WO2020137944A1

WO2020137944A1 - Film-like adhesive, laminate sheet, composite sheet, and manufacturing method for laminate

Info

Publication number: WO2020137944A1
Application number: PCT/JP2019/050292
Authority: WO
Inventors: 陽輔佐藤
Original assignee: リンテック株式会社
Priority date: 2018-12-28
Filing date: 2019-12-23
Publication date: 2020-07-02
Also published as: KR20210108359A; CN113165347A; JP7421498B2; JPWO2020137944A1; KR102703876B1; CN113165347B; TW202039722A; TWI825254B

Abstract

A film-like adhesive of this embodiment is for bonding a circuit formation surface of a chip to a light-transmissive cover. When phosphorus concentration V1 is measured by performing X-ray photoelectron spectroscopy analysis on one surface of the film-like adhesive before the film-like adhesive is heated at 260°C, and when phosphorus concentration V2 is measured by performing X-ray photoelectron spectroscopy analysis on the surface where V1 was measured on the film-like adhesive after V1 is measured and the film-like adhesive is heated for 10 minutes at 260°C, V1 is 0.1 atomic% or greater, and the rate of decrease in concentration of phosphorus calculated from V1 and V2 is 25% or less.

Description

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

The present invention relates to a film adhesive, a laminated sheet, a composite sheet, and a method for producing a laminated body.
The present application claims priority based on Japanese Patent Application No. 2018-246838 filed in Japan on December 28, 2018, the contents of which are incorporated herein by reference.

Various film adhesives are used depending on the purpose at the time of manufacturing or processing various parts constituting electronic devices.
For example, when mounting the semiconductor chip on the circuit forming surface of the substrate, a film adhesive is pasted on the back surface of the semiconductor chip, and the semiconductor chip is attached to the circuit forming surface of the substrate via this film adhesive. Adhere (die bonding). When protecting the circuit forming surface of a chip such as a sensor, the circuit forming surface is covered with a light transmissive cover via a light-transmissive film adhesive.

On the other hand, parts equipped with such a film adhesive may be exposed to high temperatures due to the heating process such as the solder reflow process. In that case, deterioration of the film adhesive due to the influence of heat may be a problem. For example, if the film adhesive having light transmittance changes color, it becomes difficult to read information through the film adhesive. The film adhesive contains a resin component in order to exhibit adhesiveness, and in some cases, contains a thermosetting component in order to impart thermosetting property, but these components are Some are unstable to heat. That is, the conventional film-like adhesive is easily discolored by heating.

As a film-like adhesive having a light-transmitting property, for example, a die-bonding film for die-bonding a semiconductor chip and having a light transmittance of 80% or more at a wavelength of 1065 nm is disclosed (see Patent Document 1).

Japanese Patent No. 6310748

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

The present invention uses a film-like adhesive that has optical transparency before and after heating and is suppressed from being colored after heating, a laminated sheet and a composite sheet using the film-like adhesive, and the film-like adhesive. It is an object of the present invention to provide a method for manufacturing a laminated body having such a structure.

The present invention relates to a film adhesive for bonding a circuit forming surface of a chip to a light-transmitting cover, wherein one surface of the film adhesive before heating at 260° C. is X-ray The surface on which the V ₁ was measured in the film adhesive after performing analysis by photoelectron spectroscopy, measuring the phosphorus concentration V ₁ , measuring the V ₁ , and heating at 260° C. for 10 minutes Was analyzed by X-ray photoelectron spectroscopy and the concentration V ₂ of phosphorus was measured, the V ₁ was 0.1 atomic% or more, and the concentration of phosphorus calculated from V ₁ and V ₂ was decreased. A film adhesive having a rate of 25% or less is provided.
In the film adhesive of the present invention, the linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive before heating at 260° C. is 90% or more, and the film adhesive is heated at 260° C. for 10 minutes. The linear adhesiveness of light having a wavelength of 400 to 800 nm may be 85% or more, and the thickness of the adhesive film may be 10 to 40 μm.
The film adhesive of the present invention may contain an aliphatic epoxy compound.
The film adhesive of the present invention contains a phenol resin (b2), and the ratio of the content of the phenol resin (b2) to the total mass of the film adhesive in the film adhesive is 10 mass. It may be less than or equal to %.

The film adhesive of the present invention may contain an aliphatic phosphite ester as an antioxidant.
In the film adhesive of the present invention, the film adhesive contains an acrylic resin and an aliphatic polyisocyanate crosslinking agent, and the acrylic resin is a functional group capable of binding to the crosslinking agent. It may have a group.
The present invention provides a laminated sheet comprising the film adhesive and a resin film provided on one surface of the film adhesive.
The present invention comprises the film adhesive and a dicing sheet provided on one surface of the film adhesive, wherein the dicing sheet is a base material and one surface of the base material. And a pressure-sensitive adhesive layer provided on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer being disposed between the substrate and the film adhesive.
The present invention, the one surface of the film adhesive, the circuit forming surface of the chip is attached, the other surface of the film adhesive, by attaching a light-transmitting cover, the chip, the Provided is a method for producing a laminate, which comprises obtaining a laminate in which a film adhesive and the light-transmitting cover are laminated in this order.

The film-like adhesive of the present invention has optical transparency before and after heating, and coloration after heating is suppressed.
By using the laminated sheet or the composite sheet of the present invention provided with the film adhesive of the present invention, the film adhesive can be provided to a component to which the film adhesive is applied.
According to the method for producing a laminated body of the present invention, it is possible to produce a laminated body including a chip, a film adhesive, and a light-transmitting cover, which are laminated in this order.

It is sectional drawing which shows typically an example of the film adhesive and laminated sheet which concern on one Embodiment of this invention. It is sectional drawing which shows typically the other example of the laminated sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the composite sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the laminated body manufactured using the film adhesive which concerns on one Embodiment of this invention. FIG. 6 is a cross-sectional view for schematically explaining an example of a method of using the composite sheet according to the embodiment of the present invention.

◇Film-like adhesive The film-like adhesive according to one embodiment of the present invention is a film-like adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, and is heated at 260° C. The one side of the film adhesive before is analyzed by X-ray photoelectron spectroscopy (which may be abbreviated as “XPS” in this specification), and the concentration of phosphorus (in this specification, "P concentration" may be abbreviated) V ₁ is measured, the V ₁ is measured, and the surface of the film adhesive after the V ₁ is measured, after being heated at 260° C. for 10 minutes Was analyzed by X-ray photoelectron spectroscopy (XPS), and when the phosphorus concentration (P concentration) V ₂ was measured, the V ₁ was 0.1 atomic% or more, and was calculated from the V ₁ and V _2. The reduction rate of the concentration of phosphorus (hereinafter sometimes abbreviated as “P concentration reduction rate”) is 25% or less.

Examples of the film-like adhesive that satisfies the conditions of V ₁ and V ₂ and the reduction ratio include those containing a trivalent phosphorus compound. Such a film-like adhesive suppresses turbidity and coloring before and after heating at 260° C. and the like, and has a wavelength of 400 to 800 nm (in the present specification, “light (400 to 800 nm)”). (It may be abbreviated) High linear transmittance.

The film-like adhesive of the present embodiment can be used for adhering an object when manufacturing or processing various parts constituting an electronic device.
For example, the circuit forming surface of a chip such as a sensor can be covered with a light transmissive cover (protective cover) via the film adhesive. That is, the film adhesive can be used as a film for adhering the cover to the circuit forming surface of the chip.
In that case, as described above, the film adhesive has high light transmittance before and after heating, and coloring is suppressed.Therefore, the visual presence present on the circuit formation surface of the chip is exceeded through the light transparent cover and the film adhesive. Information can be viewed with stability and high accuracy.

A fingerprint sensor is an example of a sensor to be covered by the light-transmitting cover (protective cover). 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 referred to as a “circuit forming surface”.
In the present specification, the mere description of “chip” does not mean only a semiconductor chip, but includes chips other than the semiconductor chip.

The film adhesive of the present embodiment preferably has thermosetting properties and preferably pressure-sensitive adhesive properties. For example, a film adhesive having both thermosetting property and pressure-sensitive adhesive property can be attached by lightly pressing to various adherends in the uncured state. Further, the film adhesive may be one that can be attached to various adherends by heating and softening. When cured, the film adhesive finally becomes a cured product having high impact resistance, and this cured product can retain sufficient adhesive properties even under severe conditions of high temperature and high humidity.

The linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment before heating at 260° C. (in this specification, may be abbreviated as “pre-heating linear transmittance”) is It is preferably 90% or more, more preferably 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 value, the film adhesive before heating has a property that an image can be correctly recognized when the image is viewed through the film adhesive (in the present specification. , It is sometimes abbreviated as "image recognition property").

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

The above-mentioned linear transmittance of light (400 to 800 nm) before heating can be appropriately adjusted within a range that is set by arbitrarily combining any of the above lower limit value and upper limit value. For example, in one embodiment, the linear transmittance before heating is preferably 90 to 99.8%, more preferably 91.5 to 99.8%, and 93 to 99.8%. It is more preferable, and it is particularly preferable that it is 94.5 to 99.8%. However, these are examples of the linear transmittance before heating.

Linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment after heating at 260° C. for 10 minutes (may be abbreviated as “linear transmittance after heating” in this specification). Is preferably 85% or more, and may be any of 87.5% or more, 90% or more, and 92% or more, for example. When the linear transmittance after heating is at least the lower limit value, the film adhesive after heating has high image recognizability.

What is the upper limit of the linear transmittance of light (400 to 800 nm) after heating. It is not particularly limited and may be 100%.
For example, the film adhesive having a linear transmittance of 99.8% or less after heating is easier to manufacture.

The linear transmittance of light (400 to 800 nm) after heating can be appropriately adjusted within a range set by arbitrarily combining any one of the above lower limit value and upper limit value. For example, in one embodiment, the linear transmittance after heating is preferably 85 to 99.8%, for example, 87.5 to 99.8%, 90 to 99.8%, and 92 to 99.%. It may be either 8%. However, these are examples of the linear transmittance after heating.

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

The heating condition of the film adhesive of 260° C. for 10 minutes when defining the linear transmittance after heating is set in consideration of the conditions in the heating process such as the solder reflow process.

The shear strength of the film adhesive of the present embodiment is not particularly limited, but is preferably 20 N/2 mm□ or more, for example, 50 N/2 mm□ or more, 60 N/2 mm□ or more, 70 N/2 mm□ or more, and It may be 80 N/2 mm or more. When the shear strength of the film adhesive is equal to or more than the lower limit value, the adhesive strength to the pasting target becomes stronger.
In the present specification, the unit “N/2 mm□” has the same meaning as “N/(2 mm×2 mm)”.

The upper limit of the shear strength of the film adhesive is also not particularly limited.
For example, a film adhesive having a shear strength of 300 N/2 mm□ or less is easier to manufacture.

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

The shear strength of the film adhesive in the present embodiment is measured by the method described below.
(Measuring method of shear strength of film adhesive)
Using a film-like adhesive having a size of 2 mm×2 mm and a thickness of 20 μm, a copper plate having a size of 30 mm×30 mm and a thickness of 300 μm, and a silicon chip, the film-like adhesive of A test piece is prepared in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate. On at least one side surface of this test piece, the side surfaces of the film adhesive and the silicon chip are aligned.
Under the temperature condition of 23° C., in the side surface where the alignment is performed in the test piece, for both the film adhesive and the silicon chip, for the other surface of the film adhesive. In a direction parallel to each other at a speed of 200 μm/s, and the maximum value of the force applied until the film adhesive is broken is defined as the shear strength (N/2 mm□ of the film adhesive. ) Is adopted as.

When XPS analysis was performed on one surface of the film adhesive before heating at 260° C. and the P concentration V ₁ was measured, V ₁ was 0.1 atomic% or more, and 0.12 atomic% or more. Is more preferable, and 0.14 atomic% or more is more preferable. For example, 0.2 atomic% or more, and 0.3 atomic% or more may be any. When V ₁ is at least the lower limit value, the effect of suppressing coloring of the film adhesive before heating (for example, heating at 260° C.) becomes high.

The upper limit value of V ₁ is not particularly limited.
For example, a film-like adhesive having V ₁ of 0.5 atomic% or less is easier to manufacture.

V ₁ can be appropriately adjusted within a range set by arbitrarily combining any of the above lower limit value and upper limit value. For example, in one embodiment, V ₁ is preferably 0.1-0.5 atomic%, more preferably 0.12-0.5 atomic%, and 0.14-0.5 atomic%. % Is more preferable, and may be either 0.2 to 0.5 atomic% or 0.3 to 0.5 atomic%.

Of the film-like adhesive after measuring V ₁ and heating at 260° C. for 10 minutes, the measurement surface of V ₁ is subjected to XPS analysis to measure P concentration V ₂ , and V ₂ is , 0.1 atomic% or more, preferably 0.12 atomic% or more, more preferably 0.14 atomic% or more, for example, 0.2 atomic% or more, and 0. It may be any of 0.3 atomic% or more. When V ₂ is equal to or more than the lower limit value, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) becomes higher.

The upper limit of V ₂ is not particularly limited.
For example, a film adhesive having V ₂ of 0.5 atomic% or less is easier to manufacture.

V ₂ can be appropriately adjusted within a range that is set by arbitrarily combining any of the above lower limit value and upper limit value. For example, in one embodiment, V ₂ is preferably 0.1 to 0.5 atomic%, more preferably 0.12 to 0.5 atomic%, and 0.14 to 0.5 atomic%. % Is more preferable, and may be either 0.2 to 0.5 atomic% or 0.3 to 0.5 atomic%.

V ₁ and V ₂ can be measured by survey-scanning an area of 0.1 mm×1 mm on one surface of the film adhesive having a thickness of 20 μm and performing XPS analysis. At this time, the measurement angle is 45° and the beam diameter is 18 μm. Aluminum can be used as the X-ray source, for example.

The P concentration decrease rate calculated from V ₁ and V ₂ is 25% or less, preferably 20% or less, more preferably 15% or less, and for example, 10% or less, 7.5. % Or less, or 5% or less. When the P concentration reduction rate is not more than the upper limit value, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is enhanced.

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

The P concentration decrease rate can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, the P concentration decrease 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 1 to 5%.

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

In the film adhesive, at least one surface thereof satisfies the above conditions of V ₁ , V ₂ and P concentration reduction rate, and both surfaces satisfy the above conditions of V ₁ , V ₂ and P concentration reduction rate. It is preferable to satisfy.
The single-layered film-like adhesive usually has no unevenness in the composition therein and has a high compositional uniformity. Therefore, there is no significant difference in the type and content of the components on both sides of the single-layer film adhesive, or even if they are observed, the effect brought by them is negligible. It is slight.
In the single-layer film adhesive, if at least one surface thereof satisfies the above conditions of V ₁ , V ₂ and P concentration reduction rate, any cross section in the film adhesive and the other surface Also, it can be determined that the above conditions of V ₁ , V ₂ and P concentration decrease rate are satisfied.

The film adhesive may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers are the same as each other. However, they may be different, and the combination of these plural layers is not particularly limited.

In addition, in the present specification, not only in the case of the film-like adhesive, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers may be the same”. May be different, or only a part of the layers may be the same", and "a plurality of layers are different from each other" means that "at least one of the constituent material and the thickness of each layer is mutually different". Means "different".

The thickness of the film adhesive is preferably 10 to 40 μm, and may be any of 10 to 35 μm, 10 to 30 μm, and 10 to 25 μm, or 13 to 40 μm and 16 to 40 μm. , And 19 to 40 μm, or 13 to 35 μm, 16 to 30 μm, and 19 to 25 μm. When the thickness of the film adhesive is not less than the above lower limit, the adhesive force of the film adhesive with respect to the object to be bonded becomes stronger. When the thickness of the film adhesive is equal to or less than the above upper limit, the linear transmittance of light (for example, light (400 to 800 nm)) of the film adhesive increases regardless of whether or not the film adhesive is heated.
Here, the "thickness of the film-like adhesive" means the thickness of the whole film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers means all the constituents of the film-like adhesive. Means the total thickness of the layers.

The film adhesive is preferably, for example, 90% or more of the linear transmittance of light (400 to 800 nm) before heating and 85% or more of the linear transmittance of light (400 to 800 nm) after heating. And the film adhesive has a thickness of 10 to 40 μm.

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

The film adhesive is preferably, for example, one or two selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). The thing containing the above is mentioned.

<< adhesive composition >>
The film adhesive is one or two selected from the group consisting of its constituent materials (for example, an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). It can be formed using an adhesive composition containing the above). For example, the film-shaped adhesive can be formed at a desired site by applying the adhesive composition to the surface on which the film-shaped adhesive is to be formed and drying it as necessary.
The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film adhesive. In addition, in the present specification, “normal temperature” means a temperature at which it is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.

The coating of the adhesive composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.

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

<Acrylic resin (a)>
The acrylic resin (a) is a component that can be regarded as formed by a polymerization reaction of one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, and derivatives thereof. is there.
In the present specification, the “derivative” means one having a structure in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified. Here, the "group" includes not only an atomic group formed by combining a plurality of atoms but also one atom.
The acrylic resin (a) is a resin component for imparting film-forming properties and flexibility to the film-like adhesive and improving the adhesiveness (sticking property) to an object to be adhered such as the chip.

In this specification, “(meth)acrylic acid” is a concept that 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 adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..

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, and more preferably 100,000 to 15,000,000. When the weight average molecular weight of the acrylic resin (a) is within such a range, it becomes easy to adjust the adhesive force between the film adhesive and the adherend within a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin (a) is not less than the lower limit value, the shape stability of the film adhesive (stability during storage) is improved. Further, when the weight average molecular weight of the acrylic resin (a) is not more than the upper limit value, the film-like adhesive easily follows the uneven surface of the adherend, so that the adhesive between the adherend and the film-like adhesive becomes Therefore, the generation of voids is further suppressed.
In addition, in this specification, a "weight average molecular weight" is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin (a) is preferably −60 to 70° C., more preferably −30 to 50° C. When the Tg of the acrylic resin (a) is at least the lower limit value, the adhesive force between the film adhesive and the adherend is suppressed, and for example, the film adhesive is provided at the time of pickup. It becomes easier to separate the chip from the dicing sheet described later. When the Tg of the acrylic resin (a) is not more than the above upper limit value, the adhesive force between the film adhesive and the adherend is improved.

Examples of the (meth)acrylic acid ester that constitutes the acrylic resin (a) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth) Decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl acrylate), (meth ) Pentadecyl acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. A (meth)acrylic acid alkyl ester whose group has a chain structure having 1 to 18 carbon atoms;
(Meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylic acid and dicyclopentanyl (meth)acrylic acid;
Aralkyl esters of (meth)acrylic acid such as benzyl (meth)acrylate;
(Meth)acrylic acid cycloalkenyl ester such as (meth)acrylic acid dicyclopentenyl ester;
(Meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl ester;
(Meth)acrylic acid imide;
Glycidyl group-containing (meth)acrylic acid ester such as glycidyl (meth)acrylate;
Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate;
Examples include substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylic acid. Here, the “substituted amino group” means a group having a structure in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

The acrylic resin (a) is, for example, one or two kinds selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. in addition to the (meth)acrylic acid ester. It may be a resin obtained by copolymerizing the above monomers.

The monomer constituting the acrylic resin (a) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The acrylic resin (a) may have a functional group capable of binding to other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a carboxy group and an isocyanate group, in addition to the above-mentioned hydroxyl group. These functional groups including the hydroxyl group of the acrylic resin (a) may be bonded to other compounds via a crosslinking agent (f) described later, or other compounds may be bonded without the crosslinking agent (f). May be directly combined with. When the acrylic resin (a) is bonded to another compound by the functional group, the reliability of the package obtained by using the film adhesive tends to be improved.

Preferred examples of the acrylic resin (a) include those having a functional group capable of binding to the crosslinking agent (f) described later.

In the adhesive composition, the ratio of the content of the acrylic resin (a) to the total content of all components other than the solvent (that is, in the film adhesive, based on the total mass of the film adhesive, the acrylic resin ( The content ratio of a) is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, further preferably 20 to 65% by mass, for example, 30 to 65% by mass. It may be% by mass. When the ratio is at least the lower limit value, the structure of the film adhesive will be more stable. When the ratio is less than or equal to the upper limit value, it becomes easy to increase the amount of the components other than the acrylic resin (a) such as the epoxy compound (b1) and the phosphorus-based antioxidant (z), and thus the acrylic-based resin The effect of using a component other than the resin (a) can be more easily obtained.

<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 compounds, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and triazine type alicyclic epoxy compound can be mentioned.

As the epoxy compound (b1), an epoxy compound having an unsaturated hydrocarbon group may be used. The epoxy compound having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin (a) than the epoxy compound having no unsaturated hydrocarbon group. Therefore, by using the epoxy compound (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film adhesive is improved.

Examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include compounds having a structure in which a part of the epoxy groups of a polyfunctional epoxy compound is converted to a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition-reacting (meth)acrylic acid or its derivative with an epoxy group.

Moreover, as the epoxy compound (b1) having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy compound can be mentioned.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth) Examples thereof include an acrylamide group, and an acryloyl group is preferable.

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

The epoxy compound (b1) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The epoxy compound (b1) is preferably an aliphatic compound. That is, the film adhesive preferably contains an aliphatic epoxy compound.
In the present specification, the "aliphatic compound" means a compound having an aliphatic group and not an aromatic group. Further, the “aliphatic group” includes a chain aliphatic group and an aliphatic cyclic group (alias: alicyclic group). Further, the “aromatic group” includes an aromatic hydrocarbon group and an aromatic heterocyclic group.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the epoxy compound (b1), the effect of suppressing coloration after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.

The epoxy compound (b1) is selected from the group consisting of 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. It is preferable not to have one kind or two or more kinds.
Coloring after heating (for example, heating at 260° C.) of the film adhesive by containing the epoxy compound (b1) having no bond or group as the epoxy compound (b1) in the adhesive composition and the film adhesive. The effect of suppressing the above is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.

The epoxy compound (b1) is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of That is, the film adhesive contains an aliphatic epoxy compound which does not have one kind or two or more kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms and a cyano group. It is preferable.
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the epoxy compound (b1), heating the film adhesive (for example, heating at 260° C.) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), the above coloring The effect of suppressing is significantly increased.

In the adhesive composition and the film 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 any of 5 to 200 parts by mass, 5 to 150 parts by mass, 5 to 110 parts by mass, and 5 to 100 parts by mass. When the content of the epoxy compound (b1) is in such a range, it becomes easier to adjust the adhesive force between the film adhesive and the resin film or the dicing sheet described below.

<Phosphoric antioxidant (z)>
Since the film adhesive contains the phosphorus-based antioxidant (z), coloring before and after heating is further suppressed.
The phosphorus-based antioxidant (z) is not particularly limited as long as it has a phosphorus atom as its constituent atom and has an antioxidant action.
Examples of the phosphorus-based antioxidant (z) include compounds in which the oxidation number of phosphorus is 3.

The phosphorus antioxidant (z) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily set. You can choose.

The phosphorus-based antioxidant (z) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the phosphorus-based antioxidant (z), coloring of the film adhesive after heating (for example, heating at 260° C.) The inhibitory effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described inhibitory effect of coloring is significantly enhanced.

The phosphorus-based antioxidant (z) is a group consisting of 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. It is preferable not to have one or more selected from
When the adhesive composition and the film adhesive contain a phosphorus-based antioxidant (z) that does not have these bonds or groups, heating of the film adhesive (for example, heating at 260° C.) After that, the effect of suppressing the coloring becomes higher, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-mentioned effect of suppressing coloration becomes remarkable. Get higher

The phosphorus-based antioxidant (z) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡). It is preferable not to have one or more selected from the group consisting of N).
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the phosphorus-based antioxidant (z), heating of the film adhesive (for example, at 260° C. The effect of suppressing coloring after heating is further increased, and by containing only an aliphatic compound having no such bond or group (in other words, not containing an aliphatic compound having these bond or group), The effect of suppressing the above coloring is significantly enhanced.

The phosphorus-based antioxidant (z) is preferably a phosphite ester because it stably exhibits an antioxidant action.
Among them, the phosphorus-based antioxidant (z) is more preferably an aliphatic phosphite ester, and further preferably an aliphatic phosphite trialkyl ester.
That is, the film adhesive, as an antioxidant, preferably contains a phosphite ester, more preferably contains an aliphatic phosphite ester, an aliphatic phosphite trialkyl ester It is more preferable to contain.

Examples of the 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 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), tris (tridecyl) phosphite ((C ₁₃ H ₂₇ O) ₃ P), tristearyl phosphite ((C ₁₈ H ₃₇ O) ₃ P), bis(decyl)pentaerythritol diphosphite (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 Fight _{_{_{_{(C 18 H 37 OP (OCH}}}} 2) 2 C (CH 2 O) 2 POC 18 H 37), hydrogenated bisphenol A- pentaerythritol diphosphite polymer (formula _{_{"- (OC 6 H 12 C (}} CH 3) 2 C ₆ H ₁₂ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ P)-” and other polymers).

In the adhesive composition, the ratio of the content of the phosphorus-based antioxidant (z) with respect to the total content of all components other than the solvent (that is, in the film-like adhesive, relative to the total mass of the film-like adhesive, The ratio of the content of the system antioxidant (z)) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.3 to 1.5% by mass. % Is more preferable. When the ratio is at least the lower limit value, the effect of using the phosphorus-based antioxidant (z) can be more remarkably obtained. When the ratio is not more than the upper limit value, excessive use of the phosphorus-based antioxidant (z) is suppressed.

In order to improve various physical properties of the film adhesive, any one of these may be used in addition to the acrylic resin (a), the epoxy compound (b1), and the phosphorus antioxidant (z) in order to improve various physical properties. It may also contain other components that do not correspond to the above.
Other components contained in the film adhesive include, for example, phenol resin (b2), curing accelerator (c), filler (d), coupling agent (e), cross-linking agent (f), energy ray. Curing resin (g), photopolymerization initiator (h), antioxidant (y) other than phosphorus-based antioxidant (z) (in the present specification, abbreviated as "other antioxidant (y)") Thermoplastic resin (x) other than acrylic resin (a) (in the present specification, may be abbreviated as "thermoplastic resin (x)"), general-purpose additive (i), etc. Are listed.

<Phenolic resin (b2)>
The phenol resin (b2) functions as a thermosetting agent for the epoxy compound (b1).
In the present embodiment, when the epoxy compound (b1) and the phenol resin (b2) are used together, these combinations function as an epoxy thermosetting resin. In the present embodiment, such an epoxy thermosetting resin may be referred to as "epoxy thermosetting resin (b)".

The phenol resin (b2) may be one having two or more phenolic hydroxyl groups in one molecule as a functional group capable of reacting with an epoxy group.

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

The phenol resin (b2) may have an unsaturated hydrocarbon group.
Examples of the other phenolic resin (b2) having an unsaturated hydrocarbon group include, for example, a compound having a structure in which a part of hydroxyl groups of the phenolic resin is replaced with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenolic resin. Examples thereof include compounds having a structure in which a group having an unsaturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the phenol resin (b2) is the same as the unsaturated hydrocarbon group in the epoxy compound having an unsaturated hydrocarbon group described above.

The phenolic resin (b2) is preferably one having a high softening point or glass transition temperature because it is easy to adjust the adhesive force of the film adhesive.

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

The phenol resin (b2) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.

When the phenol resin (b2) is used, in the adhesive composition, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent (that is, the film adhesive in the film adhesive The ratio of the content of the phenol resin (b2) with respect to the total mass) is not particularly limited, but is preferably 10% by mass or less, more preferably 7.5% by mass or less, and 5% by mass or less. Is more preferable. When the ratio is less than or equal to the upper limit value, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) becomes higher.
That is, as one preferable example of the film adhesive containing the phenol resin (b2), the ratio of the content of the phenol resin (b2) to the total mass of the film adhesive in the film adhesive is The content is 10% by mass or less.

When the phenol resin (b2) is used, in the adhesive composition, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent (that is, the film adhesive in the film adhesive The lower limit value of the ratio of the content of the phenol resin (b2) to the total mass of is not particularly limited.
For example, the above ratio is preferably 0.5% by mass or more from the viewpoint that the effect of using the phenol resin (b2) can be more remarkably obtained.

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

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

<Curing accelerator (c)>
The curing accelerator (c) is a component for controlling the curing rate of the adhesive composition and the film adhesive.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. (one or more hydrogen atoms are other than hydrogen atoms) Substituted with a group of), organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, triphenylphosphine A tetraphenylboron salt such as tetraphenylborate; an inclusion compound having the above-mentioned imidazole as a guest compound, and the like.

The curing accelerator (c) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected. ..

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film adhesive is 100 parts by mass of the total content of the epoxy compound (b1) and the phenol resin (b2). On the other hand, it is preferably 0.01 to 7 parts by mass, and more preferably 0.1 to 4 parts by mass. When the content of the curing accelerator (c) is equal to or more than the lower limit value, the effect of using the curing accelerator (c) can be more remarkably obtained. When the content of the curing accelerator (c) is less than or equal to the upper limit value, for example, the highly polar curing accelerator (c) forms a film with the adherend in a film adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the bonding interface side is enhanced, and the reliability of the package obtained by using the film adhesive is further improved. 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).

<Filler (d)>
Since the film adhesive contains the filler (d), the coefficient of thermal expansion thereof can be easily adjusted. By optimizing the coefficient of thermal expansion for the object to which the film adhesive is attached, the film adhesive The reliability of the package obtained by using the adhesive tape is further improved. In addition, by containing the filler (d) in the film adhesive, it is possible to reduce the moisture absorption rate of the cured product of the film adhesive or to improve the heat dissipation.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or a surface modified product thereof.

The average particle size of the filler (d) is not particularly limited, but is preferably 10 to 100 nm, more preferably 10 to 80 nm, and further preferably 10 to 60 nm. When the average particle diameter of the filler (d) is not more than the upper limit value, turbidity of the film adhesive is highly suppressed, and the straight line of the film adhesive before heating with light (400 to 800 nm) The transmittance and the linear transmittance after heating are improved, and as a result, the image recognizability of the film adhesive before and after heating becomes higher. When the average particle size of the filler (d) is not less than the lower limit value, the effect of using the filler (d) can be more remarkably obtained.
In the present specification, the “average particle diameter” means the value of the particle diameter (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. ..

The filler (d) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

When the filler (d) is used, in the adhesive composition, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, in the film adhesive, The ratio of the content of the filler (d) to the total mass) is preferably 7.5 to 50% by mass, more preferably 10 to 45% by mass, and 12.5 to 40% by mass. It is particularly preferable that When the content of the filler (d) is in such a range, it becomes easier to adjust the thermal expansion coefficient.

<Coupling agent (e)>
By containing the coupling agent (e), the film adhesive has improved adhesiveness and adhesion to the adherend. Further, since the film adhesive contains the coupling agent (e), the cured product has improved water resistance without impairing 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 of the acrylic resin (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. Is more preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, and 2-glycidyloxymethyldiethoxysilane. (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-amino Ethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomer type or polymer type organosiloxane, and the like. ..

The coupling agent (e) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the coupling agent (e), the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) Is further increased, and by containing only an aliphatic compound (in other words, not containing an aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.

The coupling agent (e) is selected from the group consisting of 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. It is preferable not to have one kind or two or more kinds.
Since the adhesive composition and the film adhesive contain the coupling agent (e) having no such bond or group, after the film adhesive is heated (for example, heated at 260° C.) The effect of suppressing coloration is higher, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced. ..

The coupling agent (e) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the coupling agent (e), the film adhesive is heated (for example, heated at 260° C.). ) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), The effect of suppressing coloring is significantly enhanced.

Among the coupling agents (e), more specific examples of the aliphatic compound (aliphatic coupling agent) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and the like. 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, oligomer type or polymer type organosiloxane and the like.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film adhesive is the total amount of the acrylic resin (a) and the epoxy thermosetting resin (b). The content is 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 with respect to 100 parts by mass. When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the film adhesive to the adherend is improved. The effect of using the coupling agent (e) can be more remarkably obtained. When the content of the coupling agent (e) is equal to or less than the upper limit value, the generation of outgas is further suppressed.

<Crosslinking agent (f)>
When an acrylic resin (a) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group capable of binding to the above-mentioned other compounds is used, an adhesive composition The material and the film-like adhesive may contain a cross-linking agent (f) for binding the functional group to another compound to cross-link it. By crosslinking with the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.

As the cross-linking agent (f), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), etc. Are listed.

As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound etc." Abbreviated); trimers of the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds with polyol compounds Etc. The "adduct" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil or the like. Means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct, xylylene diisocyanate adduct of trimethylol propane as described below, isophorone diisocyanate adduct of trimethylol propane, tolylene diisocyanate adduct of trimethylol propane, hexamethylene diisocyanate adduct of trimethylol propane. Etc. The term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

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

Examples of the organic polyvalent imine compound include N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinyl propionate, N,N′-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine and the like can be mentioned.

When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-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, a cross-linking structure can be easily formed on the film adhesive by the reaction between the cross-linking agent (f) and the acrylic resin (a). Can be introduced to.

The cross-linking agent (f) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the cross-linking agent (f), an effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.

The cross-linking agent (f) is selected from the group consisting of 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. It is preferable not to have one kind or two or more kinds.
Coloring after heating (for example, heating at 260° C.) of the film adhesive by containing the adhesive composition and the film adhesive which do not have these bonds or groups as the crosslinking agent (f). The effect of suppressing the above is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.

The cross-linking agent (f) is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the crosslinking agent (f), heating of the film adhesive (for example, heating at 260° C.) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), the above coloring The effect of suppressing is significantly increased.

The cross-linking agent (f) is an aliphatic organic polyvalent isocyanate compound (aliphatic polyvalent isocyanate cross-linking agent) in that it has a particularly high effect of suppressing the above coloring and has excellent properties as a cross-linking agent. Is preferred.
Specific examples of the aliphatic polyvalent isocyanate crosslinking agent include, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4′- Diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compound obtained by adding one or more of tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate to all or part of hydroxyl groups of polyols such as trimethylolpropane. Lysine diisocyanate and the like.

When the film adhesive is focused on the acrylic resin (a) and the cross-linking agent (f), the cross-linking agent (f) has a particularly high effect of suppressing the above-mentioned coloring and has excellent properties. It is preferable to contain the aliphatic polyvalent isocyanate cross-linking agent and to contain, as the acrylic resin (a), a resin having a functional group capable of binding to the aliphatic polyvalent isocyanate cross-linking agent.

The cross-linking agent (f) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition and the film adhesive is 0.3 to 100 parts by mass with respect to 100 parts by mass of the acrylic resin (a). The amount is preferably 12 parts by mass, more preferably 0.3 to 3.5 parts by mass, still more preferably 0.3 to 2 parts by mass. When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) can be obtained more significantly. Further, when the content of the crosslinking agent (f) is not more than the upper limit value, excessive use of the crosslinking agent (f) is suppressed.

<Energy ray curable resin (g)>
The adhesive composition and the film adhesive may contain an energy ray curable resin (g). Since the film adhesive contains the energy ray curable resin (g), its characteristics can be changed by irradiation with energy rays.

In the present specification, the “energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof 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 or an LED lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present specification, “energy ray curable” means a property of being cured by irradiation with energy rays, and “non-energy ray curable” means a property of not being cured by irradiation of energy rays. To do.

The energy ray-curable resin (g) is obtained by polymerizing (curing) 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 acrylate compounds having a (meth)acryloyl group are preferable.

Examples of the acrylate compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta( (Meth)acrylate containing a chain aliphatic skeleton such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; Cycloaliphatic skeleton-containing (meth)acrylate such as cyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; urethane (meth)acrylate oligomer An epoxy-modified (meth)acrylate; a polyether (meth)acrylate other than the polyalkylene glycol (meth)acrylate; an itaconic acid oligomer and the like.

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 kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.

When the energy ray-curable resin (g) is used, the ratio of the content of the energy ray-curable resin (g) to the total weight of the adhesive composition in the adhesive composition is 1 to 95% by mass. Is more preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.

<Photopolymerization initiator (h)>
When the adhesive composition and the film adhesive contain the energy ray-curable resin (g), a photopolymerization initiator (h) is added in order to efficiently proceed the polymerization reaction of the energy ray-curable resin (g). It may be contained.

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, benzoin dimethyl ketal, and other benzoin compounds; acetophenone; Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol such as 1-hydroxycyclohexyl phenyl ketone Compounds; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Examples of the photopolymerization initiator (h) also include photosensitizers such as amines.

The photopolymerization initiator (h) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the photopolymerization initiator (h), suppression of coloring after heating the film adhesive (for example, heating at 260° C.) The effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.

The photopolymerization initiator (h) is selected from the group consisting of 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. It is preferable not to have one or more selected.
After the adhesive composition and the film adhesive contain the photopolymerization initiator (h) having no such bond or group, the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and by containing only those having no such bond or group (in other words, not containing those having these bonds or groups), the above-described effect of suppressing coloration is remarkably high. Become.

The photopolymerization initiator (h) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the photopolymerization initiator (h), the film adhesive is heated (for example, at 260° C.). The effect of suppressing coloring after heating is further enhanced, and only an aliphatic compound having no such bond or group is contained (in other words, an aliphatic compound having these bond or group is not contained). The effect of suppressing the coloring is markedly increased.

Among the photopolymerization initiators (h), more specifically, as the aliphatic compound (aliphatic photopolymerization initiator), for example, an acylphosphine oxide compound; a sulfide compound such as tetramethylthiuram monosulfide; an azo Examples thereof include azo compounds such as bisisobutyronitrile; peroxide compounds; diketone compounds such as diacetyl; photosensitizers such as amines.
Among the compounds exemplified here, the compounds are aliphatic compounds, and have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). Examples of the photopolymerization initiator (h) that does not have one or more selected from the group consisting of include, for example, compounds other than azobisisobutyronitrile.

The photopolymerization initiator (h) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrarily selected. it can.

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

<Other antioxidants (y)>
The adhesive composition and the film adhesive may contain the other antioxidant (y) as long as the effect of the present invention is not impaired.
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 an organic compound or an inorganic compound.

The other antioxidant (y) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio may be arbitrarily set. You can choose.

When the other antioxidant (y) is used, the content of the other antioxidant (y) in the adhesive composition and the film adhesive is 100 parts by mass of the phosphorus-based antioxidant (z). On the other hand, it is preferably 10 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 not more than the upper limit value, the coloring of the film adhesive before and after heating is further suppressed.

The adhesive composition and the film adhesive preferably do not contain any other antioxidant (y).

<Thermoplastic resin (x)>
The adhesive composition and the film adhesive may contain the thermoplastic resin (x) as long as the effects of the present invention are not impaired.
By using the thermoplastic resin (x), for example, at the time of pickup, it becomes easier to separate the chip provided with the film adhesive from a dicing sheet described later, or a film is formed on an uneven surface of an adherend. The linear adhesive may easily follow, and the occurrence of voids and the like between the adherend and the film adhesive may be further suppressed.

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 to 150° C., more preferably −20 to 120° C.

The thermoplastic resin (x) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..

When the thermoplastic resin (x) is used, in the adhesive composition and the film adhesive, the content of the thermoplastic resin (x) is 10 parts by mass based on 100 parts by mass of the acrylic resin (a). It is preferably not more than 5 parts by mass, more preferably not more than 5 parts by mass, still more preferably not more than 1 part by mass. When the content of the thermoplastic resin (x) is equal to or less than the upper limit value, the effect of using the acrylic resin (a) can be more significantly obtained.

It is preferable that the adhesive composition and the film adhesive do not contain the thermoplastic resin (x).

<General-purpose additive (i)>
The general-purpose additive (i) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferable general-purpose additives (I) include plasticizers, antistatic agents, colorants (dyes and pigments), gettering agents, and the like.

When the general-purpose additive (i) is an organic compound, such general-purpose additive (i) (abbreviated as “organic general-purpose additive” in the present specification) is preferably an aliphatic compound. ..
Since the adhesive composition and the film adhesive contain an aliphatic compound as an organic general-purpose additive, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is further improved. The effect of suppressing the above-mentioned coloring is significantly increased by containing only the aliphatic compound (in other words, not containing the aromatic compound).

The organic general-purpose additive is selected from the group consisting of 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. It is preferable not to have one kind or two or more kinds.
Since the adhesive composition and the film adhesive contain the organic general-purpose additive that does not have these bonds or groups, coloring of the film adhesive after heating (for example, heating at 260° C.) The suppression effect is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.

The organic general-purpose additive is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group.
After the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as an organic general-purpose additive, the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and only the aliphatic compound having no such bond or group is contained (in other words, the aliphatic compound having these bond or group is not contained), the above-mentioned coloring The suppression effect is remarkably enhanced.

The general-purpose additive (i) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
The content of the general-purpose additive (i) in the adhesive composition and the film 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 good handleability.
The solvent is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the adhesive composition may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof may be arbitrarily selected.

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

<<Production Method of Adhesive Composition>>
The adhesive composition can be obtained by blending each component for constituting the adhesive composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by preliminarily diluting this compounding ingredient by mixing the solvent with any compounding ingredient other than the solvent, or diluting any compounding ingredient other than the solvent beforehand. Alternatively, the solvent may be used as a mixture with these compounding ingredients.

The method of mixing the components at the time of blending is not particularly limited, and a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by adding ultrasonic waves It may be selected appropriately.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

FIG. 1 is a sectional view schematically showing a film adhesive according to one embodiment of the present invention. It should be noted that, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there may be a case where an essential part is enlarged, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The film adhesive 13 shown here is provided with a first release film 151 on one surface (sometimes referred to as “first surface” in the present specification) 13a thereof, and the first surface 13a is The second release film 152 is provided on the other surface (may be referred to as “second surface” in this specification) 13b on the opposite side. Here, reference numeral 109 is given to the laminated sheet configured by laminating the first release film 151, the film adhesive 13 and the second release film 152 in this order in this order in the thickness direction. ing.
Such a film-like adhesive 13 (laminated sheet 109) is suitable for storage as a roll, 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 conditions of V ₁ , V ₂ and P concentration reduction rate described above.
The thickness of the film adhesive 13 is preferably 10 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 ones.
The first release film 151 and the second release film 152 may be the same as each other, or different from each other, such as different release forces required when releasing from the film adhesive 13. Good.

In the film adhesive 13 shown in FIG. 1, one of the first peeling film 151 and the second peeling film 152 is removed, and the exposed surface thus formed becomes the sticking surface to the sticking target. Here, as the pasting target, for example, the chip and the like can be mentioned. In the case of the chip, the surface on which the film adhesive 13 is attached becomes the circuit forming surface.

As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
One surface of the film adhesive before heating at 260° C. is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , the V ₁ is measured, and Of the film adhesive after being heated for a minute, the surface on which the V ₁ was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, the V ₁ was 0.1 atomic. % Or more, the reduction rate of the phosphorus concentration calculated from V ₁ and V ₂ is 25% or less,
Using the film adhesive having a size of 2 mm×2 mm and a thickness of 20 μm, the copper plate having a size of 30 mm×30 mm and a thickness of 300 μm, and a silicon chip, the film adhesive , A test piece in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate, and the side surfaces of the film adhesive and the silicon chip are aligned. Under a temperature condition of 23° C., in the aligned side surface in the test piece, for both the film adhesive and the silicon chip, the other of the film adhesive A force is applied in a direction parallel to the surface at a speed of 200 μm/s, and the maximum value of the force applied until the film adhesive is broken is defined as the shear strength (N /2 mm□), the shear strength is 20 N/2 mm□ or more.

As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
One surface of the film adhesive before heating at 260° C. is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , the V ₁ is measured, and Of the film adhesive after being heated for a minute, the surface on which the V ₁ was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, the V ₁ was 0.1 atomic. % Or more, the reduction rate of the phosphorus concentration calculated from V ₁ and V ₂ is 25% or less,
The film adhesive contains a phosphorus-based antioxidant (z),
The phosphorus-based antioxidant (z) is an aliphatic compound, and is one selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Or the thing which does not have 2 or more types is mentioned.

As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
One surface of the film adhesive before heating at 260° C. is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , the V ₁ is measured, and Of the film adhesive after being heated for a minute, the surface on which the V ₁ was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, the V ₁ was 0.1 atomic. % Or more, the reduction rate of the phosphorus concentration calculated from V ₁ and V ₂ is 25% or less,
The film adhesive contains an epoxy compound (b1),
The epoxy compound (b1) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above.

As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
One surface of the film adhesive before heating at 260° C. is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , the V ₁ is measured, and Of the film adhesive after being heated for a minute, the surface on which the V ₁ was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, the V ₁ was 0.1 atomic. % Or more, the reduction rate of the phosphorus concentration calculated from V ₁ and V ₂ is 25% or less,
The film adhesive contains an acrylic resin (a) and a crosslinking agent (f),
The acrylic resin (a) has a functional group capable of binding to the crosslinking agent (f),
The cross-linking agent (f) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above are included.

As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
One surface of the film adhesive before heating at 260° C. is analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V ₁ , the V ₁ is measured, and Of the film adhesive after being heated for a minute, the surface on which the V ₁ was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, the V ₁ was 0.1 atomic. % Or more, the reduction rate of the phosphorus concentration calculated from V ₁ and V ₂ is 25% or less,
The film adhesive contains a filler (d),
The filler (d) has an average particle diameter of 10 to 100 nm.

◇ Laminated sheet and composite sheet A laminated sheet according to an embodiment of the present invention is configured to include the film adhesive and a resin film provided on one surface of the film adhesive. ..
A composite sheet according to an embodiment of the present invention includes the film adhesive and a dicing sheet provided on one surface of the film adhesive, and the dicing sheet is a base material. And a pressure-sensitive adhesive layer provided on one surface of the base material, and the pressure-sensitive adhesive layer is disposed between the base material and the film adhesive.

The laminated sheet, as long as the resin film is provided on at least one side of the film-like adhesive, the resin film may be provided only on one side, or on both sides (that is, the one side A resin film may be provided on the surface of (1) and on the other surface on the opposite side.

When the resin film is provided on both sides of the film 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 resin film may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other. The combination of these plural layers is not particularly limited.

The resin film may be a sheet containing only resin as a constituent material, or may be a sheet containing resin and other components as constituent materials and resin as a major constituent material.

Examples of the resin that is a constituent material of the resin film include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene. Polyolefin other than polyethylene such as norbornene resin; ethylene such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer -Based copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene; Polycycloolefins; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyetherketone and the like. To be
Examples of the resin also include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more of the resins exemplified so far; modification of an ionomer or the like using one or more of the resins exemplified so far Resins are also included.

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

The release film includes, for example, a multi-layered film including a resin layer and a release treatment layer provided on one surface of the resin layer.

The release film can be manufactured by subjecting one surface of the resin layer to a release treatment.
The resin layer can be prepared by molding or coating a resin composition containing a resin and drying it as necessary.

The resin that is a constituent material of the resin layer is the same as the resin that is a constituent material of the resin film.
The peeling treatment of the resin layer can be performed with various known peeling agents such as alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents.
The release agent is preferably an alkyd-based, silicone-based or fluorine-based release agent in terms of heat resistance.

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

As a laminated sheet configured by providing the release film as a resin film on both surfaces of the film adhesive, for example, the laminated sheet 109 shown in FIG. 1 can be cited.

As a laminated sheet configured by providing a resin film only on one surface of the film adhesive, for example, the laminated sheet 108 shown in FIG. 2 can be cited.
2 and subsequent figures, the same components as those shown in the already described figures are designated by the same reference numerals as those in the already described figures, and detailed description thereof will be omitted.

The laminated sheet 108 shown here is configured by including the resin film 19 on the first surface 13 a of the film adhesive 13.
The resin film 19 is as described above, and may be a release film (for example, the first release film 151 or the second release film 152 in FIG. 1) or a base material described later.

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

The laminated sheet of the present embodiment is not limited to the one shown in FIG. 2, and a configuration in which a part of the configuration shown in FIG. 2 is changed or deleted, or is described so far, within a range that does not impair the effects of the present invention. Other configurations may be added to the above configuration. More specifically, it is as follows.

For example, the laminated sheet of the present embodiment may have nothing on the second surface of the film adhesive, but the laminated sheet may be provided on the second surface of the film adhesive in a region near the peripheral portion. A jig adhesive layer for fixing to a jig such as a ring frame may be provided.
The adhesive layer for a jig may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet as a core material. It may be one.

For example, the surface area of the film-like adhesive and the resin film may be the same or almost the same when the laminated sheet is viewed from above the film-like adhesive side or the resin film side and viewed in a plan view. In the laminated sheet of the embodiment, the surface area of the film adhesive may be smaller than the surface area of the resin film, and a partial region of the resin film may be exposed. In that case, for example, at least the peripheral portion in the width direction of the resin film may be exposed without being covered with the film adhesive. Such a laminated sheet may be provided with the jig adhesive layer on the exposed surface of the resin film.

FIG. 3 is a sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention.
The composite sheet 101 shown here includes a film adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film adhesive 13, and the dicing sheet 10 includes a base material 11 and The pressure-sensitive adhesive layer 12 provided on one surface (sometimes referred to as “first surface” in the present specification) 11a of the base material 11, and the pressure-sensitive adhesive layer 12 is a base material. 11 and the film adhesive 13 are arranged and configured.
In other words, the composite sheet 101 is configured by laminating the base material 11, the adhesive layer 12, and the film adhesive 13 in this order in the thickness direction thereof.
The surface 10 a of the dicing sheet 10 on the film adhesive 13 side (may be referred to as “first surface” in the present specification) is a surface opposite to the base material 11 side of the pressure-sensitive adhesive layer 12 (the book). In the specification, it may be referred to as a "first surface") 12a.

The composite sheet 101 further includes a release film 15 on the film adhesive 13.
In the composite sheet 101, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the film adhesive 13 is laminated on the entire surface or almost all of the first surface 12a of the pressure-sensitive adhesive layer 12 to form a film. The release film 15 is laminated on the entire surface or almost the entire surface of the first surface 13 a of the adhesive 13.

The dicing sheet 10 may be a known one.
The base material 11 and the pressure-sensitive adhesive layer 12 in the dicing sheet 10 will be sequentially described.

The base material 11 in the dicing sheet 10 has a sheet shape or a film shape, and examples of the constituent material thereof include various resins. Examples of the resin which is a constituent material of the dicing sheet 10 include the same resin as a constituent material of the resin film in the laminated sheet.

The resin constituting the base material may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

The thickness of the base material 11 is preferably 50 to 300 μm, more preferably 60 to 150 μm. When the thickness of the base material 11 is in such a range, the flexibility of the composite sheet 101 and the sticking property to the sticking target are further improved.
Here, the “thickness of the base material” means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all layers constituting the base material. means.

It is preferable that the base material 11 has a high thickness accuracy, that is, a material in which the thickness variation is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to form such a highly accurate base material include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Are listed.

The base material 11 contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst and a softening agent (plasticizer) in addition to the main constituent materials such as the resin. May be

The base material 11 may be transparent or opaque, and may be colored depending on the purpose, or another layer may be vapor-deposited.

The base material 11 has a roughening treatment such as a sand blasting treatment or a solvent treatment, a corona discharge treatment, an electron beam treatment, or the like in order to improve the adhesion with other layers (here, the pressure-sensitive adhesive layer 12) provided thereon. The surface may be subjected to irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, or the like.
Further, the base material 11 may have a surface subjected to a primer treatment.
Further, the base material 11 is an antistatic coating layer; a layer that prevents the base material 11 from adhering to another sheet and the base material 11 from adhering to the suction table when the composite sheets are stored in a stacked state. Etc. may be included.

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

The pressure-sensitive adhesive layer 12 in the dicing sheet 10 has a sheet shape or a film shape and contains a pressure-sensitive adhesive.
Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin, and acrylic resin is preferable. ..

In the present specification, "adhesive resin" includes both a resin having an adhesive property and a resin having an adhesive property. For example, the adhesive resin is not only the resin having adhesiveness itself, but also the resin that exhibits adhesiveness when used in combination with other components such as additives, and the adhesiveness due to the presence of a trigger such as heat or water. Resins and the like indicating are also included.

The pressure-sensitive adhesive layer 12 may be composed of one layer (single layer) or may be composed of two or more layers. When composed of a plurality of layers, these layers may be the same as each other. They may be different, and the combination of these plural layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer 12 is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the whole pressure-sensitive adhesive layer, for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

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

The pressure-sensitive adhesive layer 12 can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive composition can be applied to the surface on which the pressure-sensitive adhesive layer 12 is to be formed and, if necessary, dried to form the pressure-sensitive adhesive layer 12 at a desired site. In the pressure-sensitive adhesive composition, the content ratio of the components that do not vaporize at room temperature is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer 12. In the present specification, the “normal temperature” means a temperature at which it is not cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.

The coating of the adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater. Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.

When the pressure-sensitive adhesive layer 12 is provided on the base material 11, for example, the pressure-sensitive adhesive composition is applied on the base material 11 and dried as necessary to form the pressure-sensitive adhesive layer 12 on the base material 11. It may be laminated. When the pressure-sensitive adhesive layer 12 is provided on the base material 11, for example, the pressure-sensitive adhesive composition is applied on the release film and dried as necessary to form the pressure-sensitive adhesive layer 12 on the release film. Even if the pressure-sensitive adhesive layer 12 is laminated on the base material 11 by forming it and bonding the exposed surface of the pressure-sensitive adhesive layer 12 to one surface (here, the first surface 11 a) of the base material 11. Good. In this case, the release film may be removed at any timing during the manufacturing process or the use process of the composite sheet 101.

When the pressure-sensitive adhesive layer 12 is energy ray-curable, the energy ray-curable pressure-sensitive adhesive composition may be, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, referred to as “pressure-sensitive adhesive (I -1a)") and an energy ray-curable compound; and an unsaturated group in the side chain of the adhesive resin (I-1a). A pressure-sensitive adhesive composition (I-2) containing the introduced energy ray-curable pressure-sensitive adhesive resin (I-2a) (hereinafter, may be abbreviated as “adhesive resin (I-2a)”); Examples thereof include an adhesive composition (I-3) containing an adhesive resin (I-2a) and an energy ray-curable compound.

When the pressure-sensitive adhesive layer 12 is non-energy ray curable, the non-energy ray curable pressure sensitive adhesive composition is, for example, a pressure sensitive adhesive composition (I-4) containing the pressure sensitive adhesive resin (I-1a). Etc.

The release film 15 is similar to the first release film 151 or the second release film 152 shown in FIG.

Not limited to the case of the composite sheet 101, in the composite sheet of the present embodiment, the release film (for example, the release film 15 shown in FIG. 3) has any configuration, and the composite sheet of the present embodiment includes the release film. It may or may not be provided.

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

The composite sheet of the present embodiment is not limited to the one shown in FIG. 3, and a part of the configuration shown in FIG. 3 has been changed or deleted, or has been described so far, as long as the effect of the present invention is not impaired. Other configurations may be added to the above configuration. More specifically, it is as follows.

Up to this point, the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment may include a dicing sheet including only the base material. .. That is, the composite sheet comprises a base material and a film adhesive provided on one surface of the base material, and a pressure-sensitive adhesive layer is provided between the base material and the film adhesive. It may be configured without being arranged. An example of such a composite sheet is the laminated sheet 108 shown in FIG. 2 in which the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3).

So far, the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment includes an intermediate layer in addition to the base material and the pressure-sensitive adhesive layer. You may provide the comprised dicing sheet. As such a dicing sheet, for example, a base material, a pressure-sensitive adhesive layer provided on one surface of the base material, and a surface of the pressure-sensitive adhesive layer opposite to the base material side are provided. And an intermediate layer. When such a dicing sheet is used, an intermediate layer is arranged between the pressure-sensitive adhesive layer and the film adhesive in the composite sheet.

For example, the composite sheet of the present embodiment may include only the release film on the first surface of the film adhesive, but in the first surface of the film adhesive, in the region near the peripheral edge, A jig adhesive layer for fixing the composite sheet to a jig such as a ring frame may be provided.
The jig adhesive layer in this case is the same as that described above.

For example, the surface area of the film-like adhesive and the dicing sheet may be the same or almost the same when the composite sheet is viewed from above the film-like adhesive side or the dicing sheet side and viewed in a plane. In the composite sheet of the embodiment, the surface area of the film adhesive may be smaller than the surface area of the dicing sheet, and a partial area of the dicing sheet (for example, the pressure-sensitive adhesive layer) may be exposed. In that case, for example, at least the peripheral portion in the width direction of the dicing sheet may be exposed without being covered with the film adhesive. Such a composite sheet may include the jig adhesive layer on the exposed surface of the dicing sheet.

Up to this point, a substrate, a pressure-sensitive adhesive layer, an intermediate layer, a film adhesive, a jig adhesive layer and a release film have been shown as constituting the composite sheet, but the composite sheet of the present embodiment is Other layers that do not correspond to any of these may be provided.
When the composite sheet includes the other layer, the arrangement position 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.

◇ Usage of laminated sheet (film adhesive) <<<Laminate and its manufacturing method>>
The film adhesive in the laminated sheet of the present embodiment can be used as a film for adhering the light-transmitting cover to the circuit forming surface of a chip such as a sensor.
More specifically, by using the film adhesive, the chip, the film adhesive provided on the circuit forming surface of the chip, and the surface of the film adhesive opposite to the chip side. It is possible to manufacture a laminated body including the light-transmitting cover provided above. In the laminate, one or both of the chip-side surface of the film adhesive and the light-transmissive cover-side surface satisfy the above-described conditions of V ₁ , V ₂ and P concentration reduction rate, It is preferable that both satisfy the conditions of the above-described V ₁ , V ₂ and P concentration reduction rates.

FIG. 4 is a sectional view schematically showing an example of the laminated body.
The laminated body 801 shown here is the chip 8, the film adhesive 13 provided on the circuit forming surface 8a of the chip 8, and the surface of the film adhesive 13 opposite to the chip 8 side (first surface). And a light-transmitting cover 7 provided on 13a.

In the laminated body 801, the surfaces of the chip 8 and the film adhesive 13 that face each other, that is, the circuit forming surface 8a of the chip 8 and the surface (second surface) 13b of the film adhesive 13 on the chip 8 side are formed. , Are in direct contact. In addition, the film adhesive 13 and the light transmissive cover 7 face each other, that is, the first surface 13a of the film adhesive 13 and the film adhesive 13 side of the light transmissive cover 7 (the book In the specification, it may be referred to as the "second surface") 7b, and is in direct contact.
As described above, in the laminated body 801, the chip 8, the film adhesive 13, and the light transmissive cover 7 are laminated in this order in the thickness direction thereof, and the circuit forming surface 8a of the chip 8 is in the film form. It is arranged and configured on the adhesive 13 side.

The film adhesive 13 in the laminated body 801 is, for example, the laminated sheet 109 shown in FIG. 1 from which the first release film 151 and the second release film 152 are removed, or the laminated sheet 108 shown in FIG. The resin film 19 is removed.
In the laminated body 801, one or both 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 both of them are as described above. It is preferable that the conditions of V ₁ , V ₂ and P concentration reduction rate are satisfied.

Note that the circuit of the chip 8 is not shown in FIG. Reference numeral 7a indicates a surface of the light transmissive cover 7 opposite to the second surface 7b (may be referred to as "first surface" in the present specification).

The light transmissive cover 7 protects the circuit forming surface 8a of the chip 8 and makes the outside of the second surface 7b side visible from the outside of the first surface 7a side.
On the other hand, the film adhesive 13 has the above-mentioned light transmittance. Therefore, in the laminated body 801, the visual information existing on the circuit forming surface 8a of the chip 8 through the light transmissive cover 7 and the film adhesive 13 (through the light transmissive cover 7 and the film adhesive 13). However, it is visible.
Furthermore, as described above, the film adhesive 13 has high light transmittance before and after heating and is suppressed from being colored. Therefore, the laminated body 801 can visually recognize the visual information on the chip 8 stably and with high accuracy.

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

The laminated body using the film adhesive is not limited to that shown in FIG. 4, and a part of the configuration shown in FIG. 4 is changed or deleted within a range not impairing the effects of the present invention. Further, other configurations may be added to those described above.

In the laminated body, for example, one surface (second surface) of the film adhesive is attached to a circuit forming surface of the chip, and the other surface (first surface) of the film adhesive is optically transparent. It can be manufactured by laminating a flexible cover.

◇How to use composite sheet <<<Laminate and its manufacturing method>>
The composite sheet of this embodiment can be used in the same manner as in the case of known composite sheets.
FIG. 5: is sectional drawing for demonstrating an example of the usage method of the composite sheet of this embodiment typically. Here, the case where the composite sheet 101 shown in FIG. 3 is used is shown.

As shown here, the composite sheet 101 is used by removing the release film 15 and then attaching the first surface 13a of the film adhesive 13 to the circuit forming surface 8a of the chip 8.

After attaching the composite sheet 101 to the chip 8, for example, the chip 8 is diced into individual pieces, and the film adhesive 13 is cut along the outer periphery of the individual chips 8. At this time, the chip 8 can be divided into individual pieces and the film adhesive 13 can be cut by a known method. For example, these can be performed at the same time, or the chip 8 can be divided into individual pieces and then separated. The film adhesive 13 may be cut.

Next, the individual chips 8 are separated from the dicing sheet 10 together with the cut film adhesive 13 and picked up. When the pressure-sensitive adhesive layer 12 is energy ray-curable, the pressure-sensitive adhesive layer 12 is cured with energy rays to reduce the adhesive strength to the film adhesive 13 and then picked up to make the pickup easier. It can be carried out.

Next, the above-mentioned laminated body (for example, laminated body 801 shown in FIG. 4) can be manufactured by attaching a light-transmitting cover to the second surface of the film adhesive 13 after cutting and picking up.
In the laminate, one or both of the first surface and the second surface of the film-like adhesive satisfy the above conditions of V ₁ , V ₂ and P concentration reduction rate, and both of them are the above V ₁ , It is preferable to satisfy the conditions of the V ₂ and P concentration reduction rates.

Here, in this way, the film-like adhesive in the composite sheet is stuck to the chip, and after the chip is divided into pieces and the film-like adhesive is cut, a light-transmitting cover is attached to the cut film-like adhesive. Although the case of laminating is explained, the order of laminating the chip and the light-transmitting cover to the film adhesive may be reversed. That is, after sticking the first surface of the film-like adhesive to the second surface of the light-transmitting cover, the light-transmitting cover is diced into individual pieces, and the film-like adhesive is cut, and if necessary, After curing the pressure-sensitive adhesive layer with energy rays, the light-transmitting cover after separation into pieces is separated from the dicing sheet together with the film adhesive after cutting and picked up, and then the film bonding after cutting and picking up The laminated body (for example, the laminated body 801 shown in FIG. 4) can also be manufactured by bonding a chip to the first surface of the agent.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples described below.

<Manufacturing raw material for adhesive composition>
The raw materials used in the production of the adhesive compositions in the examples and comparative examples are shown below.

[Acrylic resin (a)]
(A)-1: An acrylic resin (weight average molecular weight 800,000, glass transition temperature 6° C.) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass).
(A)-2: An acrylic resin (weight average molecular weight 800,000, 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: Acryloyl group-added cresol novolac type epoxy resin (“CNA147” manufactured by Nippon Kayaku Co., epoxy equivalent 518 g/eq, number average molecular weight 2100, unsaturated group content and epoxy group content) Is equal to
(B1)-2: Hydrogenated bisphenol A type epoxy resin (“Epolite 4000” manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 310 to 340 g/eq)
[Phenolic resin (b2)]
(B2)-1: Aralkyl type phenolic resin (“HE100C-10” manufactured by Air Water Chemical Co., Ltd.)
[Curing accelerator (c)]
(C)-1: triphenylphosphine (manufactured by Kitako Chemical Co., Ltd.)
[Filler (d)]
(D)-1: Spherical silica modified with methacryl group ("YA050C-MJE" manufactured by Admatechs Co., Ltd., average particle diameter 50 nm)
(D)-2: Spherical silica modified with an epoxy group ("YA050C-MKK" manufactured by Admatex Co., average particle size 50 nm)
(D)-3: Silica filler modified with epoxy group (“SC2050MA” manufactured by Admatechs Co., Ltd., average particle diameter 500 nm)
[Crosslinking agent (f)]
(F)-1: Tolylene 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, Inc.)
[Phosphoric antioxidant (z)]
(Z)-1: Bis(decyl)pentaerythritol diphosphite (“JPE-10” manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite ester)

[Example 1]
<<Production of film adhesive>>
<Production of adhesive composition>
Acrylic resin (a)-1 (57.2 parts by mass), epoxy compound (b1)-1 (18 parts by mass), phenolic resin (b2)-1 (3 parts by mass), curing accelerator (c)-1 (0.5 parts by mass), filler (d)-1 (20 parts by mass), crosslinking agent (f)-1 (0.5 parts by mass) and phosphorus antioxidant (z)-1 (0.8). (Parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23° C. to obtain an adhesive composition in which the total concentration of all components other than methyl ethyl ketone was 32% by mass. In addition, the compounding amounts of the components other than the methyl ethyl ketone shown here are all compounding amounts of the target product containing no solvent component.

<Production of film adhesive>
A polyethylene terephthalate (PET) film has a release film (one side of which has been subjected to a release treatment by silicone treatment) (SP-PET381031 manufactured by Lintec Co., Ltd., thickness: 38 μm), and the above-mentioned release treatment is applied to the release-treated surface. The adhesive composition is applied and dried by heating at 100° C. for 2 minutes to form a film adhesive having a thickness of 20 μm, and the release film and the film adhesive are laminated in the thickness direction thereof. A structured adhesive sheet was obtained.

<<Evaluation of film adhesive>>
<Measurement of shear strength>
Using a tape mounter (“Adwill RAD2500 m/12” manufactured by Lintec Co., Ltd.), a dicing sheet (“Adwill D-678” manufactured by Lintec Co., Ltd.) was prepared on a 6-inch silicon wafer under conditions of a bonding temperature of 23° C. and a bonding speed of 20 mm/s. It was attached to a thickness of 350 μm), and the laminate of the dicing sheet and the silicon wafer was fixed to a ring frame.
Then, using a dicing device (“DFD6362” manufactured by DISCO), a dicing blade (“NBC-ZH2050-SE27HECC manufactured by DISCO”) was used to perform dicing at a blade rotation speed of 30,000 rpm and a cutting speed of 40 mm/s. A plurality of 2 mm×2 mm silicon chips (hereinafter sometimes referred to as “silicon chip group”) were obtained, and the dicing sheet is formed by laminating a base material and an adhesive layer, and Occasionally, the dicing blade was used to cut into a region having a depth of 20 μm in the dicing sheet.

Next, the adhesive sheet obtained above was attached to the silicon chip group obtained above while being heated to 60° C. with the film-like adhesive therein. At this time, the adhesive sheet was attached to the surface (exposed surface) opposite to the side to which the dicing sheet was attached, of the silicon chips in the silicon chip group. Then, the adhesive sheet after the attachment was cut along the outer periphery of the silicon chip.
As described above, the dicing sheet, the silicon chip, and the adhesive sheet were laminated in this order in the thickness direction to obtain a laminate having a size of 2 mm×2 mm.

Then, the release film was removed from the film adhesive in this laminate, and the exposed surface of the newly formed film adhesive was measured with a manual die bonder to have a size of 30 mm×30 mm and a thickness of 300 μm. It was attached to the surface of a copper plate. At this time, the film adhesive was applied by applying a force of 2.45 N (250 gf) to the copper plate while heating it to 125°C. Further, the bonded pieces were heated at 175° C. for 5 hours to obtain a test piece.

Next, using a universal bond tester (“DAGE4000” manufactured by Nordson Advanced Technology Co., Ltd.), at a temperature of 23° C., with a shear tool, at a speed of 200 μm/s, at the side surface of the test piece, film-like adhesion was performed. A force was applied to both the agent and the silicon chip in a direction parallel to the surface of the film adhesive to be attached to the copper plate. Then, the maximum value of the force applied until the film adhesive was broken was confirmed, and this was adopted as the shear strength (N/2 mm□) of the film adhesive. The results are shown in Table 1.

<Measurement of linear transmittance of light (400 to 800 nm) before heating>
The film adhesive obtained above was attached to one surface of a glass slide (thickness 0.9 mm) while heating at 40°C. The film adhesive was not subjected to heat treatment immediately after its production and before this attachment.
Then, of the film adhesive after sticking, the part protruding from the glass slide is cut, and the film adhesive of the same size and the glass slide are in a state where the positions of these peripheral portions are the same, A test piece (hereinafter referred to as a “pre-heating test piece”) configured by stacking in the thickness direction was obtained.

Regarding the glass preparation used in the preparation of the pre-heating test piece, a straight line of light (400 to 800 nm) was prepared in advance using a spectrophotometer (“UV-3101PC” manufactured by Shimadzu Co.) before the preparation of the pre-heating test piece. The transmittance (hereinafter, referred to as “reference linear transmittance”) was measured.
The linear transmittance of light (400 to 800 nm) was also measured for the pre-heated test piece obtained above by the same method.
The value obtained by subtracting the measured value of the reference linear transmittance at the same wavelength from the measured value of the linear transmittance of light (400 to 800 nm) at each wavelength of the test piece before heating is the film before heating. It was adopted as the linear transmittance of light (400 to 800 nm) of the linear adhesive (that is, the linear transmittance before heating). The results are shown in Table 1.

<Measurement of linear transmittance after heating with light (400 to 800 nm)>
An electric furnace was used to heat the test piece after measuring the linear transmittance of the light (400 to 800 nm) before heating at 260° C. for 10 minutes.
Then, the heated test piece was allowed to cool to the same temperature as room temperature.
Then, the linear transmittance of light (400 to 800 nm) of the test piece after heating and cooling (hereinafter, referred to as “test piece after heating”) is measured by the same method as in the case of the test piece before heating. did.
The value obtained by subtracting the measured value of the reference linear transmittance at the same wavelength from the measured value of the linear transmittance of light (400 to 800 nm) at each wavelength of the test piece after heating, the film after heating It was adopted as the linear transmittance of light (400 to 800 nm) of the linear adhesive (that is, the linear transmittance after heating). The results are shown in Table 1.

<Evaluation of fingerprint recognition by RGB before heating>
A digital camera (“IXY650” manufactured by Canon Inc.) is placed in front of the ball of the left index finger, and the distance between the surface of the ball of the left index finger and the surface of the camera lens is adjusted to 50 mm. Imaging data of the fingerprint of the left index finger (hereinafter referred to as “reference imaging data”) was acquired in macro mode.
While maintaining the positional relationship between the left index finger and the digital camera, the pre-heating test piece was further arranged between the belly of the left index finger and the digital camera. At this time, a straight line connecting the pad of the left index finger and the digital camera is to the exposed surface of the glass slide in the pre-heating test piece (that is, the surface opposite to the surface where the film adhesive is attached). The test pieces before heating were arranged so that they were orthogonal to each other and the exposed surface was on the digital camera side. Under this condition, the imaging data of the fingerprint of the left index finger (hereinafter, referred to as "pre-heating transmission imaging data") was acquired in the macro mode by the same method as the acquisition of the reference imaging data.

Using the graphic software (“Paint” manufactured by Microsoft Corporation), expand the standard imaging data and the pre-heating transmission imaging data obtained above, extract the color of the ridges and valleys of the fingerprint from each data, It was converted into numerical values in RGB.
The value obtained by subtracting the R value of the fingerprint mountain portion acquired from the reference imaging data from the R value of the fingerprint mountain portion acquired from the pre-heating transmission imaging data is the R value of the fingerprint mountain portion at the time of pre-heating evaluation. Adopted as a value. In the same manner as above, the G value and B value of the ridge portion of the fingerprint at the time of evaluation before heating were obtained.
In the same manner as above, the value obtained by subtracting the R value of the valley portion of the fingerprint acquired from the reference imaging data from the R value of the valley portion of the fingerprint acquired from the transmission imaging data before heating is obtained during the pre-heating evaluation. It was adopted as the R value of the valley part of the fingerprint. In the same manner as above, the G value and B value of the valley portion of the fingerprint at the time of evaluation before heating 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 (hereinafter sometimes referred to as “absolute value ΔR”) is calculated, and the G value of the mountain portion and the valley portion are calculated. The absolute value of the difference between the B value of the mountain portion and the B value of the valley portion (hereinafter, referred to as “absolute value ΔG”) is calculated. “Absolute value ΔB” may be described) was calculated.

Based on these calculated values, the fingerprint recognizability of the film adhesive before heating by RGB was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: At least one of the absolute value ΔR, the absolute value ΔG, and the absolute value ΔB is 10 or more.
B: The absolute value ΔR, the absolute value ΔG, and the absolute value ΔB are all less than 10, and at least one of the absolute value ΔR, the absolute value ΔG, and the 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 with RGB>
Fingerprints of the film adhesive after heating by RGB in the same manner as in the above-mentioned “Evaluation of fingerprint recognition property before heating” except that the post-heating test piece was used instead of the pre-heating test piece. The recognizability was evaluated.
More specifically, at the time of this evaluation, “post-heating transmission imaging data” was acquired instead of the pre-heating transmission imaging data. Further, using the post-heating transmission imaging data, instead of the R value, G value, and B value of the fingerprint ridge portion during the pre-heating evaluation, the R value, G value, and The B value was obtained, and instead of the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation before heating, the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation after heating were obtained. Further, from these R value, G value and B value, instead of the absolute value ΔR, absolute value ΔG and absolute value ΔB at the time of evaluation before heating, the absolute value ΔR, absolute value ΔG and absolute value ΔB at the time of evaluation after heating are used. Was calculated. The results are shown in Table 1.

<Evaluation of fingerprint recognition by visual inspection before heating>
Five observers were randomly selected and the fingerprints were visually observed one by one by the method described below.
That is, one observer is placed in front of the ball of the left index finger, the distance between the surface of the ball of the left index finger and the eyes of the observer is adjusted to 150 mm, and in this state, The fingerprint was directly observed visually.
The pre-heating test piece was further arranged between the observer and the belly of the left index finger while maintaining the positional relationship between the left index finger and the observer. At this time, the arrangement form of the pre-heating test piece was the same as that of the pre-heating test piece in the above-mentioned “evaluation of fingerprint recognition property before heating by RGB”. Under this condition, the fingerprint of the left index finger was visually observed through the pre-heating test piece as in the case of direct visual observation as described above.

By this method, all five observers visually observed the fingerprint directly and over the test piece before heating, and the appearance of the fingerprint through the test piece before heating and the appearance of the fingerprint by direct visual observation. According to the following criteria, the fingerprint recognizability of the film adhesive before heating was evaluated by visual observation. The results are shown in Table 1. The numerical value in parentheses in the column of "Fingerprint recognition" in Table 1 indicates "the number of observers (persons) judged to have no difference in the appearance of fingerprints".
A: All five observers judged that there was no difference in the appearance of fingerprints.
B: 4 out of 5 observers judged that there was no difference in the appearance of fingerprints.
C: Two or more out of five observers determined that the fingerprints had different colors and had different appearances.

<Evaluation of visual recognition of fingerprint after heating>
Except that the post-heating test piece was used in place of the pre-heating test piece, in the same manner as in the above-mentioned "evaluation of fingerprint recognition property before heating by visual observation", the film adhesive after visual heating was used. The fingerprint recognizability was evaluated. The results are shown in Table 1.

<Measurement of V ₁ >
Using an X-ray photoelectron spectroscopy analyzer ("Quantera SXM" manufactured by ALBAC PHI), one of the surfaces of the film adhesive (hereinafter, referred to as "pre-heating film adhesive") obtained above was 0. XPS analysis was performed by survey-scanning a region of 1 mm×1 mm at a measurement angle of 45° and a beam diameter of 18 μm, and the P concentration V ₁ on this surface was measured. At this time, the peak detected in the binding energy range of 123 to 143 eV was determined to be the P2p spectrum. Aluminum was used as the X-ray source. The film adhesive was not heat-treated immediately after its production and before this measurement. The results are shown in Table 1.

<Measurement of V ₂ >
The film adhesive before heating after measuring V ₁ was heated at 260° C. for 10 minutes using an electric furnace.
Then, the film adhesive after heating was allowed to cool to the same temperature as room temperature.
Next, of the film adhesive after heating and cooling (hereinafter, referred to as “film adhesive after heating”), the measurement surface of V ₁ is the same as the case of the film adhesive before heating described above. By the method, XPS analysis was performed to measure the P concentration V ₂ . The results are shown in Table 1.

<Calculation of P concentration decrease rate>
The P concentration decrease rate was calculated from V ₁ and V ₂ obtained above. The results are shown in Table 1.

<<Production and Evaluation of Film Adhesive>>
[Examples 2 to 5]
One or both of the types and the amounts of the compounding components during the production of the adhesive composition are changed so that the types and the amounts of the components of the adhesive composition are as shown in Table 1. A film adhesive was produced and evaluated in the same manner as in Example 1 except for the above. The results are shown in Table 1.

[Comparative Examples 1 and 2]
Either or both of the type and the amount of the compounding component at the time of manufacturing the adhesive composition are changed so that the type and the content of the component of the adhesive composition are as shown in Table 2. The production and evaluation of the film adhesive were tried in the same manner as in Example 1 except for the above. The results are shown in Table 2.

In addition, the description of "-" in the column of the contained component in Tables 1 and 2 means that the adhesive composition does not contain the component.
In addition, the description of “-” in the column of the evaluation result in Tables 1 and 2 indicates that the item cannot be evaluated (when the data could not be obtained, and the data was less than the detection limit value. (Including cases), or it means that the data could not be calculated.

As is clear from the above results, in Examples 1 to 5, the film adhesives before and after heating at 260° C. all had high light transmittance, suppressed coloring, and had high fingerprint recognizability. In Examples 1 to 5, the linear adhesiveness of light (400 to 800 nm) of the film adhesive before heating at 260° C. was 95% or more (95 to 97%), and the film adhesive after heating at 260° C. The linear transmittance of light (400 to 800 nm) of the adhesive was 85% or more (85 to 94%).

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

In Examples 1 to 5, V ₁ was 0.15 atomic% or more (0.15 to 0.40 atomic %) and V ₂ was 0.14 atomic% or more (0.14 to 0.39 atomic %). ), and the P concentration reduction rate was 14.3% or less (2.5 to 14.3%), which was small.
As described above, in Examples 1 to 5, the concentration of phosphorus in the film adhesive before and after heating was high, and the film adhesive after heating was in an amount sufficient to exhibit a sufficient antioxidant action. It was confirmed to contain the phosphorus-based antioxidant (z).

On the other hand, in Comparative Example 1, the film adhesive before heating at 260° C. had high light transmittance and the coloring was suppressed, but the film adhesive after heating at 260° C. did not transmit light. The fingerprint was not easily recognized, the coloring was not suppressed, and the fingerprint recognizability was low.
In Comparative Example 1, since the film adhesive did not contain an antioxidant, it was speculated that coloring due to heating was not suppressed.
In Comparative Example 1, naturally, V ₁ and V ₂ were less than the detection limit value, and the P concentration decrease rate could not be calculated.

In Comparative Example 2, the film adhesive before heating at 260° C. had low light transmittance, was cloudy in white, and had low fingerprint recognizability. Therefore, the film adhesive even after heating at 260° C. remained white and cloudy, and the fingerprint recognizability was low.
In Comparative Example 2, since the filler (d)-3 having a large average particle diameter was used, it was presumed that the film adhesive was turbid white. This is also clear from the comparison between the film adhesive of Example 4 and the film adhesive of Comparative Example 2 which are very similar in composition, except that the type of the filler (d) used is different. Met.
In Comparative Example 2, it was not possible to confirm the presence or absence of suppression of coloring due to heating due to the effect of this turbidity, but naturally the coloring due to heating was not suppressed because the film adhesive did not contain an antioxidant. It was speculated that
In Comparative Example 2, naturally, V ₁ and V ₂ were less than the detection limit value, and the P concentration decrease rate could not be calculated.

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

The present invention can be used as an adhesive at the time of manufacturing or processing various parts constituting an electronic device.

101... Composite sheet, 108, 109... Laminated sheet, 10... Dicing sheet, 11... Base material, 11a... First surface of base material, 12... Adhesive layer, 13 ... film adhesive, 13a ... first surface of film adhesive, 13b ... second surface of film adhesive, 151 ... first release film, 152 ... second release Film, 19... Resin film, 7... Light transmissive cover, 8... Chip, 8a... Chip circuit forming surface, 801... Laminated body

Claims

A film adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover,
One side of the film adhesive before heating at 260° C. was analyzed by X-ray photoelectron spectroscopy to measure the phosphorus concentration V 1 .
Of the film adhesive after measuring V 1 and heating at 260° C. for 10 minutes, the surface on which V 1 was measured was analyzed by X-ray photoelectron spectroscopy, and the phosphorus concentration V 2 Is measured,
V 1 is 0.1 atomic% or more,
A film-like adhesive having a reduction rate of the phosphorus concentration calculated from V 1 and V 2 of 25% or less.
The linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive before heating at 260° C. is 90% or more,
The linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive after heating at 260° C. for 10 minutes is 85% or more,
The film-like adhesive according to claim 1, wherein the film-like adhesive has a thickness of 10 to 40 μm.
The film adhesive according to claim 1 or 2, wherein the film adhesive contains an aliphatic epoxy compound.
The film adhesive contains a phenol resin (b2),
The ratio of the content of the phenolic resin (b2) with respect to the total mass of the film adhesive in the film adhesive is 10% by mass or less. Film adhesive.
The film adhesive according to any one of claims 1 to 4, wherein the film adhesive contains an aliphatic phosphite ester as an antioxidant.
The film adhesive contains an acrylic resin and an aliphatic polyvalent isocyanate crosslinking agent,
The film adhesive according to any one of claims 1 to 5, wherein the acrylic resin has a functional group capable of binding to the crosslinking agent.
A laminated sheet comprising the film adhesive according to any one of claims 1 to 6 and a resin film provided on one surface of the film adhesive.
A film-like adhesive according to any one of claims 1 to 6, and a dicing sheet provided on one surface of the film-like adhesive,
The dicing sheet comprises a base material, and an adhesive layer provided on one surface of the base material,
The composite sheet, wherein the pressure-sensitive adhesive layer is disposed between the base material and the film adhesive.
7. The circuit forming surface of the chip is attached to one surface of the film-like adhesive according to claim 1, and the light-transmitting cover is attached to the other surface of the film-like adhesive. Thus, a method for manufacturing a laminated body, in which the chip, the film adhesive, and the light transmissive cover are laminated in this order to obtain a laminated body.