%, further preferably 1% to 15%, for example, 1% to 10%, 1% to 7.5%, and any one from 1% to 5%.

The P concentration reduction rate can be calculated by the following formula. P concentration reduction rate = (V ₁ - V ₂ )/V ₁ ×100

Among the aforementioned film-like adhesives, at least one side of the film-like adhesive satisfies the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate, and preferably both sides satisfy the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate. . The composition of a single layer of the film-like adhesive usually does not vary among the film-like adhesives, and the composition has high uniformity. Therefore, on both sides of the single-layer film-like adhesive, no significant difference was observed in the types and contents of the components contained, or even if it was confirmed, the effects brought about by this were slight to a negligible level. In the single layer of the aforementioned film-like adhesive, if at least one side of the film-like adhesive satisfies the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate, then any cross-section and the other side of the film-like adhesive can be determined It also satisfies the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate.

The aforementioned film-like adhesive may be composed of one layer (single layer), or may be composed of two or more multiple layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other. There is no particular combination of these multiple layers. limited.

In addition, in this specification, it is not limited to the case of film-like adhesives. The term "multiple layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only part of the layers may be different." "Same", and further, "multiple layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the aforementioned film-like adhesive is preferably 10 μm to 40 μm, for example, it may be any one of 10 μm to 35 μm, 10 μm to 30 μm, and 10 μm to 25 μm, or it may be 13 μm to 40 μm, 16 μm to 40 μm, and 19 μm to 40 μm. Either one may be any one of 13 μm to 35 μm, 16 μm to 30 μm, and 19 μm to 25 μm. When the thickness of the film adhesive is equal to or greater than the aforementioned lower limit, the adhesion force of the film adhesive to the object to be adhered becomes stronger. When the thickness of the film-like adhesive is equal to or less than the aforementioned upper limit, the linear transmittance of the film-like adhesive for light (for example, light (400 nm to 800 nm)) becomes high regardless of heating. Here, the "thickness of the film-like adhesive" means the thickness of the entire film-like adhesive. For example, the thickness of the film-like adhesive composed of multiple layers means the total of all the layers constituting the film-like adhesive. thickness.

Preferable examples of the film-like adhesive include a linear transmittance of 90% or more before heating to light (400 nm to 800 nm) and a linear transmittance of 85% after heating to light (400 nm to 800 nm). As mentioned above, the thickness of the aforementioned film-like adhesive is a film-like adhesive of 10 μm to 40 μm.

The above-mentioned physical properties of the above-mentioned film adhesive (linear transmittance to light (400nm to 800nm) before the above-mentioned heating, linear transmittance to light (400nm to 800nm) after the above-mentioned heating, shear strength, V ₁ and V ₂ ) For example, it can be adjusted by adjusting the type and content of the components contained in the film adhesive agent.

Preferable examples of the film-like adhesive include one or two selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). More than one type of film adhesive.

[Adhesive composition] The aforementioned film-like adhesive can use a constituent material containing the film-like adhesive (for example, 1 selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus-based antioxidant (z). one or more than two) adhesive compositions. For example, the adhesive composition can be applied to a surface to be formed with a film-like adhesive and dried if necessary, thereby forming a film-like adhesive at the target site. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is generally the same as the content ratio of the above-mentioned components in the film adhesive agent. In addition, in this specification, "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, an ordinary temperature. Examples thereof include a temperature of 15°C to 25°C.

The adhesive composition can be applied by a known method. For example, the following methods can be used: air knife coater, blade coater, rod coater, gravure coater, roller coater. Cloth coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferable to perform heat drying. The adhesive composition containing a solvent is preferably dried at 70°C to 130°C for 10 seconds to 5 minutes, for example. Hereinafter, components contained in the film adhesive and the adhesive composition will be described in detail.

[Acrylic resin (a)] The acrylic resin (a) can be regarded as a component formed by the polymerization reaction of one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, and derivatives thereof. In addition, in this specification, "derivative" means a compound having a structure in which one or more groups of the original compound are substituted with a group (substituent) other than the group, unless otherwise specified. Here, the so-called "group" includes not only an atomic group composed of a plurality of atoms bonded together, but also a single atom. The acrylic resin (a) is a resin component for imparting film-forming properties, flexibility, etc. to the film-like adhesive, and for improving the adhesiveness (adhesiveness) to an adherent object such as the wafer.

In this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

The acrylic resin (a) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

Examples of the acrylic resin (a) include known acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin (a) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin (a) is within such a range, the adhesive force between the film adhesive and the adherend can be easily adjusted to a preferable range. On the other hand, when the weight average molecular weight of the acrylic resin (a) is equal to or more than the aforementioned lower limit, the shape stability (time stability during storage) of the film-like adhesive is improved. In addition, since the weight average molecular weight of the acrylic resin (a) is equal to or less than the aforementioned upper limit, the film-like adhesive becomes easy to conform to the uneven surface of the adherend, and interference between the adherend and the film-like adhesive can be further suppressed. Create gaps etc. In addition, in this specification, the so-called "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin (a) is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin (a) is equal to or higher than the lower limit, the bonding force between the film adhesive and the adherend is suppressed. For example, when picking up, it is easier to remove the wafer provided with the film adhesive as described later. The cutting blade pulls away. When the Tg of the acrylic resin (a) is equal to or less than the aforementioned upper limit, the adhesive force between the film adhesive and the adherend is improved.

Examples of the (meth)acrylate constituting the acrylic resin (a) include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid ester Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate , hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylate ) n-nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate ((meth)acrylic acid Lauryl ester), tridecyl (meth)acrylate, myristyl (meth)acrylate (myristyl acrylate), pentadecyl (meth)acrylate, (meth)acrylate ) Cetyl acrylate (palm ester (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group of the alkyl ester is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, etc. (methyl) Cycloalkyl acrylate; aralkyl (meth)acrylate such as benzyl (meth)acrylate; cycloalkyl acrylate such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid (Meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenoxyethyl ester; (meth)acrylimine; (meth)acrylic acid glycidyl ester and other glycidyl-containing (meth)acrylic acids Esters; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2 -Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; N-methylaminoethyl (meth)acrylate (Meth)acrylates containing substituted amine groups, etc. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms.

The acrylic resin (a) may be, for example, in addition to the aforementioned (meth)acrylate, or may be selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethyl A resin obtained by copolymerizing one or more monomers such as acrylamide.

The monomer constituting the acrylic resin (a) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

In addition to the above-mentioned hydroxyl group, the acrylic resin (a) may also have functional groups capable of bonding with other compounds, such as a vinyl group, a (meth)acryl group, an amine group, a carboxyl group, and an isocyanate group. These functional groups represented by the hydroxyl group of the acrylic resin (a) may be bonded to other compounds via the cross-linking agent (f) described below, or may be directly bonded to other compounds without the cross-linking agent (f). Since the acrylic resin (a) is bonded to other compounds using the aforementioned functional groups, the reliability of the package obtained using the film adhesive tends to be improved.

Preferable acrylic resins (a) include, for example, resins having a functional group capable of bonding to the crosslinking agent (f) described below.

In the adhesive composition, the ratio of the content of the acrylic resin (a) to the total content of all components except the solvent (that is, the ratio of the content of the acrylic resin (a) in the film adhesive to the total content of the film adhesive) The proportion of the total mass) is preferably 10 mass% to 90 mass%, more preferably 15 mass% to 70 mass%, further preferably 20 mass% to 65 mass%, for example, it can also be 30 mass% to 65 mass% %. When the ratio is equal to or higher than the lower limit, the structure of the film-like adhesive is further stabilized. When the aforementioned ratio is equal to or less than the aforementioned upper limit, it is easier to increase the usage amount of components other than the acrylic resin (a) such as the epoxy compound (b1) and the phosphorus antioxidant (z), thereby making it easier to obtain an acrylic resin by using the acrylic resin. Effects caused by components other than resin (a).

[Epoxy compound (b1)] The epoxy compound (b1) may be either a resin component or a non-resin component. Examples of the epoxy compound (b1) include known epoxy compounds, and examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products of bisphenol A diglycidyl ether, O-cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenyl skeleton type epoxy resin , triazine-type alicyclic epoxy compounds and other epoxy compounds with more than two functions.

As the epoxy compound (b1), an epoxy compound having an unsaturated hydrocarbon group can also be used. An epoxy compound having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin (a) than an epoxy compound not having an unsaturated hydrocarbon group. Therefore, by using the epoxy compound (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained using the film adhesive is improved.

Examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include compounds having a structure in which part of the epoxy group of a polyfunctional epoxy compound is converted into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by addition reaction of (meth)acrylic acid or a derivative of (meth)acrylic acid and an epoxy group.

Examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy compound. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylyl, (meth)acrylyl, meth)acrylamide group, etc., preferably acrylyl group.

The number average molecular weight of the epoxy compound (b1) (in other words, the epoxy resin (b1)) as the resin component is not particularly limited. In terms of the curability of the film adhesive, the strength and heat resistance of the cured product of the film adhesive, In terms of sex, 300 to 30,000 is preferred, 400 to 10,000 is more preferred, and 500 to 3,000 is particularly preferred. The epoxy equivalent of the epoxy compound (b1) is preferably 100g/eq to 1000g/eq, more preferably 120g/eq to 600g/eq.

The epoxy compound (b1) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

The epoxy compound (b1) is preferably an aliphatic compound. That is, it is preferable that the said film adhesive agent contains an aliphatic epoxy compound. In this specification, "aliphatic compound" means a compound having an aliphatic group and not having an aromatic group. In addition, the "aliphatic group" includes a chain aliphatic group and an aliphatic cyclic group (alias: alicyclic group). In addition, the "aromatic group" includes an aromatic hydrocarbon group and an aromatic heterocyclic group. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the epoxy compound (b1), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes higher. By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring suppressing effect is significantly increased.

The epoxy compound (b1) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N), and an aromatic group. 1 or 2 or more types in a group. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the epoxy compound (b1), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes Furthermore, by containing only compounds that do not have these bonds or groups (in other words, not containing compounds that have these bonds or groups), the above-described coloring inhibitory effect becomes significantly higher.

The epoxy compound (b1) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). ) 1 or 2 or more types in the group composed of. That is, the film-like adhesive preferably contains one or more aliphatic rings selected from the group consisting of triple bonds between carbon atoms, double bonds between carbon atoms, and cyano groups. oxygen compounds. By the adhesive composition and the film-shaped adhesive containing an aliphatic compound that does not have these bonds or groups as the epoxy compound (b1), the coloring of the film-shaped adhesive after heating (for example, heating at 260°C) is suppressed. The effect becomes higher, and by containing only the aliphatic compound which does not have these bonds or groups (in other words, does not contain the aliphatic compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

In the adhesive composition and the film-like adhesive, the content of the epoxy compound (b1) is preferably 5 to 500 parts by mass relative to 100 parts by mass of the acrylic resin (a). For example, it may be 5 parts by mass. Any one of 200 parts by mass, 5 parts by mass and 150 parts by mass, 5 parts by mass and 110 parts by mass, and 5 parts by mass and 100 parts by mass. When the aforementioned content of the epoxy compound (b1) is in this range, it is easier to adjust the adhesive force between the film-like adhesive agent and the resin film or dicing sheet described below.

[Phosphorus antioxidant (z)] By containing a phosphorus-based antioxidant (z), the film-like adhesive further suppresses coloration before and after heating. The phosphorus-based antioxidant (z) is not particularly limited as long as it is a compound having a phosphorus atom as a constituent atom of the phosphorus-based antioxidant and having an antioxidant effect. Examples of the phosphorus-based antioxidant (z) include compounds having an oxidation number of phosphorus of 3.

The phosphorus antioxidant (z) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

The phosphorus antioxidant (z) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the phosphorus-based antioxidant (z), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloration suppressing effect is significantly increased.

The phosphorus antioxidant (z) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N), and an aromatic group. 1 or 2 or more types in the group. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the phosphorus-based antioxidant (z), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive changes. Even higher, by containing only compounds that do not have these bonds or groups (in other words, not containing compounds that have these bonds or groups), the above-mentioned coloration inhibitory effect becomes significantly higher.

The phosphorus-based antioxidant (z) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡ N) 1 or 2 or more types in the group composed of. The adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the phosphorus antioxidant (z), and the film-like adhesive is colored after heating (for example, heating at 260°C) The inhibitory effect becomes higher, and by containing only the aliphatic compound which does not have these bonds or groups (in other words, does not contain the aliphatic compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

In terms of stably exhibiting an antioxidant effect, the phosphorus-based antioxidant (z) is preferably a phosphite. Among them, the phosphorus-based antioxidant (z) is more preferably an aliphatic phosphite, and further preferably an aliphatic trialkyl phosphite. That is, the film-like adhesive preferably contains phosphite as an antioxidant, more preferably contains aliphatic phosphite, and further preferably contains aliphatic trialkyl phosphite.

Examples of aliphatic trialkyl phosphite include: triethyl phosphite ((C ₂ H ₅ O) ₃ P), tris(2-ethylhexyl) phosphite ((CH ₃ CH ₂ CH ₂ CH ₂ CH(CH ₂ CH ₃ )CH ₂ O) ₃ P), tridecyl phosphite ((C ₁₀ H ₂₁ O) ₃ P), trilauryl phosphite ((C ₁₂ H ₂₅ O) ₃ P ), tridecyl phosphite ((C ₁₃ H ₂₇ O) ₃ P), tristearyl phosphite ((C ₁₈ H ₃₇ O) ₃ P), bis(decyl) pentaerythritol diacetate Phosphate ester (C ₁₀ H ₂₁ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ POC ₁₀ H ₂₁ ), bis(tridecyl)pentaerythritol diphosphite (C ₁₃ H ₂₇ OP(OCH ₂ ) ₂ C (CH ₂ O) ₂ POC ₁₃ H ₂₇ ), distearyl pentaerythritol diphosphite (C ₁₈ H ₃₇ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ POC ₁₈ H ₃₇ ), hydrogenated bisphenol A- Pentaerythritol phosphite polymer (having repeating units represented by the formula "-(OC ₆ H ₁₂ C(CH ₃ ) ₂ C ₆ H ₁₂ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ P)-" polymer) etc.

In the adhesive composition, the ratio of the content of the phosphorus-based antioxidant (z) to the total content of all components except the solvent (that is, the content of the phosphorus-based antioxidant (z) in the film-like adhesive relative to the total content of the film-like adhesive) The proportion of the total mass of the adhesive) is preferably 0.1 mass% to 5 mass%, more preferably 0.2 mass% to 3 mass%, and further preferably 0.3 mass% to 1.5 mass%. When the said ratio is more than the said lower limit value, the effect brought about by using a phosphorus-type antioxidant (z) can be obtained more remarkably. When the ratio is equal to or less than the upper limit, excessive use of the phosphorus-based antioxidant (z) is suppressed.

In the aforementioned film-like adhesive, in order to improve various physical properties of the film-like adhesive, in addition to the acrylic resin (a), the epoxy compound (b1), and the phosphorus-based antioxidant (z), in addition to the acrylic resin (a), the epoxy compound (b1), and the phosphorus-based antioxidant (z) may be further contained as necessary. Other ingredients consistent with any of these ingredients. Examples of other components contained in the film-like adhesive include: phenol resin (b2), hardening accelerator (c), filler (d), coupling agent (e), cross-linking agent (f), and energy rays Curable resin (g), photopolymerization initiator (h), antioxidant (y) other than phosphorus-based antioxidant (z) (may be referred to as "other antioxidant (y)" in this specification), acrylic acid Thermoplastic resin (x) other than resin (a) (maybe referred to as "thermoplastic resin (x)" in this specification), general-purpose additive (i), etc.

[Phenolic resin (b2)] The phenol resin (b2) functions as a thermosetting agent for the epoxy compound (b1). In this embodiment, when the epoxy compound (b1) and the phenol resin (b2) are used together, the combination functions as an epoxy-based thermosetting resin. In this embodiment, this kind of epoxy-based thermosetting resin may be called "epoxy-based thermosetting resin (b)".

The phenol resin (b2) only needs to have two or more phenolic hydroxyl groups as functional groups capable of reacting with the epoxy group in one molecule.

Examples of the phenol resin (b2) include polyfunctional phenol resins, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl-type phenol resins, and the like.

The phenol resin (b2) may have an unsaturated hydrocarbon group. Examples of the other phenol resin (b2) having an unsaturated hydrocarbon group include a compound having a structure in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a compound having an aromatic ring directly bonded to the phenol resin. Compounds with an unsaturated hydrocarbon base structure, etc. The unsaturated hydrocarbon group in the phenol resin (b2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy compound having an unsaturated hydrocarbon group.

In order to easily adjust the adhesive force of the film adhesive, the phenol resin (b2) preferably has a high softening point or glass transition temperature.

The number average molecular weight of the phenol resin (b2) is preferably 300 to 30,000, more preferably 400 to 10,000, even more preferably 500 to 3,000.

The phenol resin (b2) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

When phenol resin (b2) is used, the ratio of the content of phenol resin (b2) to the total content of all components except the solvent in the adhesive composition (that is, the phenol resin (b2) in the film adhesive ) content relative to the total mass of the film adhesive) is not particularly limited, but is preferably 10 mass% or less, more preferably 7.5 mass% or less, and still more preferably 5 mass% or less. When the ratio is equal to or less than the upper limit, the effect of inhibiting coloration after heating (for example, heating at 260° C.) of the film-like adhesive becomes higher. That is, as a preferred example of the film-like adhesive containing the phenol resin (b2), the ratio of the content of the phenol resin (b2) in the film-like adhesive to the total mass of the film-like adhesive can be cited It is a film-like adhesive of less than 10% by mass.

When phenol resin (b2) is used, the ratio of the content of phenol resin (b2) to the total content of all components except the solvent in the adhesive composition (that is, the phenol resin (b2) in the film adhesive ) content relative to the total mass of the film adhesive agent, the lower limit value is not particularly limited. For example, in order to obtain the effect brought about by using the phenol resin (b2) more significantly, the said ratio is preferably 0.5 mass % or more.

When the phenol resin (b2) is used, the above-mentioned ratio can be appropriately adjusted to be within a range set by any combination of the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, the aforementioned proportion is preferably 0.5 mass% to 10 mass%, more preferably 0.5 mass% to 7.5 mass%, and further preferably 0.5 mass% to 5 mass%.

When the phenol resin (b2) is used, the content of the phenol resin (b2) in the adhesive composition and the film-like adhesive may be 3 to 100 parts by mass relative to 100 parts by mass of the epoxy compound (b1). Any one of 30 parts by mass, 3 parts by mass to 25 parts by mass, and 3 parts by mass to 20 parts by mass, or 5 parts by mass to 30 parts by mass, 10 parts by mass to 30 parts by mass, and 15 parts by mass to 30 parts by mass Any one of parts by mass may be 5 to 25 parts by mass, and any one of 10 to 20 parts by mass.

[Harding accelerator (c)] The hardening accelerator (c) is a component used to adjust the hardening speed of the adhesive composition and film-like adhesive. Preferred hardening accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazole in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (more than one hydrogen atom is substituted by a group other than a hydrogen atom); Phosphines in which hydrogen atoms are substituted with organic groups); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; inclusion compounds using the aforementioned imidazoles as guest compounds )wait.

The hardening accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

When a hardening accelerator (c) is used, the content of the hardening accelerator (c) in the adhesive composition and film adhesive is based on 100 mass of the total content of the epoxy compound (b1) and the phenolic resin (b2). parts, preferably 0.01 to 7 parts by mass, more preferably 0.1 to 4 parts by mass. When the content of the hardening accelerator (c) is equal to or higher than the lower limit, the effect of using the hardening accelerator (c) can be more significantly obtained. By keeping the content of the hardening accelerator (c) below the above-mentioned upper limit, for example, the highly polar hardening accelerator (c) is suppressed from being directed toward the bonding interface side with the adherend in the film-like adhesive under high temperature and high humidity conditions. The effect of movement and segregation becomes higher, and the reliability of the package obtained using the film adhesive further improves. In addition, when the phenol resin (b2) is not used, the total content of the epoxy compound (b1) and the phenol resin (b2) means the content of the epoxy compound (b1).

[Filling material (d)] By containing the filler (d) in the film-like adhesive, the thermal expansion coefficient of the film-like adhesive can be easily adjusted, and the film-like adhesive can be used by optimizing the thermal expansion coefficient with respect to the object to which the film-like adhesive is attached. The reliability of the obtained package is further improved. In addition, when the film-like adhesive contains the filler (d), the moisture absorption rate of the cured product of the film-like adhesive can be reduced or the heat dissipation property can be improved.

The filler material (d) can be either an organic filler material or an inorganic filler material, and is preferably an inorganic filler material. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride, etc.; these inorganic fillers are formed into spherical shapes. Beads; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, etc. Among these, the inorganic filler material is preferably silica or a surface-modified product of silica.

The average particle diameter of the filler (d) is not particularly limited, but is preferably from 10 nm to 100 nm, more preferably from 10 nm to 80 nm, and further preferably from 10 nm to 60 nm. By having the average particle diameter of the filler (d) below the upper limit, the turbidity of the film-like adhesive is highly suppressed, and the linear transmittance and heating of the film-like adhesive before light (400 nm to 800 nm) are The rear linear transmittance increases, and as a result, the image visibility of the film-like adhesive before and after heating becomes higher. When the average particle diameter of the filler (d) is equal to or greater than the aforementioned lower limit, the effect of using the filler (d) can be more significantly obtained. In addition, in this specification, the "average particle diameter" means the particle diameter (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction and scattering method, unless otherwise specified. value.

The filler material (d) contained in the adhesive composition and the film-like adhesive agent may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

When a filler (d) is used, the ratio of the content of the filler (d) to the total content of all components except the solvent in the adhesive composition (that is, the filler (d) in the film adhesive ) content relative to the total mass of the film adhesive) is preferably 7.5 mass% to 50 mass%, more preferably 10 mass% to 45 mass%, particularly preferably 12.5 mass% to 40 mass%. By setting the content of the filler (d) within this range, it is easier to adjust the thermal expansion coefficient.

[Coupling agent (e)] By containing the coupling agent (e), the film-like adhesive improves the adhesiveness and adhesion to the adherend. In addition, since the film-like adhesive contains the coupling agent (e), the cured product of the film-like adhesive improves the water resistance without impairing the heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the acrylic resin (a), the epoxy thermosetting resin (b), etc., and is more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyltriethyloxysilane, imidazolesilane, oligomer or polymer organosiloxane, etc.

The coupling agent (e) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the coupling agent (e), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes higher. Containing only aliphatic compounds (in other words, not containing aromatic compounds) significantly increases the above-mentioned coloring inhibitory effect.

The coupling agent (e) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N), and an aromatic group. 1 or 2 or more species in the group. When the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the coupling agent (e), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes even greater. High, by containing only compounds that do not have these bonds or groups (in other words, not containing compounds that have these bonds or groups), the above-mentioned coloration inhibitory effect becomes significantly higher.

The coupling agent (e) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). 1 or 2 or more types in the group. The adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the coupling agent (e), thereby inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) To become higher, by containing only the aliphatic compound which does not have these bonds or groups (in other words, does not contain the aliphatic compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

Among the coupling agents (e), more specific examples of the aliphatic compound (aliphatic coupling agent) include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-Aminoethylamino)propylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethyl Oxysilane, oligomer or polymer organosiloxane, etc.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive agent may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and film adhesive is relative to the total of the acrylic resin (a) and the epoxy thermosetting resin (b). The content is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the aforementioned content of the coupling agent (e) is equal to or higher than the aforementioned lower limit, the following effects brought about by the use of the coupling agent (e) can be more significantly obtained: the dispersibility of the filler (d) in the resin is improved, and The adhesion between the film adhesive and the adherend is improved, etc. When the content of the coupling agent (e) is equal to or less than the upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (f)] When using a resin having a functional group capable of bonding to other compounds mentioned above, such as vinyl, (meth)acrylyl, amine, hydroxyl, carboxyl, isocyanate, etc., as the acrylic resin (a), The adhesive composition and the film-like adhesive may also contain a cross-linking agent (f) for bonding the aforementioned functional group to other compounds to perform cross-linking. By cross-linking using a cross-linking agent (f), the initial adhesive strength and cohesive force of the film adhesive can be adjusted.

Examples of the cross-linking agent (f) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate-based cross-linking agents (cross-linking agents having a metal chelate structure), and aziridine-based cross-linking agents. Agent (cross-linking agent with aziridine group), etc.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Terpolymers, isocyanurates and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; urethane prepolymers of terminal isocyanates obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. wait. The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant made of low molecular weight active hydrogen compounds. Examples of the adduct include: xylylene diisocyanate adduct of trimethylolpropane, isophorone diisocyanate adduct of trimethylolpropane, and trimethylolpropane. Toluene diisocyanate adduct of propane, hexamethylene diisocyanate adduct of trimethylolpropane, etc. In addition, the "isocyanate-terminated urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

More specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylenedimethyldiisocyanate; 1,4-xylenedimethyldiisocyanate Diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Ertone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Any one or two or more compounds of isocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinemethane), trimethylolpropane-tris-β-nitrogen Propiridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene Based on melamine, etc.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (f), it is preferable to use a hydroxyl-containing polymer as the acrylic resin (a). When the cross-linking agent (f) has an isocyanate group and the acrylic resin (a) has a hydroxyl group, the cross-linked structure can be easily introduced through the reaction between the cross-linking agent (f) and the acrylic resin (a). Film adhesive.

The cross-linking agent (f) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the cross-linking agent (f), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes higher. By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring suppressing effect is significantly increased.

The cross-linking agent (f) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. 1 or 2 or more types in a group. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the cross-linking agent (f), the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes Furthermore, by containing only compounds that do not have these bonds or groups (in other words, not containing compounds that have these bonds or groups), the above-described coloring inhibitory effect becomes significantly higher.

The cross-linking agent (f) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). ) 1 or 2 or more types in the group composed of. By the adhesive composition and the film-shaped adhesive containing an aliphatic compound that does not have these bonds or groups as the cross-linking agent (f), the coloring of the film-shaped adhesive after heating (for example, heating at 260°C) is suppressed. The effect becomes higher, and by containing only the aliphatic compound which does not have these bonds or groups (in other words, does not contain the aliphatic compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

The crosslinking agent (f) is preferably an aliphatic organic polyisocyanate compound (aliphatic polyisocyanate crosslinking agent) in that the above-mentioned coloring inhibitory effect is particularly high and has excellent characteristics as a crosslinking agent. . More specific examples of the aliphatic polyisocyanate crosslinking agent include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate, isophor added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Any one or two or more compounds of ketone diisocyanate and hexamethylene diisocyanate; lysine diisocyanate, etc.

Regarding the film-like adhesive, when focusing on the acrylic resin (a) and the cross-linking agent (f), the above-mentioned coloring inhibitory effect is particularly high and has excellent characteristics, preferably: The aliphatic polyvalent isocyanate cross-linking agent is contained as the cross-linking agent (f), and a compound having a functional group capable of being bonded to the aliphatic polyvalent isocyanate cross-linking agent is contained as the acrylic resin (a).

The cross-linking agent (f) contained in the adhesive composition and the film-like adhesive agent may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition and the film-like adhesive is preferably 0.3 parts by mass relative to 100 parts by mass of the content of the acrylic resin (a). part to 12 parts by mass, more preferably 0.3 to 3.5 parts by mass, further preferably 0.3 to 2 parts by mass. When the content of the cross-linking agent (f) is equal to or higher than the lower limit, the effect of using the cross-linking agent (f) can be more significantly obtained. In addition, when the content of the cross-linking agent (f) is equal to or less than the upper limit, excessive use of the cross-linking agent (f) is suppressed.

[Energy ray curable resin (g)] The adhesive composition and film-like adhesive may contain energy ray curable resin (g). By containing the energy ray curable resin (g), the film adhesive can change its characteristics by irradiating energy rays.

In this specification, "energy rays" mean electromagnetic waves or charged particle beams having energy quanta. Examples of the energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can irradiate an electron beam generated by an electron beam accelerator or the like. In this specification, "energy ray hardenability" means the property of being hardened by irradiation with energy rays, and "non-energy ray hardenability" means the property of not being hardened even if energy rays are irradiated.

Energy ray curable resin (g) is obtained by polymerizing (hardening) an energy ray curable compound. Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and preferably are acrylate compounds having a (meth)acrylyl group.

Examples of the acrylate compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. hydroxy) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylates and other (meth)acrylates containing a chain aliphatic skeleton; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyethylene glycol Polyalkylene glycol (meth)acrylate such as di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylic urethane oligomer; epoxy modified (meth)acrylate (meth)acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.

The energy ray curable resin (g) contained in the adhesive composition may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

When an energy ray curable resin (g) is used, the ratio of the content of the energy ray curable resin (g) in the adhesive composition to the total mass of the adhesive composition is preferably 1 to 95 mass %. %, more preferably 5% by mass to 90% by mass, even more preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain the energy ray curable resin (g), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (g), a photopolymerization initiator (h) may also be included. ).

Examples of the photopolymerization initiator (h) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one Acetophenone compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxides Compounds; thioether compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketool compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; diocene compounds Titanium and other titanocene compounds; thioxanthone and other thioxanthone compounds; peroxide compounds; diethyl and other diketone compounds; benzil; diphenyl; benzophenone; 2,4- Diethylthioxanthone; 1,2-diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 1-chloroanthraquinone, 2 -Quinone compounds such as chloroanthraquinone, etc. Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

The photopolymerization initiator (h) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the photopolymerization initiator (h), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. , by containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring inhibitory effect is significantly increased.

The photopolymerization initiator (h) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N), and an aromatic group. 1 or 2 or more types in a group composed of bases. The adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the photopolymerization initiator (h), thereby inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) As it becomes higher, by containing only the compound which does not have these bonds or groups (in other words, does not contain the compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

The photopolymerization initiator (h) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C ≡N) One or more types in the group composed of. When the adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the photopolymerization initiator (h), the coloring of the film-like adhesive after heating (for example, heating at 260°C) By containing only aliphatic compounds that do not have these bonds or groups (in other words, not containing aliphatic compounds that have these bonds or groups), the inhibitory effect of the above-mentioned coloration becomes significantly higher.

Among the photopolymerization initiators (h), as the aliphatic compound (aliphatic photopolymerization initiator), more specific examples include: acylphosphine oxide compounds; tetramethylthiuram monosulfide, etc. Sulfide compounds; azo compounds such as azobisisobutyronitrile; peroxide compounds; diketone compounds such as diethyl; amines and other photosensitizers, etc. Among the compounds exemplified here, they are aliphatic compounds and do not have any compound selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). Examples of one or more photopolymerization initiators (h) in the group include compounds other than azobisisobutyronitrile.

The photopolymerization initiator (h) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. .

When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is preferably 0.1 with respect to 100 parts by mass of the energy ray curable resin (g). The amount is from 20 parts by mass to 20 parts by mass, more preferably from 1 to 10 parts by mass, and even more preferably from 2 to 5 parts by mass.

[Other antioxidants(y)] The aforementioned adhesive composition and film-like adhesive may also contain the aforementioned other antioxidant (y) within a range that does not impair the effects of the present invention. The other antioxidant (y) is not particularly limited as long as it is an antioxidant other than the phosphorus-based antioxidant (z), and may be either an organic compound or an inorganic compound.

The other antioxidant (y) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

When using another antioxidant (y), the content of the other antioxidant (y) in the adhesive composition and film adhesive is preferably 10 parts by mass relative to 100 parts by mass of the phosphorus-based antioxidant (z). Parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. When the content of the other antioxidant (y) is equal to or less than the upper limit, the coloring of the film adhesive before and after heating is further suppressed.

The adhesive composition and film-like adhesive preferably do not contain other antioxidants (y).

[Thermoplastic resin (x)] The aforementioned adhesive composition and film-like adhesive may contain the aforementioned thermoplastic resin (x) within a range that does not impair the effects of the present invention. By using the thermoplastic resin (x), for example, it may be easier to separate the wafer provided with the film-like adhesive from the dicing blade described later when picking up, or the film-like adhesive may easily follow the uneven surface of the adherend. This can further suppress the occurrence of gaps between the adherend and the film-like adhesive.

The thermoplastic resin (x) is not particularly limited as long as it is a thermoplastic resin other than the acrylic resin (a). Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.

The weight average molecular weight of the thermoplastic resin (x) is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin (x) is preferably -30°C to 150°C, more preferably -20°C to 120°C.

The thermoplastic resin (x) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

When the thermoplastic resin (x) is used, the content of the thermoplastic resin (x) in the adhesive composition and the film-like adhesive is preferably 10 parts by mass or less based on 100 parts by mass of the content of the acrylic resin (a). , more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. When the content of the thermoplastic resin (x) is equal to or less than the upper limit, the effect of using the acrylic resin (a) can be more significantly obtained.

The adhesive composition and film-like adhesive preferably do not contain the thermoplastic resin (x).

[General Additive (i)] The general-purpose additive (i) can be a publicly known additive and can be selected arbitrarily according to the purpose, and is not particularly limited. Preferred general-purpose additives (i) include, for example, plasticizers, antistatic agents, colorants (dyes, pigments), gettering agents, and the like.

When the general-purpose additive (i) is an organic compound, the general-purpose additive (i) (herein referred to as "organic general-purpose additive" in this specification) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as an organic general-purpose additive, the effect of inhibiting coloration after heating (for example, heating at 260°C) of the film-like adhesive becomes higher. By containing only Aliphatic compounds (in other words, not containing aromatic compounds) significantly increase the above-mentioned coloring inhibitory effect.

The organic general additive preferably does not have a group selected from the group consisting of triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C=C), cyano groups (-C≡N) and aromatic groups. 1 or 2 or more species in the group. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as an organic general-purpose additive, the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. By containing only the compound which does not have these bonds or groups (in other words, does not contain the compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

The organic general additive is preferably an aliphatic compound and does not have a compound selected from the group consisting of triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C=C) and cyano groups (-C≡N). 1 or 2 or more species in the group. Since the adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as an organic general-purpose additive, the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes Furthermore, by containing only the aliphatic compound which does not have these bonds or groups (in other words, does not contain the aliphatic compound which has these bonds or groups), the above-mentioned coloration inhibitory effect becomes remarkably high.

The general additive (i) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily. The content of the general-purpose additive (i) in the adhesive composition and film-like adhesive is not particularly limited and may be appropriately selected depending on the purpose.

[solvent] The adhesive composition preferably further contains a solvent. The adhesive composition containing a solvent has improved workability. The solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amide such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds )wait. The solvent contained in the adhesive composition may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents may be selected arbitrarily.

From the viewpoint that the components contained in the adhesive composition can be mixed more uniformly, the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like.

[Production method of adhesive composition] The adhesive composition is obtained by blending each component constituting the adhesive composition. The order in which each component is added is not particularly limited, and two or more components may be added at the same time. When a solvent is used, it can be used in the following manner: the solvent is mixed with any preparation ingredient other than the solvent and the preparation ingredients are pre-diluted; it can also be used without pre-diluting any preparation ingredient other than the solvent and the solvent is mixed with any preparation ingredient other than the solvent. These ingredients are mixed.

The method of mixing each component during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade, mixing with a mixer, and mixing by applying ultrasonic waves. methods, etc. The temperature and time when adding and mixing each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.

FIG. 1 is a cross-sectional view schematically showing a film adhesive according to an embodiment of the present invention. In addition, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention and for convenience, main parts may be enlarged in some cases, and the dimensional ratios of each component may not be the same as the actual ones.

The film adhesive 13 shown here is provided with a first release film 151 on one side (sometimes referred to as "the first side" in this specification) 13a of the film adhesive 13, and is connected to the first side 13a. The second release film 152 is provided on the other side 13b on the opposite side (sometimes referred to as the "second side" in this specification). Here, the laminated sheet formed by laminating the first release film 151, the film-like adhesive 13, and the second release film 152 in this order in the thickness direction of these layers is assigned the reference numeral 109. Such film-like adhesive 13 (laminated sheet 109) is suitable for storage in a roll shape, for example.

The film adhesive 13 has the above-mentioned light transmittance. For example, at least one of the first surface 13a and the second surface 13b of the film adhesive 13 satisfies the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate. The thickness of the film adhesive 13 is preferably 10 μm to 40 μm. The film adhesive 13 can be formed using the above-mentioned adhesive composition.

Both the first release film 151 and the second release film 152 may be known release films. The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other. For example, the peeling forces required for peeling off from the film-like adhesive 13 may be different from each other.

The film-like adhesive 13 shown in FIG. 1 is obtained by removing either the first release film 151 or the second release film 152, and the resulting exposed surface becomes the adhesive surface of the film-like adhesive 13 to the attached object. Attached. Here, examples of the attachment target include the aforementioned wafers and the like. In the case of the above-mentioned wafer, the adhesion surface of the film adhesive 13 becomes the circuit formation surface of the wafer.

As a preferred embodiment of the film adhesive, for example, the following film adhesive is used to bond the circuit formation surface of the chip and the light-transmitting cover; and when the film before heating at 260°C On one side of the film-like adhesive, analyze by X _- ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , and measure the aforementioned V ₁ in the aforementioned film-like adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less; Using the aforementioned film adhesive with a size of 2 mm × 2 mm and a thickness of 20 μm, a copper plate with a size of 30 mm × 30 mm and a thickness of 300 μm, and a silicon wafer, make one side of the aforementioned film adhesive that is attached to the entire surface of the silicon wafer. surface, and the other side is entirely attached to the surface of the aforementioned copper plate, and the aforementioned film-like adhesive is aligned with the side surface of the aforementioned silicon wafer. Under the temperature condition of 23°C, the aforementioned test piece is Through the aligned side surfaces, apply force at a speed of 200 μm/s to both the film-like adhesive and the silicon wafer in a direction parallel to the other side of the film-like adhesive until the film-like adhesive is When the maximum value of the force applied until the agent is destroyed is the shear strength (N/2mm□) of the film-like adhesive, the shear strength is 20 N/2mm□ or more.

As a preferred embodiment of the film adhesive, for example, the following film adhesive is used to bond the circuit formation surface of the chip and the light-transmitting cover; and when the film before heating at 260°C On one side of the film-like adhesive, analyze by X _- ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , and measure the aforementioned V ₁ in the aforementioned film-like adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less; The aforementioned film-like adhesive contains a phosphorus-based antioxidant (z); the aforementioned phosphorus-based antioxidant (z) is an aliphatic compound and does not have a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. 1 or 2 or more types in the group.

As a preferred embodiment of the film adhesive, for example, the following film adhesive is used to bond the circuit formation surface of the chip and the light-transmitting cover; and when the film before heating at 260°C On one side of the film-like adhesive, analyze by X _- ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , and measure the aforementioned V ₁ in the aforementioned film-like adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less; The aforementioned film adhesive contains an epoxy compound (b1); the aforementioned epoxy compound (b1) is an aliphatic compound and does not have a compound selected from the group consisting of triple bonds between carbon atoms, double bonds between carbon atoms, and cyano groups. 1 or 2 or more species in the group.

As a preferred embodiment of the film adhesive, for example, the following film adhesive is used to bond the circuit formation surface of the chip and the light-transmitting cover; and when the film before heating at 260°C On one side of the film-like adhesive, analyze by X _- ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , and measure the aforementioned V ₁ in the aforementioned film-like adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less; The aforementioned film-like adhesive contains an acrylic resin (a) and a cross-linking agent (f); the aforementioned acrylic resin (a) has a functional group capable of bonding with the aforementioned cross-linking agent (f); the aforementioned cross-linking agent (f) ) is an aliphatic compound and does not have one or more types selected from the group consisting of triple bonds between carbon atoms, double bonds between carbon atoms, and cyano groups.

As a preferred embodiment of the film adhesive, for example, the following film adhesive is used to bond the circuit formation surface of the chip and the light-transmitting cover; and when the film before heating at 260°C On one side of the film-like adhesive, analyze by X _- ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , and measure the aforementioned V ₁ in the aforementioned film-like adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the aforementioned V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the aforementioned V ₁ and V ₂ is 25% or less; The film-like adhesive contains a filler (d); the average particle size of the filler (d) is 10 nm to 100 nm.

◇Laminated sheets and composite sheets A laminated sheet according to an embodiment of the present invention includes the film-like adhesive and a resin film provided on one side of the film-like adhesive. In addition, a composite sheet according to an embodiment of the present invention includes the film-like adhesive and a dicing sheet provided on one side of the film-like adhesive. The dicing sheet includes a base material and a dicing sheet provided on one side of the base material. An adhesive layer is arranged between the base material and the film-like adhesive.

The above-mentioned laminated sheet only needs to be provided with a resin film on at least one side of the aforementioned film-like adhesive. The resin film may be provided on only one side, or may be provided on both sides (that is, on the aforementioned one side and with the aforementioned A resin film is provided on the other side (one side is the opposite side).

In the case where the resin films are provided on both sides of the film-like adhesive in the laminated sheet, these resin films may be the same or different from each other, and the combination of these resin films is not particularly limited.

The aforementioned resin film may be composed of one layer (single layer), or may be composed of two or more layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The resin film may be a sheet made only of resin as a constituent material, or may be a sheet made of resin and components other than resin as a constituent material and with resin as a main constituent material.

Examples of the resin that constitute the resin film include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE). Density Polyethylene) and other polyethylenes; polyolefins other than polyethylene such as polypropylene, polybutylene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(methyl ) Ethylene-based copolymers (copolymers obtained using ethylene as a monomer) such as acrylic copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers; polyvinyl chloride, vinyl chloride copolymers, etc. Vinyl chloride resin (resin obtained using vinyl chloride as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate Polyesters such as polyethylene isophthalate, polyethylene-2,6-naphthalate, fully aromatic polyesters in which all structural units have aromatic ring groups; two or more of the above-mentioned polyesters Copolymer; poly(meth)acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene Ether; polyphenylene sulfide; polypropylene; polyetherketone, etc. Examples of the resin include polymer alloys such as mixtures of the polyester and resins other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester. Examples of the resin include cross-linked resins obtained by cross-linking one or more of the above-described resins; ionic polymerization using one or two or more of the above-described resins; Materials and other modified resins.

The resin film may be a release film or a base material described below. The base material will be described in detail separately.

Examples of the release film include a multi-layered film including a resin layer and a release treatment layer provided on one side of the resin layer.

The release film can be produced by subjecting one side of the resin layer to a release process. The resin layer can be produced by molding or applying a resin composition containing resin and drying it as necessary.

The resin constituting the resin layer is the same as the resin constituting the resin film. The peeling treatment of the resin layer can be performed using various known release agents such as alkyd-based, polysiloxane-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents. In terms of heat resistance, the release agent is preferably an alkyd-based, polysiloxane-based or fluorine-based release agent.

The aforementioned resin layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

An example of a laminated sheet in which the release film is provided as a resin film on both sides of the film-like adhesive is the laminated sheet 109 shown in FIG. 1 .

An example of a laminated sheet in which a resin film is provided on only one side of the film-like adhesive is the laminated sheet 108 shown in FIG. 2 . In addition, in the drawings after FIG. 2 , the same components as those shown in the previously described drawings are assigned the same reference numerals as in the previously described drawings, and detailed descriptions of the structural elements are omitted.

The laminated sheet 108 shown here is composed of a resin film 19 on the first surface 13 a of the film-like adhesive 13 . As mentioned above, the resin film 19 may be a release film (for example, the 1st release film 151 or the 2nd release film 152 in FIG. 1), or may be a base material mentioned later.

The thickness of the resin film can be set arbitrarily according to the purpose and is not particularly limited. The thickness of the resin film may be, for example, 10 μm to 200 μm.

The laminated sheet of this embodiment is not limited to the laminated sheet shown in FIG. 2. Within the scope that does not impair the effect of the present invention, part of the structure of the laminated sheet shown in FIG. Laminated sheets further add other components. More specifically, as described below.

For example, the laminated sheet of this embodiment may not have any layer on the second surface of the film-like adhesive, or may have a layer for fixing the laminated sheet on the second surface of the film-like adhesive in a region near the peripheral edge. Adhesive layer for fixtures such as ring frames. The adhesive layer for a jig may have a single-layer structure containing an adhesive component, for example, or may have a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet serving as a core material.

For example, when the laminated sheet is viewed from above the film adhesive side or the resin film side of the laminated sheet, the surface areas of the film adhesive and the resin film may be equal or substantially equal. In the laminated sheet of this embodiment, the surface areas are also equal to that of the resin film. The surface area of the film-like adhesive is smaller than the surface area of the resin film, and a part of the resin film is exposed. In this case, for example, at least the peripheral edge portion in the width direction of the resin film may not be covered with the film-like adhesive and may be exposed. Such a laminated sheet may be provided with the above-mentioned adhesive layer for a jig on the exposed surface of the resin film.

FIG. 3 is a cross-sectional view schematically showing an example of the composite sheet according to one embodiment of the present invention. The composite sheet 101 shown here includes a film-like adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film-like adhesive 13. The dicing sheet 10 includes a base material 11 and a dicing sheet 10 provided on the base material 11. The adhesive layer 12 on one side (sometimes referred to as the "first side" in this specification) 11a is configured by disposing the adhesive layer 12 between the base material 11 and the film-like adhesive 13. In other words, the composite sheet 101 is formed by laminating the base material 11, the adhesive layer 12, and the film-like adhesive 13 in this order in the thickness direction of these layers. The surface 10a of the dicing sheet 10 on the film adhesive 13 side (sometimes referred to as the "first surface" in this specification) and the surface of the adhesive layer 12 opposite to the base material 11 side (herein referred to as the "first surface" in this specification) (called "Side 1")) 12a is the same.

The composite sheet 101 further includes a release film 15 on the film-like adhesive 13 . In the composite sheet 101, an adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a film-like adhesive 13 is laminated on the entire or substantially entire surface of the first surface 12a of the adhesive layer 12. The release film 15 is laminated on the entire surface or substantially the entire surface of the first surface 13 a of the adhesive agent 13 .

The cutting blade 10 may be a well-known cutting blade. The base material 11 and the adhesive layer 12 in the cutting sheet 10 will be described in sequence.

The base material 11 in the dicing sheet 10 is in the form of a sheet or a film. Examples of the constituent material of the dicing sheet 10 include various resins. Examples of the resin constituting the dicing sheet 10 include the same resin as the resin constituting the resin film in the laminated sheet.

The resin constituting the base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

The base material may be composed of one layer (single layer), or may be composed of two or more multiple layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the base material 11 is preferably 50 μm to 300 μm, more preferably 60 μm to 150 μm. When the thickness of the base material 11 is within this range, the flexibility of the composite sheet 101 and the adhesion to an object to be adhered are further improved. Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of multiple layers means the total thickness of all the layers constituting the base material.

It is preferable that the base material 11 has high thickness accuracy, that is, it is preferable that thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to form such a base material with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer. wait.

The base material 11 may contain various well-known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like, in addition to the main constituent materials such as the aforementioned resins.

The base material 11 may be transparent or opaque, may be colored according to the purpose, and may be evaporated with other layers.

In order to improve the adhesion between the base material 11 and other layers (here, the adhesive layer 12 ) provided on the base material 11 , the surface of the base material 11 may also be roughened by sand blasting, solvent treatment, etc. ; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments, etc. In addition, the surface of the base material 11 may also be subjected to primer treatment. In addition, the base material 11 may also have an antistatic coating, a layer that prevents the base material 11 from adhering to other sheets or the base material 11 from adhering to the adsorption table when the composite sheets are stacked and stored.

The base material 11 can be produced by a known method. For example, the resin-containing base material 11 can be produced by molding a resin composition containing the aforementioned resin.

The adhesive layer 12 in the cutting sheet 10 is in a sheet or film shape and contains adhesive. Examples of the adhesive include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin and other adhesives. The resin is preferably an acrylic resin.

In addition, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resin includes not only resins that have adhesive properties by themselves, but also resins that exhibit adhesiveness by being used in combination with other components such as additives, and resins that exhibit adhesiveness by the presence of a trigger such as heat or water. Resin etc.

The adhesive layer 12 may be composed of one layer (single layer), or may be composed of two or more layers. When it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited. .

The thickness of the adhesive layer 12 is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.

The adhesive layer 12 may be formed using an energy ray curable adhesive or a non-energy ray curable adhesive. That is, the adhesive layer 12 may be either energy ray curable or non-energy ray curable. The physical properties of the energy ray curable adhesive layer 12 before and after curing can be easily adjusted. For example, by hardening the energy ray curable adhesive layer 12, the adhesive force of the adhesive layer 12 to the object to be attached can be easily adjusted.

The adhesive layer 12 can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer 12 can be formed on the target site by applying the adhesive composition on the surface to be formed of the adhesive layer 12 and drying it as needed. The ratio of the contents of components that do not vaporize at normal temperature in the adhesive composition to each other is generally the same as the ratio of the contents of the aforementioned components to each other in the adhesive layer 12 . In this specification, "normal temperature" means a temperature that is not particularly cold or hot, that is, an ordinary temperature. For example, a temperature of 15°C to 25°C can be cited.

The adhesive composition can be coated by any known method. For example, the following methods can be used: air knife coater, blade coater, rod coater, gravure coater, roller coater. Cloth coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.

When the adhesive layer 12 is provided on the base material 11 , for example, the adhesive composition is applied on the base material 11 and dried if necessary, thereby laminating the adhesive layer 12 on the base material 11 . In addition, when the adhesive layer 12 is provided on the base material 11, for example, the adhesive layer 12 can also be laminated on the base material 11 in the following manner: apply an adhesive composition on the release film, and apply it as needed. By drying, the adhesive layer 12 is preliminarily formed on the release film, and the exposed surface of the adhesive layer 12 is bonded to one surface of the base material 11 (here, the first surface 11a). In this case, the release film can be removed at any time point during the manufacturing process or use of the composite sheet 101 .

When the adhesive layer 12 is energy ray curable, examples of the energy ray curable adhesive composition include the following adhesive compositions: Adhesive composition (I-1), containing non-energy rays Curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-1a)") and energy ray curable compound; adhesive composition (I-2) contained in the aforementioned adhesive Adhesive resin (I-2a) (hereinafter, sometimes referred to as "adhesive resin (I-2a)") in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) has energy ray curability; adhesive resin The composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

When the adhesive layer 12 is non-energy ray curable, examples of the non-energy ray curable adhesive composition include the adhesive composition (I-4) containing the aforementioned adhesive resin (I-1a). wait.

The film adhesive 13 has the above-mentioned light transmittance. For example, at least one of the first surface 13a and the second surface 13b of the film adhesive 13 satisfies the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate. The thickness of the film adhesive 13 is preferably 10 μm to 40 μm. The film adhesive 13 can be formed using the above-mentioned adhesive composition.

The release film 15 is the same as the first release film 151 or the second release film 152 shown in FIG. 1 .

It is not limited to the case of the composite sheet 101. In the composite sheet of this embodiment, the release film (for example, the release film 15 shown in FIG. 3) may have any structure, and the composite sheet of this embodiment may or may not include a release film.

The composite sheet 101 is used by attaching an object (for example, the circuit formation surface of a chip) to the first surface 13 a of the film-like adhesive 13 with the release film 15 removed.

The composite sheet of this embodiment is not limited to the composite sheet shown in Figure 3. Within the scope that does not impair the effects of the present invention, a part of the composition of the composite sheet shown in Figure 3 can be changed or deleted, or the composite sheet described above can be modified. The film further adds other components. More specifically, as described below.

The composite sheet including the dicing sheet composed of a base material and an adhesive layer has been described above. However, the composite sheet of this embodiment may also include a dicing sheet composed only of the base material. That is, the composite sheet may include a base material and a film-like adhesive provided on one side of the base material, and may be configured without placing an adhesive layer between the base material and the film-like adhesive. An example of such a composite sheet is a composite sheet in which the laminated sheet 108 shown in FIG. 2 and the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3 ).

The composite sheet including a dicing sheet composed of a base material and an adhesive layer has been described above. However, the composite sheet of this embodiment may also include a dicing sheet composed of an intermediate layer in addition to the base material and adhesive layer. Examples of such a dicing sheet include a base material, an adhesive layer provided on one side of the base material, and an intermediate layer provided on a surface of the adhesive layer opposite to the side of the base material. Cutting pieces. When using such a cutting sheet, an intermediate layer is disposed between the adhesive layer and the film-like adhesive in the composite sheet.

For example, the composite sheet of this embodiment may be provided with only the peeling film on the first surface of the film-like adhesive, or may be provided with a film for fixing the composite sheet in a region near the peripheral edge of the first surface of the film-like adhesive. Use an adhesive layer for fixtures such as ring frames. The adhesive layer for a jig in this case is the same as the adhesive layer for a jig demonstrated above.

For example, when the composite sheet is viewed from above the film adhesive side or the diced sheet side, the surface areas of the film adhesive and the diced sheet may be equal or substantially equal. In the composite sheet of this embodiment, the surface areas are also equal to that of the diced sheet. The surface area of the film-like adhesive is smaller than the surface area of the cutting sheet, and a part of the cutting sheet (for example, the adhesive layer) is exposed. In this case, for example, at least the peripheral edge portion in the width direction of the dicing sheet may not be covered with the film-like adhesive and may be exposed. This kind of composite sheet may also be provided with the above-mentioned adhesive layer for a jig on the exposed surface of the cutting sheet.

In the foregoing, as the layers constituting the composite sheet, the base material, the adhesive layer, the intermediate layer, the film adhesive, the adhesive layer for the jig, and the release film are cited. However, the composite sheet of this embodiment may also have layers that do not comply with the requirements. any of these other layers. When the composite sheet includes the other layers, the arrangement position of the other layers is not particularly limited.

In the composite sheet of this embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.

◇How to use the laminated sheet (film-like adhesive) [Laminated body and its manufacturing method] The film-like adhesive in the laminated sheet of this embodiment can be used as a circuit forming surface of a chip such as a sensor. Then use the translucent cover film. More specifically, by using the film-like adhesive, it is possible to manufacture a device including a wafer, a film-like adhesive provided on a circuit forming surface of the wafer, and a side opposite to the side of the film-like adhesive provided on the side of the wafer. A laminated body composed of a translucent cover on the surface. In the above-mentioned laminated body, any one or both of the surface of the film adhesive on the chip side and the surface on the translucent cover side satisfy the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate, preferably both of them Satisfy the above conditions of V ₁ , V ₂ and P concentration reduction rate.

FIG. 4 is a cross-sectional view schematically showing an example of the laminated body. The laminated body 801 shown here includes a wafer 8, a film-like adhesive 13 provided on the circuit formation surface 8a of the wafer 8, and a surface of the film-like adhesive 13 provided on the opposite side to the wafer 8 side (the wafer 8). It is composed of a translucent cover 7 on one side) 13a.

In the laminated body 801, the opposing surfaces of the wafer 8 and the film-like adhesive 13, that is, the circuit-formed surface 8a of the wafer 8 and the surface (second surface) 13b of the film-like adhesive 13 on the wafer 8 side are in direct contact. In addition, the respective opposing surfaces of the film-like adhesive 13 and the translucent cover 7, that is, the first surface 13a of the film-shaped adhesive 13 and the surface of the translucent cover 7 on the film-shaped adhesive 13 side (this specification (sometimes called "Side 2") 7b is in direct contact. In this way, the laminated body 801 is composed of the wafer 8, the film adhesive 13, and the translucent cover 7 that are sequentially laminated in the thickness direction of these layers, and the circuit forming surface 8a of the wafer 8 is arranged on the film adhesive 13 side.

The film-like adhesive 13 in the laminated body 801 is obtained by removing the first release film 151 and the second release film 152 from the laminated sheet 109 shown in FIG. 1 , or by removing it from the laminated sheet 108 shown in FIG. 2 Resin film 19 obtained. In the laminated body 801, any one or both surfaces of the first surface 13a and the second surface 13b of the film adhesive 13 satisfy the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate, and preferably both of them satisfy the above-mentioned conditions. Conditions for V ₁ , V ₂ and P concentration reduction rate.

In addition, the circuit of the wafer 8 is omitted from illustration in FIG. 4 . In addition, symbol 7a represents the surface of the translucent cover 7 opposite to the aforementioned second surface 7b (sometimes referred to as "the first surface" in this specification).

The translucent cover 7 can protect the circuit formation surface 8 a of the wafer 8 and allow the outside of the second surface 7 b side of the translucent cover 7 to be recognized from the outside of the first surface 7 a side of the translucent cover 7 . On the other hand, the film-like adhesive 13 has the above-mentioned light transmittance. Therefore, in the laminated body 801, the visual information present on the circuit formation surface 8a of the wafer 8 can be recognized through the translucent cover 7 and the film-like adhesive 13 (the translucent cover 7 and the film-like adhesive 13 are interposed). Furthermore, as mentioned above, the film adhesive 13 has high light transmittance before and after heating, and coloring is suppressed. Therefore, the laminated body 801 can recognize the visual information on the wafer 8 stably and with high accuracy.

As the chip 8, for example, a fingerprint sensor can be used. In this case, the laminated body 801 can be used as a fingerprint sensor module.

The laminated body before using the film-like adhesive is not limited to the laminated body shown in FIG. 4. Within the scope that does not impair the effect of the present invention, a part of the composition of the laminated body shown in FIG. 4 may be changed or deleted, or Further, other structures are added to the laminated body described above.

The laminated body can be produced, for example, by bonding one side (the second side) of the film-like adhesive to the circuit formation surface of the chip and bonding a translucent cover to the other side (the first side) of the film-like adhesive.

◇How to use composite tablets [Laminated body and manufacturing method thereof] The composite sheet of this embodiment can be used in the same manner as a known composite sheet. FIG. 5 is a cross-sectional view schematically illustrating an example of how to use the composite sheet according to this embodiment. Here, the case of using the composite sheet 101 shown in FIG. 3 is shown.

As shown here, the composite sheet 101 is used by attaching the first surface 13a of the film-like adhesive 13 to the circuit formation surface 8a of the wafer 8 after removing the release film 15 .

After the composite sheet 101 is attached to the wafer 8 , for example, the wafer 8 is cut into individual pieces, and the film-like adhesive 13 is cut along the outer periphery of the individualized wafer 8 . At this time, the singulation of the wafer 8 and the cutting of the film-like adhesive 13 can be performed by known methods. For example, these operations can be performed at the same time, or after the wafer 8 is singulated, the film-like adhesive 13 can be cut separately. break.

Then, the singulated wafer 8 together with the cut film adhesive 13 is pulled away from the dicing sheet 10 and picked up. When the adhesive layer 12 is energy ray curable, the adhesive layer 12 is energy ray cured to reduce the adhesive force to the film adhesive 13 before picking up, thereby making it easier to pick up.

Then, the aforementioned laminated body (for example, the laminated body 801 shown in FIG. 4 ) can be manufactured by bonding a translucent cover to the second surface of the cut and picked-up film-like adhesive 13 . In the above-mentioned laminated body, any one or both surfaces of the first and second surfaces of the film-like adhesive satisfy the above-mentioned conditions of V ₁ , V ₂ and P concentration reduction rate, and preferably both of them satisfy the above-mentioned V ₁ , V 2 and P concentration reduction rate. Conditions for V ₂ and P concentration reduction rate.

Here, the film-like adhesive in the composite sheet is bonded to the wafer in this way. After the wafer is singulated and the film-like adhesive is cut, a light-transmitting cover is bonded to the cut film-like adhesive. The case has been described, but the order of laminating the wafer and the translucent cover to the film-like adhesive can also be reversed. That is, the above-mentioned laminated body (for example, the laminated body 801 shown in FIG. 4) can also be manufactured by attaching the first side of the film-like adhesive to the second side of the translucent cover, and then attaching the transparent adhesive to the second side of the translucent cover. The optical mask is cut into individual pieces, the film-like adhesive is cut, and the adhesive layer is cured with energy rays if necessary, and then the individualized light-transmitting cover is self-cut together with the cut film-like adhesive. The sheet is pulled off and picked up, and then the wafer is bonded to the first surface of the film-like adhesive after cutting and picking up. [Example]

Hereinafter, the present invention will be described in more detail through specific examples. However, the present invention is not limited at all by the examples shown below.

[Raw materials for manufacturing adhesive compositions] The raw materials used for manufacturing the adhesive composition in this Example and a Comparative Example are shown below.

[Acrylic resin (a)] (a)-1: Acrylic resin (weight average molecular weight 800000, glass transition temperature 6°C) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). (a)-2: Acrylic resin (weight average molecular weight 800000, glass transition temperature 9°C) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass). [Epoxy compound (b1)] (b1)-1: Cresol novolac type epoxy resin with an added acryl group ("CNA147" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518g/eq, number average molecular weight 2100, unsaturated group content and The content of epoxy groups is equal) (b1)-2: Hydrogenated bisphenol A type epoxy resin ("Epolight 4000" manufactured by Kyeisha Chemical Co., Ltd., epoxy equivalent 310g/eq to 340g/eq) [Phenolic resin (b2)] (b2)-1: Aralkyl type phenol resin ("HE100C-10" manufactured by Air Water Chemical Co., Ltd.) [Harding accelerator (c)] (c)-1: Triphenylphosphine (manufactured by Bukheung Chemical Industry Co., Ltd.) [Filling material (d)] (d)-1: Methacrylate-modified spherical silica ("YA050C-MJE" manufactured by Admatechs, average particle size 50 nm) (d)-2: Epoxy-modified spherical silica ("YA050C-MKK" manufactured by Admatechs, average particle size 50 nm) (d)-3: Epoxy-modified silica filler ("SC2050MA" manufactured by Admatechs, average particle size 500nm) [Crosslinking agent (f)] (f)-1: Toluene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh Corporation) (f)-2: Isophorone diisocyanate trimer adduct of trimethylolpropane ("D-140N" manufactured by Mitsui Chemicals Co., Ltd.) [Phosphorus antioxidant (z)] (z)-1: Bis(decyl)pentaerythritol diphosphite ("JPE-10" manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite)

[Example 1] [Manufacture of film adhesive] [Manufacture of adhesive composition] Acrylic resin (a)-1 (57.2 parts by mass), epoxy compound (b1)-1 (18 parts by mass), phenol resin (b2)-1 (3 parts by mass), and hardening accelerator (c)-1 (0.5 parts by mass), filler (d)-1 (20 parts by mass), cross-linking agent (f)-1 (0.5 parts by mass) and phosphorus antioxidant (z)-1 (0.8 parts by mass) are dissolved or dispersed The adhesive composition was obtained by stirring at 23° C. in methyl ethyl ketone and having a total concentration of all components except methyl ethyl ketone of 32% by mass. In addition, the compounding amounts of components other than methyl ethyl ketone shown here are all the compounding amounts of the target substance which does not contain a solvent component.

[Manufacture of film adhesive] A release film made of polyethylene terephthalate (PET; polyethylene terephthalate) and peeled off on one side by polysiloxane treatment ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm), The adhesive composition obtained above was applied to the release-treated surface of the release film, and heated and dried at 100° C. for 2 minutes to form a film-like adhesive with a thickness of 20 μm. The release film and film-form adhesive were obtained from these. A bonding sheet composed of layers stacked in the thickness direction.

[Evaluation of film adhesives] [Measurement of shear strength] Using a tape mounter ("Adwill RAD2500 m/12" manufactured by Lintec Corporation), the cutting sheet (manufactured by Lintec Corporation) was placed under the conditions of a mounting temperature of 23°C and an attachment speed of 20mm/s. "Adwill D-678") is attached to a 6-inch silicon wafer (thickness 350 μm), and the laminate of the diced piece and the silicon wafer is fixed to the ring frame. Then, a cutting device ("DFD6362" manufactured by DISCO) was used to cut with a cutting blade ("NBC-ZH2050-SE27HECC" manufactured by DISCO) at a blade rotation speed of 30000 rpm and a cutting speed of 40 mm/s to obtain A plurality of silicon wafers with a size of 2mm×2mm (hereinafter sometimes referred to as "silicon wafer group"). The above-mentioned dicing sheet is composed of a base material and an adhesive layered in layers. During cutting, a cutting blade is used to cut into a 20 μm deep region of the base material in the dicing sheet.

Next, while heating the adhesive sheet obtained above to 60° C., it was attached to the silicon wafer group obtained above via the film-like adhesive in the adhesive sheet. At this time, the adhesive sheet is attached to the surface (exposed surface) of the silicon wafer in the silicon wafer group that is opposite to the side to which the dicing sheet is attached. Then, the attached adhesive sheet is cut along the outer periphery of the silicon wafer. Through the above steps, a laminated product with a size of 2 mm × 2 mm is obtained by laminating cutting sheets, silicon wafers and bonding sheets sequentially in the thickness direction of these layers.

Then, the peeling film was removed from the film-like adhesive in the laminate, and the exposed surface of the newly produced film-like adhesive was attached to the copper plate with a size of 30 mm × 30 mm and a thickness of 300 μm using a manual die bonding machine. surface. At this time, the film-like adhesive is adhered by applying a force of 2.45N (250gf) against the copper plate while heating it to 125°C. Furthermore, these laminated bodies were heated at 175° C. for 5 hours to obtain test pieces.

Then, a universal bonding strength testing machine ("DAGE4000" manufactured by Nordson Advanced Technology) was used to test the side of the test piece using a shearing tool at a speed of 200 μm/s at a temperature of 23°C. Both the film adhesive and the silicon wafer apply force in a direction parallel to the surface where the film adhesive adheres to the copper plate. Then, the maximum value of the force applied until the film-like adhesive is destroyed is confirmed, and this maximum value is adopted as the shear strength (N/2mm□) of the film-like adhesive. The results are shown in Table 1.

[Measurement of linear transmittance before heating of light (400nm to 800nm)] The film-like adhesive obtained above was attached to one side of a glass slide (thickness: 0.9 mm) while being heated at 40°C. The film-like adhesive is not heat-treated between the time it is produced and the time it is attached. Next, the portion of the attached film-like adhesive extruded from the glass carrier was cut to obtain film-like adhesives and glass carriers of the same size in which the positions of the peripheral portions of these layers were consistent. A test piece composed of layers stacked in the thickness direction (hereinafter referred to as "test piece before heating").

For the glass slide used to prepare the test piece before heating, a spectrophotometer ("UV-3101PC" manufactured by Shimadzu Co., Ltd.) was used to measure the straight line under light (400nm to 800nm) before making the test piece before heating. Transmittance (hereinafter referred to as "reference linear transmittance"). For the test piece before heating obtained above, the linear transmittance in light (400nm to 800nm) was also measured using the same method. From the measured value of the linear transmittance of light at each wavelength (400nm to 800nm) of the test piece before heating, subtract the measured value of the aforementioned reference linear transmittance at the same wavelength, and use the value obtained by subtraction as the value before heating. The linear transmittance of the film adhesive in light (400nm to 800nm) (that is, the linear transmittance before heating). The results are shown in Table 1.

[Measurement of linear transmittance after heating of light (400nm to 800nm)] Using an electric furnace, the test piece for which the linear transmittance before heating of light (400 nm to 800 nm) was measured was heated at 260° C. for 10 minutes. Then, the heated test piece was left to cool to the same temperature as room temperature. Then, with respect to the heated and left to cool test piece (hereinafter referred to as the "heated test piece"), the linear transmission of light (400nm to 800nm) was measured using the same method as the above-mentioned test piece before heating. Rate. The measured value of the linear transmittance of light at each wavelength (400nm to 800nm) of the test piece after self-heating is subtracted from the measured value of the aforementioned reference linear transmittance at the same wavelength, and the value obtained by subtraction is used as the value after heating. The linear transmittance of the film adhesive in light (400nm to 800nm) (that is, the linear transmittance after heating). The results are shown in Table 1.

[Evaluation of fingerprint recognition performance before heating based on RGB] A digital camera ("IXY650" manufactured by Canon) was placed in front of the left index finger, and the distance between the surface of the left index finger and the surface of the camera lens was adjusted to 50 mm. In this state, the left index finger was captured in macro mode. The image data of the fingerprint (hereinafter referred to as the "base image data"). Keeping the arrangement relationship between the left index finger and the digital camera unchanged, place the aforementioned pre-heating test piece between the left index finger pulp and the digital camera. At this time, the straight line connecting the pulp of the left index finger and the digital camera is aligned with the exposed surface of the glass slide in the test piece before heating (that is, the surface opposite to the surface where the film-like adhesive is attached). Then, arrange the test piece before heating so that the exposed surface becomes the digital camera side. Under this condition, the image data of the fingerprint of the left index finger (hereinafter referred to as "pre-heating transmission image data") is acquired in macro mode using the same method as when acquiring the aforementioned reference image data.

Using drawing software ("Paint" manufactured by Microsoft Corporation), the above-obtained reference image data and the pre-heating through-image data are expanded, and the colors of the mountain and valley parts of the fingerprint are extracted from the respective data, and the colors of the mountains and valleys of the fingerprint are extracted using RGB (Red). Green Blue; red, green, blue) numerically. The R value of the mountain portion of the fingerprint obtained from the image data before free heating is subtracted from the R value of the mountain portion of the fingerprint obtained from the reference image data. The value obtained by the subtraction is used as the value of the mountain portion of the fingerprint during evaluation before heating. R-value. Using the same method as described above, the G value and the B value of the mountain portion of the fingerprint during the pre-heating evaluation were determined. Using the same method as above, subtract the R value of the valley part of the fingerprint obtained from the reference image data from the R value of the valley part of the fingerprint obtained from the image data before free heating, and use the value obtained by the subtraction as the pre-heating evaluation. The R value of the valley of the fingerprint. Using the same method as described above, the G value and B value of the valley portion of the fingerprint during pre-heating evaluation were determined. Furthermore, the absolute value of the difference between the R value of the mountain portion and the R value of the valley portion is calculated (hereinafter, sometimes referred to as "absolute value ΔR"), and the G value of the mountain portion and the G value of the valley portion are calculated. The absolute value of the difference (hereinafter, sometimes described as "absolute value ΔG") is calculated as the absolute value of the difference between the B value of the mountain portion and the B value of the valley portion (hereinafter, sometimes described as "absolute value ΔB"). .

Based on these calculated values, the fingerprint recognition properties of the film-like adhesive before heating based on RGB were evaluated based on the following criteria. The results are shown in Table 1. (evaluation criteria) A: At least one of absolute value ΔR, absolute value ΔG, and absolute value ΔB is 10 or more. B: Absolute value ΔR, absolute value ΔG, and absolute value ΔB are all less than 10, and at least one of absolute value ΔR, absolute value ΔG, and absolute value ΔB is 5 or more. C: Absolute value ΔR, absolute value ΔG, and absolute value ΔB are all less than 5.

[Evaluation of fingerprint recognition after heating based on RGB] The test piece after heating was used instead of the test piece before heating. Except for this point, the same method as in the above "evaluation of fingerprint recognition before heating" was used to evaluate the film-like adhesive based on RGB after heating. Fingerprint recognition. More specifically, in this evaluation, "post-heating transmission image data" was obtained instead of the aforementioned pre-heating transmission image data. In addition, using the transmission image data after heating, the R value, G value, and B value of the mountain portion of the fingerprint during evaluation after heating were obtained instead of the R value, G value, and B value of the mountain portion of the fingerprint during evaluation before heating. , instead of the R value, G value, and B value of the valley portion of the fingerprint during evaluation before heating, the R value, G value, and B value of the valley portion of the fingerprint during evaluation after heating are obtained. Furthermore, the absolute value ΔR, the absolute value ΔG, and the absolute value ΔB during the post-heating evaluation were calculated from these R values, G values, and B values in place of the aforementioned absolute values ΔR, absolute value ΔG, and absolute value ΔB during the pre-heating evaluation. The results are shown in Table 1.

[Evaluation of fingerprint recognition properties before heating based on visual inspection] Five observers are randomly selected and the fingerprints are visually observed one by one using the method shown below. That is, an observer is placed in front of the pulp of the left index finger, the distance between the surface of the pulp of the left index finger and the observer's eyes is adjusted to 150 mm, and the fingerprint of the left index finger is directly visually observed in this state. Keeping the arrangement relationship between the left index finger and the observer unchanged, place the aforementioned pre-heating test piece between the left index finger pulp and the observer. The arrangement form of the test piece before heating at this time is the same as that of the test piece before heating in the above-mentioned "evaluation of fingerprint recognition properties before heating based on RGB". Under these conditions, the fingerprint of the left index finger was visually observed through the test piece before heating, in the same manner as in the case of direct visual observation as described above.

Through this method, all five observers were allowed to visually observe the fingerprints directly and across the pre-heated test piece. By comparing the viewing results of the fingerprints through the pre-heating test piece and the direct visual viewing results, the basis The fingerprint recognition properties of the film-like adhesive before heating were evaluated based on visual inspection based on the following criteria. The results are shown in Table 1. The numerical value in parentheses in the "Fingerprint Recognizability" column of Table 1 indicates "the number of observers (persons) who judged that there is no difference in the fingerprint viewing results." A: All five observers judged that there was no difference in the fingerprint viewing results. B: Four out of five observers judged that there was no difference in the fingerprint viewing results. C: More than 2 out of 5 observers judged that the colors of the fingerprints were different from each other, resulting in differences in the viewing results.

[Evaluation of fingerprint recognition ability after heating based on visual inspection] The test piece after heating was used instead of the test piece before heating. Except for this point, the same method as in the above "evaluation of fingerprint recognition before heating by visual inspection" was used to evaluate the film shape after heating by visual inspection. Fingerprint recognition of adhesives. The results are shown in Table 1.

[Measurement of V ₁ ] The film-like adhesive obtained above (hereinafter referred to as A 0.1mm×1mm area on one side of the "film-like adhesive before heating") was surveyed and scanned, and XPS analysis was performed to measure the P concentration V ₁ on the side. At this time, the peak detected in the bonding energy range of 123eV to 143eV is determined to be the P2p spectrum. As an X-ray source, aluminum is used. The film-like adhesive was not heated between the time of production and the measurement. The results are shown in Table 1.

[Measurement of V ₂ ] Using an electric furnace, the pre-heated film adhesive after measuring V ₁ was heated at 260°C for 10 minutes. Then, the heated film adhesive is left to cool to the same temperature as room temperature. Next, for the measurement surface of _V1 in the film-like adhesive after heating and cooling (hereinafter referred to as "heated film-like adhesive"), the same measurement surface as in the case of the film-like adhesive before heating was used. Method, XPS analysis was performed to determine the P concentration V ₂ . The results are shown in Table 1.

[Calculation of P concentration reduction rate] Calculate the P concentration reduction rate from V ₁ and V ₂ obtained above. The results are shown in Table 1.

[Manufacture and evaluation of film adhesives] [Example 2 to Example 5] Except for changing any or both of the types and amounts of components to be prepared when producing the adhesive composition so that the types and contents of the components contained in the adhesive composition are as shown in Table 1, In the same manner as in Example 1, a film-like adhesive was produced and evaluated. The results are shown in Table 1.

[Comparative Example 1 to Comparative Example 2] Except for changing any or both of the types and amounts of components to be prepared when producing the adhesive composition so that the types and contents of the components contained in the adhesive composition are as shown in Table 2, Using the same method as in Example 1, the production and evaluation of the film adhesive were attempted. The results are shown in Table 2.

In addition, when "-" is written in the column of contained ingredients in Tables 1 and 2, it means that the adhesive composition does not contain the ingredient. In addition, when "-" is recorded in the evaluation result column in Tables 1 and 2, it means that the item cannot be evaluated (including the situation where the data cannot be obtained, and the situation where the data does not reach the detection limit), or the data cannot be calculated.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Ingredients contained in the adhesive composition (parts by mass) Acrylic resin (a) (a)-1 57.2 43.3 - 58 - (a)-2 - - 61.8 - 61 Epoxy compound(b1) (b1)-1 18 - 6 18 6 (b1)-2 - 40 - - - Phenolic resin (b2) (b2)-1 3 - 1 3 1 Hardening accelerator (c) (c)-1 0.5 1.2 0.2 - - Filling material(d) (d)-1 20 - 30 20 30 (d)-2 - 15 - - - (d)-3 - - - - - Cross-linking agent (f) (f)-1 0.5 - - 0.5 - (f)-2 - - - - 1 Phosphorus antioxidant(z) (z)-1 0.8 0.5 1 0.5 1 Evaluation results Shear strength (N/2mm□) 84 95 58 63 48 Linear transmittance before heating (%) 97 95 96 97 97 Linear transmittance after heating (%) 88 85 91 92 94 Fingerprint recognition before heating based on RGB Yamabe R 214 192 185 220 192 G 147 130 120 158 127 B 149 135 118 161 131 Tanibe R 204 188 189 216 187 G 142 115 109 143 110 B 147 122 110 152 118 Absolute value ΔR 10 4 4 4 5 Absolute value ΔG 5 15 11 15 17 Absolute value ΔB 2 13 8 9 13 Fingerprint recognition A A A A A Visual evaluation of fingerprint recognition before heating A(5) A(5) A(5) A(5) A(5) Fingerprint recognition after heating based on RGB Yamabe R 201 202 213 189 215 G 135 121 147 128 166 B 141 128 149 133 163 Tanibe R 200 199 204 183 225 G 130 116 142 112 160 B 134 126 147 120 166 Absolute value ΔR 1 3 9 6 10 Absolute value ΔG 5 5 5 16 6 Absolute value ΔB 7 2 2 13 3 Fingerprint recognition B B B A A Visual evaluation of fingerprint recognition after heating B(4) B(4) A(5) A(5) A(5) V ₁ (atomic %) 0.21 0.40 0.28 0.15 0.25 V ₂ (atomic %) 0.18 0.39 0.26 0.14 0.24 P concentration reduction rate (%) 14.3 2.5 7.1 6.7 4.0

[Table 2] Comparative example 1 Comparative example 2 Ingredients contained in the adhesive composition (parts by mass) Acrylic resin (a) (a)-1 40 58.5 (a)-2 - - Epoxy compound (b1) (b1)-1 - 18 (b1)-2 40 - Phenolic resin (b2) (b2)-1 - 3 Hardening accelerator (c) (c)-1 - - Filling material(d) (d)-1 - - (d)-2 20 - (d)-3 - 20 Cross-linking agent (f) (f)-1 - 0.5 (f)-2 - - Phosphorus antioxidant(z) (z)-1 - - Evaluation results Shear strength (N/2mm□) 44 50 Linear transmittance before heating (%) 96 35 Linear transmittance after heating (%) 77 28 Fingerprint recognition before heating based on RGB Yamabe R 198 192 G 125 127 B 132 123 Tanibe R 183 192 G 108 131 B 112 126 Absolute value ΔR 15 0 Absolute value ΔG 17 4 Absolute value ΔB 20 3 Fingerprint recognition A C Visual evaluation of fingerprint recognition before heating A(5) C(0) Fingerprint recognition after heating based on RGB Yamabe R 154 164 G 94 110 B 96 87 Tanibe R 153 166 G 90 106 B 92 84 Absolute value ΔR 1 2 Absolute value ΔG 4 4 Absolute value ΔB 4 3 Fingerprint recognition C C Visual evaluation of fingerprint recognition after heating C(2) C(0) V ₁ (atomic %) - - V ₂ (atomic %) - - P concentration reduction rate (%) - -

From the above results, it is clear that in Examples 1 to 5, the film adhesive before and after heating at 260° C. has high light transmittance, suppresses coloration, and has high fingerprint recognition properties. In Examples 1 to 5, the linear transmittance of the film adhesive in light (400nm to 800nm) before heating at 260°C is 95% or more (95% to 97%), and the film after heating at 260°C The linear transmittance of the adhesive in light (400nm to 800nm) is over 85% (85% to 94%).

In Examples 1 to 5, the shear strength of the film-like adhesive is 48N/2mm□ or more (48N/2mm□ to 95N/2mm□), and the adhesive force of the film-like adhesive is sufficiently strong.

In Examples 1 to 5, V ₁ is 0.15 atomic % or more (0.15 atomic % to 0.40 atomic %), V ₂ is 0.14 atomic % or more (0.14 atomic % to 0.39 atomic %), and the P concentration reduction rate is 14.3 % (2.5% to 14.3%) and small. In this way, it was proven that in Examples 1 to 5, the concentration of phosphorus in the film-like adhesive before and after heating was high, and the film-like adhesive after heating also contained phosphorus in a sufficient amount to show a sufficient antioxidant effect. Phosphorus antioxidant (z).

On the other hand, in Comparative Example 1, although the translucency of the film-like adhesive before heating at 260°C was high and the coloring was suppressed, the translucency of the film-like adhesive after heating at 260°C was low and the coloring was suppressed. Unsuppressed, low fingerprint readability. In Comparative Example 1, since the film adhesive does not contain an antioxidant, it is presumed that coloration due to heating is not suppressed. In Comparative Example 1, naturally V ₁ and V ₂ did not reach the detection limit value, and the P concentration reduction rate could not be calculated.

In Comparative Example 2, the film-like adhesive at the stage before heating at 260° C. already had low light transmittance, generated white turbidity, and had low fingerprint recognition properties. Therefore, the film adhesive after being heated at 260°C is still in a white and turbid state, and has low fingerprint recognition ability. In Comparative Example 2, since the filler (d)-3 with a large average particle diameter was used, it is presumed that the film-like adhesive becomes cloudy. This can also be clearly understood from a comparison between the film adhesive agent of Example 4 and the film adhesive agent of Comparative Example 2, which have very similar compositions except for the type of filler (d) used. In Comparative Example 2, it was not possible to confirm whether the coloring caused by heating was suppressed due to the influence of the turbidity. However, since the film adhesive does not contain an antioxidant, it is presumed that the coloring caused by heating was not suppressed. In Comparative Example 2, naturally V ₁ and V ₂ did not reach the detection limit, and the P concentration reduction rate could not be calculated.

Furthermore, in Comparative Example 1, the shear strength of the film adhesive was 44 N/2mm□, and the adhesive force of the film adhesive was weaker than in Examples 1 to 5. [Industrial Availability]

The present invention can be used as an adhesive when manufacturing or processing various parts constituting electronic equipment.

7: Translucent cover 7a: The first side of the translucent cover 7b: The second side of the translucent cover 8:wafer 8a: Circuit formation surface of the wafer 10: Cutting piece 10a: Side 1 of cutting piece 11:Substrate 11a:Side 1 of the substrate 12: Adhesive layer 12a: Side 1 of adhesive layer 13: Film adhesive 13a: The first side of film adhesive 13b: The second side of the film adhesive 15: Peel off film 19:Resin film 101:Composite tablet 108,109:Laminated chip 151: 1st peeling film 152: 2nd peeling film 801:Laminated body

[Fig. 1] is a cross-sectional view schematically showing an example of a film adhesive and a laminated sheet according to an embodiment of the present invention. [Fig. 2] is a cross-sectional view schematically showing another example of the laminated sheet according to one embodiment of the present invention. [Fig. 3] is a cross-sectional view schematically showing an example of the composite sheet according to one embodiment of the present invention. [Fig. 4] A cross-sectional view schematically showing an example of a laminated body produced using the film adhesive agent according to one embodiment of the present invention. FIG. 5 is a cross-sectional view schematically illustrating an example of a method of using the composite sheet according to the embodiment of the present invention.

13: Film adhesive

13a: The first side of film adhesive

13b: The second side of the film adhesive

109:Laminated sheet

151: 1st peeling film

152: 2nd peeling film

Claims (10)

A film-like adhesive used to bond the circuit formation surface and the light-transmitting cover of the chip; contains: acrylic resin (a), epoxy compound (b1), phosphorus antioxidant (z), and filler material ( d); the aforementioned phosphorus-based antioxidant (z) is a trivalent phosphorus compound; the average particle size of the aforementioned filling material (d) is 10 nm to 100 nm; the content of the aforementioned acrylic resin (a) in the aforementioned film-like adhesive is relatively The proportion of the total mass of the aforementioned film adhesive is 30 mass % to 65 mass %; the content of the aforementioned epoxy compound (b1) is 5 mass parts to 100 mass parts relative to 100 mass parts of the aforementioned acrylic resin (a). parts; the content of the phosphorus-based antioxidant (z) in the aforementioned film-like adhesive relative to the total mass of the aforementioned film-like adhesive is 0.3% by mass to 1.5% by mass; when the aforementioned film-like adhesive before heating at 260°C One side of the adhesive was analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V _{1 ,} and the V ₁ was measured in the film adhesive after heating at 260°C for 10 minutes. When the phosphorus concentration V ₂ is measured by X-ray photoelectron spectroscopy analysis, the V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the V ₁ and V ₂ is 25% or less. A film-like adhesive used to bond the circuit formation surface and the light-transmitting cover of the chip; contains: acrylic resin (a), epoxy compound (b1), phosphorus antioxidant (z), and aliphatic polyvalent resin Isocyanate cross-linking agent; the acrylic resin (a) has a functional group capable of bonding with the aliphatic polyisocyanate cross-linking agent; the content of the acrylic resin (a) in the film adhesive is relative to the The proportion of the total mass of the film adhesive is 30 to 65 mass %; the content of the aforementioned epoxy compound (b1) is 5 to 100 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic resin (a); The content of the phosphorus-based antioxidant (z) in the film-like adhesive relative to the total mass of the film-like adhesive is 0.3 mass% to 1.5 mass%; when the film-like adhesive before heating at 260°C On one side, the phosphorus concentration V ₁ is measured by analyzing by X-ray photoelectron spectroscopy, and on the side on which _the aforementioned V ₁ is measured in the aforementioned film-like adhesive after heating at 260° C. for 10 minutes, When the phosphorus concentration V ₂ is measured by analysis by X-ray photoelectron spectroscopy, the V ₁ is 0.1 atomic % or more, and the reduction rate of the phosphorus concentration calculated from the V ₁ and V ₂ is 25% or less. The film adhesive as described in claim 1 or 2, wherein the linear transmittance of the film adhesive before heating at 260°C for light with a wavelength of 400nm to 800nm is more than 90%; after heating at 260°C for 10 minutes The linear transmittance of the aforementioned film-like adhesive for light with a wavelength of 400 nm to 800 nm is more than 85%; the thickness of the aforementioned film-like adhesive is 10 μm to 40 μm. The film adhesive according to claim 1 or 2, wherein the film adhesive contains an aliphatic epoxy compound as the epoxy compound (b1). The film adhesive according to claim 1 or 2, wherein the film adhesive contains a phenol resin (b2); the content of the phenol resin (b2) in the film adhesive is relative to the content of the film adhesive. The proportion of the total mass is 10% by mass or less. The film adhesive according to claim 1 or 2, wherein the film adhesive contains an aliphatic phosphite as the phosphorus antioxidant (z). The film adhesive according to claim 1, wherein the film adhesive contains an aliphatic polyisocyanate cross-linking agent; and the acrylic resin has a functional group capable of bonding with the cross-linking agent. A laminated sheet including the film-like adhesive according to any one of claims 1 to 7, and a resin film provided on one side of the film-like adhesive. A composite sheet comprising a film-like adhesive as described in any one of claims 1 to 7, and a cutting sheet provided on one side of the film-like adhesive; the cutting sheet includes a base material, and is provided on the base An adhesive layer on one side of the material; the adhesive layer is arranged between the base material and the film-like adhesive. A method for manufacturing a laminated body in which the circuit formation surface of a wafer is bonded to one side of the film-like adhesive as described in any one of claims 1 to 7, and a light-transmitting layer is bonded to the other side of the film-like adhesive. cover, thereby obtaining a laminated body in which the wafer, the film-like adhesive, and the translucent cover are sequentially laminated.

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