JPWO2020137944A1 - Method for manufacturing film-like adhesive, laminated sheet, composite sheet, and laminated body - Google Patents

Abstract

The film-like adhesive of the present embodiment is for bonding the circuit forming surface of the chip and the light-transmitting cover, and X-ray photoelectron spectroscopy is performed on one surface of the film-like adhesive before heating at 260 ° C. Analysis was performed by the method, the phosphorus concentration V1 was measured, the V1 was measured, and the surface of the film-like adhesive after heating at 260 ° C. for 10 minutes was subjected to X-ray photoelectron. When the phosphorus concentration V2 is measured by analysis by spectroscopic method, the V1 is 0.1 atomic% or more, and the reduction rate of the phosphorus concentration calculated from the V1 and V2 is 25% or less.

Description

The present invention relates to a film-like 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.

When manufacturing or processing various parts constituting an electronic device, various film-like adhesives are used depending on the purpose.
For example, when mounting a semiconductor chip on the circuit forming surface of a substrate, a film-like adhesive is attached to the back surface of the semiconductor chip, and the semiconductor chip is attached to the circuit forming surface of the substrate via the film-like adhesive. Adhesion (die bonding). Further, when protecting the circuit forming surface of a chip such as a sensor, the circuit forming surface is covered with a light transmitting cover via a film-like adhesive having light transmission.

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

As a film-like adhesive having light transmittance, for example, a die bond film for die bonding of 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 the physical characteristics after heating, such as the color of the die bond film after heating.

The present invention uses a film-like adhesive that has light transmission before and after heating and suppresses coloring 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 producing a laminated body.

The present invention is a film-like adhesive for bonding a circuit-forming surface of a chip and a light-transmitting cover, and X-rays are provided on one surface of the film-like adhesive before heating at 260 ° C. The surface of the film-like adhesive after analysis by photoelectron spectroscopy _{, measuring the phosphorus concentration V 1} , measuring the V ₁ , and heating at 260 ° C. for 10 minutes, where 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, and the decrease in the phosphorus concentration calculated from the _{V 1} and V _{2 was reduced.} Provided is a film-like adhesive having a ratio of 25% or less.
In the film-like adhesive of the present invention, the linear transmittance of light having a wavelength of 400 to 800 nm of the film-like adhesive before heating at 260 ° C. is 90% or more, and the film-like adhesive is heated at 260 ° C. for 10 minutes. The linear transmittance of light having a wavelength of 400 to 800 nm of the film-like adhesive after the film may be 85% or more, and the thickness of the film-like adhesive may be 10 to 40 μm.
The film-like adhesive of the present invention may contain an aliphatic epoxy compound.
The film-like 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-like adhesive in the film-like adhesive is 10 mass by mass. It may be less than or equal to%.

The film-like adhesive of the present invention may contain an aliphatic phosphite ester as an antioxidant.
In the film-like adhesive of the present invention, the film-like adhesive contains an acrylic resin and an aliphatic polyhydric isocyanate-based cross-linking agent, and the acrylic resin is functionally capable of binding to the cross-linking agent. It may have a group.
The present invention provides a laminated sheet comprising the film-like adhesive and a resin film provided on one surface of the film-like adhesive.
The present invention comprises the film-like adhesive and a dicing sheet provided on one surface of the film-like adhesive, wherein the dicing sheet is a base material and one surface of the base material. Provided is a composite sheet comprising a pressure-sensitive adhesive layer provided above, wherein the pressure-sensitive adhesive layer is arranged between the base material and the film-like adhesive.
In the present invention, the chip and the circuit-forming surface of the chip are attached to one surface of the film-like adhesive, and a light-transmitting cover is attached to the other surface of the film-like adhesive. Provided is a method for producing a laminated body, which obtains a laminated body in which a film-like adhesive and the light-transmitting cover are laminated in this order.

The film-like adhesive of the present invention has light transmission before and after heating, and coloring after heating is suppressed.
By using the laminated sheet or composite sheet of the present invention provided with the film-like adhesive of the present invention, the film-like adhesive can be provided on a component to which the film-like adhesive is applied.
According to the method for producing a laminate of the present invention, a laminate composed of a chip, a film-like adhesive, and a light-transmitting cover laminated in this order can be produced.

It is sectional drawing which shows typically an example of the film-like adhesive and laminated sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically another 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 by using the film-like adhesive which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining an example of the usage method of the composite sheet which concerns on one Embodiment of this invention.

◇ Film-shaped adhesive The film-shaped adhesive according to the embodiment of the present invention is a film-shaped adhesive for bonding the circuit forming surface of the chip and the light transmissive cover, and is heated at 260 ° C. One surface of the previous film-like adhesive was analyzed by X-ray photoelectron spectroscopy (sometimes abbreviated as "XPS" in the present specification) and the concentration of phosphorus (in the present specification, it may be abbreviated as "XPS"). _{Of the film-like adhesive after measuring V 1 (} which may be abbreviated as "P concentration"), measuring the V ₁ , and heating at 260 ° C. for 10 minutes, the surface on _{which the V 1 was measured.} 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 rate of decrease in the concentration of phosphorus to be produced (in this specification, it may be abbreviated as "rate of decrease in P concentration") is 25% or less.

Examples of the film-like adhesive satisfying the conditions of V ₁ , V ₂ and the reduction rate include those containing a trivalent phosphorus compound. In such a film-like adhesive, turbidity and coloring are suppressed before and after heating at 260 ° C. or the like, and light having a wavelength of 400 to 800 nm (in the present specification, "light (400 to 800 nm)"). (May be abbreviated) has high linear transmittance.

The film-like adhesive of the present embodiment can be used for adhering an object at the time of 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-like adhesive. That is, the film-like 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-like adhesive has high light transmission before and after heating, and coloring is suppressed. Therefore, the visual sense present on the circuit forming surface of the chip through the light-transmitting cover and the film-like adhesive. Information can be viewed stably and with high accuracy.

Examples of the sensor covered by the light transmissive cover (protective cover) include a fingerprint sensor. However, this is an example of a sensor.

In the present specification, the surface on which the circuit of the substrate and the chip is formed is referred to as a “circuit forming surface”.
In addition, in this specification, the description of a simple "chip" does not mean only a semiconductor chip, but also includes a chip other than the semiconductor chip.

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

The linear transmittance of light (400 to 800 nm) (in this specification, it may be abbreviated as "linear transmittance before heating") of the film-like adhesive of the present embodiment before heating at 260 ° C. It is preferably 90% or more, more preferably 91.5% or more, further preferably 93% or more, and particularly preferably 94.5% or more. When the linear transmittance before heating is at least the lower limit value, the film-like adhesive before heating has a property of being able to correctly recognize the image when the image is viewed through the film-like adhesive (the present specification). In, it may be abbreviated as "image recognition").

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-like adhesive having a linear transmittance before heating of 99.8% or less is easier to manufacture.

The pre-heating linear transmittance of light (400 to 800 nm) can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the pre-heating linear transmittance 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-like adhesive of the present embodiment after heating at 260 ° C. for 10 minutes (in this specification, it may be abbreviated as "linear transmittance after heating"). Is preferably 85% or more, and may be, for example, 87.5% or more, 90% or more, and 92% or more. When the linear transmittance after heating is at least the lower limit value, the film-like adhesive after heating has high image recognition.

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-like 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 of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the linear transmittance after heating is preferably 85 to 99.8%, for example, 87.5 to 99.8%, 90 to 99.8%, and 92 to 99. It may be any of 8%. However, these are examples of the linear transmittance after heating.

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

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

The shear strength of the film-like 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 any of 80 N / 2 mm □ or more. When the shear strength of the film-like adhesive is at least the above lower limit value, the adhesive strength to the object to be attached becomes stronger.
In addition, in this specification, the unit "N / 2mm □" is synonymous with "N / (2mm × 2mm)".

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

The shear strength of the film-like adhesive can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. 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 80. It may be any of 300 N / 2 mm □. However, these are examples of the shear strength.

The shear strength of the film-like adhesive in the present embodiment is measured by the method shown below.
(Measuring method of shear strength of film adhesive)
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 were used to prepare the film-like adhesive. A test piece is produced 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 the test piece, the side surfaces of the film-like adhesive and the silicon chip are aligned.
Under the temperature condition of 23 ° C., on the aligned side surface of the test piece, with respect to both the film-like adhesive and the silicon chip, with respect to the other surface of the film-like adhesive. A force is applied at a speed of 200 μm / s in parallel directions, and the maximum value of the force applied until the film-like adhesive is broken is the shear strength (N / 2 mm □) of the film-like adhesive. ).

When XPS analysis was performed on one surface of the film-like 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. It is preferably 0.14 atomic% or more, and for example, it may be either 0.2 atomic% or more and 0.3 atomic% or more. When V ₁ is at least the above lower limit value, the effect of suppressing coloring of the film-like adhesive before heating (for example, heating at 260 ° C.) is enhanced.

The upper limit 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-mentioned lower limit values and upper limit values. For example, in one embodiment, V ₁ is preferably 0.1 to 0.5 atomic%, more preferably 0.12 to 0.5 atomic%, and 0.14 to 0.5 atomic. It is more preferably%, and may be, for example, either 0.2 to 0.5 atomic% and 0.3 to 0.5 atomic%.

Of the film-like adhesive after measuring V ₁ and heating at 260 ° C. for 10 minutes, when _{the measurement surface of V 1} was subjected to XPS analysis and the P concentration V ₂ was measured, V ₂ was found. , 0.1 atomic% or more, more preferably 0.12 atomic% or more, still more preferably 0.14 atomic% or more, for example, 0.2 atomic% or more, and 0. .3 It may be any of 3 atomic% or more. When V ₂ is at least the above lower limit value, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.) becomes higher.

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

V ₂ can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. 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. It is more preferably%, and may be, for example, either 0.2 to 0.5 atomic% and 0.3 to 0.5 atomic%.

V ₁ and V ₂ can be measured by survey scanning a region of 0.1 mm × 1 mm on one surface of the film-like 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. As the X-ray source, for example, aluminum can be used.

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

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

The P concentration reduction 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 reduction rate is preferably 1 to 25%, more preferably 1 to 20%, still more preferably 1 to 15%, for example, 1 to 10%. %, 1-7.5%, and 1-5%.

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

In the film-like adhesive, at least one surface _{satisfies the above-mentioned V 1} , V ₂ and P concentration reduction rate conditions, and both surfaces satisfy the above-mentioned V ₁ , V ₂ and P concentration reduction rate conditions. It is preferable to satisfy.
The composition of the single-layer film-like adhesive is usually not biased, and the composition is highly uniform. Therefore, there is no significant difference in the types and contents of the components contained in both sides of the single-layer film-like adhesive, or even if they are observed, the effect brought about by the difference is negligible. It is minor.
In the single-layer film-like adhesive, if at least one of the surfaces _{satisfies the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate, any cross section of the film-like adhesive and the other surface are satisfied. Also, it can be judged that the conditions of the above-mentioned V ₁ , V _{2 and P concentration reduction rates are satisfied.}

The film-like adhesive may be composed of one layer (single layer), 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 multiple layers is not particularly limited.

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

The thickness of the film-like adhesive is preferably 10 to 40 μm, for example, it may be any of 10 to 35 μm, 10 to 30 μm, and 10 to 25 μm, and 13 to 40 μm and 16 to 40 μm. , And 19-40 μm, or 13-35 μm, 16-30 μm, and 19-25 μm. When the thickness of the film-like adhesive is at least the above lower limit value, the adhesive force of the film-like adhesive to the object to be adhered becomes stronger. When the thickness of the film-shaped adhesive is not more than the upper limit value, the linear transmittance of light (for example, light (400 to 800 nm)) of the film-shaped adhesive is increased regardless of the presence or absence of heating.
Here, the "thickness of the film-like adhesive" means the thickness of the entire film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers is all that constitute the film-like adhesive. Means the total thickness of the layers of.

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

The above-mentioned physical characteristics of the film-like 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 determined. For example, it can be adjusted by adjusting the type and content of the components contained in the film-like adhesive.

Preferred film-like adhesives are, for example, one or two selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus-based antioxidant (z). Those containing the above can be mentioned.

<< Adhesive composition >>
The film-like 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-based antioxidant (z). It can be formed by using an adhesive composition containing the above). For example, the film-like adhesive can be formed on a target portion by applying the adhesive composition to the surface to be formed of the film-like adhesive and drying it if 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-like adhesive. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The adhesive composition may be applied 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, and a screen coater. , 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 a solvent described later, it is preferable to heat-dry the adhesive composition. 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-like 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 being 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. be.
In the present specification, the term "derivative" means a compound 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 composed of a plurality of atoms bonded to each other but also one atom.
The acrylic resin (a) is a resin component for imparting film-forming property, flexibility, etc. to the film-like adhesive and improving the adhesiveness (stickability) to the adhesive object such as the chip.

In the present 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-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

Examples of the acrylic resin (a) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin (a) is preferably 1000 to 2000000, and more preferably 100,000 to 1500,000. 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-like adhesive and the adherend within a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin (a) is at least the above lower limit value, the shape stability (stability with time during storage) of the film-like adhesive is improved. Further, when the weight average molecular weight of the acrylic resin (a) is not more than the above upper limit value, the film-like adhesive can easily follow the uneven surface of the adherend, and between the adherend and the film-like adhesive. The generation of voids and the like is further suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the 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 above lower limit value, the adhesive force between the film-like adhesive and the adherend is suppressed, and for example, the film-like adhesive is provided at the time of pick-up. The chip can be easily separated 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-like adhesive and the adherend is improved.

Examples of the (meth) acrylic acid ester constituting the acrylic resin (a) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl 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 (meth) acrylate), (Meta) ) Pentadecyl acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc. A (meth) acrylic acid alkyl ester in which the group has a chain structure having 1 to 18 carbon atoms;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) acrylate imide;
A 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-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof 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 a group other than the hydrogen atom.

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

The monomer constituting the acrylic resin (a) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The 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 such as the hydroxyl group of the acrylic resin (a) may be bonded to another compound via a cross-linking agent (f) described later, or the other compound may be bonded without the cross-linking 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-like adhesive tends to be improved.

Preferred acrylic resins (a) include, for example, those having a functional group capable of binding to the cross-linking 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, the acrylic resin (that is, the total mass of the film-like adhesive in the film-like adhesive). 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, and 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-like adhesive is more stabilized. When the ratio is not more than the upper limit value, it becomes easy to increase the amount of components other than the acrylic resin (a) such as the epoxy compound (b1) and the phosphorus-based antioxidant (z), and the acrylic-based The effect of using the 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 ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene type epoxy resin. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, triazine type alicyclic epoxy compound, and other bifunctional or higher functional epoxy compounds 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-like adhesive is improved.

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

Further, examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include 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.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) group. Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy compound (b1) (in other words, the epoxy resin (b1)), which is a resin component, is not particularly limited, but the curability of the film-like adhesive and the strength and heat resistance of the cured product of the film-like adhesive. From this point of view, it is preferably 300 to 30,000, more preferably 400 to 10000, and particularly preferably 500 to 3000.
The epoxy equivalent of the epoxy compound (b1) is preferably 100 to 1000 g / eq, more preferably 120 to 600 g / eq.

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

The epoxy compound (b1) is preferably an aliphatic compound. That is, the film-like adhesive preferably contains an aliphatic epoxy compound.
As used herein, the term "aliphatic compound" means a compound having an aliphatic group and no aromatic group. Further, the "aliphatic group" includes a chain aliphatic group and an aliphatic cyclic group (also known as an alicyclic group). Further, the "aromatic group" includes an aromatic hydrocarbon group and an aromatic heterocyclic group.
By containing the aliphatic compound as the epoxy compound (b1) in the adhesive composition and the film-like adhesive, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.) can be obtained. Further, by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-mentioned effect of suppressing coloring is remarkably increased.

The epoxy compound (b1) is selected from the group consisting of triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C = C), cyano groups (-C≡N) and aromatic groups. It is preferable not to have one kind or two or more kinds.
The adhesive composition and the film-like adhesive contain the epoxy compound (b1) that does not have these bonds or groups, so that the film-like adhesive is colored after heating (for example, heating at 260 ° C.). The effect of suppressing the above-mentioned coloration is remarkably increased by containing only those having no such bond or group (in other words, not containing the one having these bonds or groups).

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. That is, the film-like adhesive contains an aliphatic epoxy compound that does not have one or more selected from the group consisting of triple bonds between carbon atoms, double bonds between carbon atoms, and cyano groups. Is preferable.
The adhesive composition and the film-like adhesive contain the aliphatic compound having no bond or group as the epoxy compound (b1) to heat the film-like adhesive (for example, heating at 260 ° C.). The effect of suppressing the subsequent coloring becomes higher, and the above coloring is performed by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bonds or groups). Suppressive effect is remarkably increased.

In the adhesive composition and the film-like adhesive, the content of the epoxy compound (b1) is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the content 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-like adhesive and the resin film or dicing sheet described later.

<Phosphorus-based antioxidant (z)>
Since the film-like adhesive contains a 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 effect.
Examples of the phosphorus-based antioxidant (z) include compounds having a phosphorus oxidation number of 3.

The phosphorus-based antioxidant (z) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.

The phosphorus-based antioxidant (z) is preferably an aliphatic compound.
The adhesive composition and the film-like adhesive contain an aliphatic compound as the phosphorus-based antioxidant (z) to color the film-like 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-mentioned coloring inhibitory effect is remarkably 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.
The adhesive composition and the film-like adhesive contain a phosphorus-based antioxidant (z) that does not have these bonds or groups, whereby the film-like adhesive is heated (for example, heating at 260 ° C.). The subsequent effect of suppressing coloring becomes higher, and by containing only those having no such bond or group (in other words, not containing those having these bonds or groups), the above-mentioned effect of suppressing coloration becomes remarkable. It gets 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).
The adhesive composition and the film-like adhesive contain the aliphatic compound having no bond or group as the phosphorus-based antioxidant (z), whereby the film-like adhesive is heated (for example, at 260 ° C.). The effect of suppressing coloration after (heating) is higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bonds or groups). The above-mentioned effect of suppressing coloring is remarkably enhanced.

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

Examples of the aliphatic phosphite trialkyl ester include triethyl phosphite ((C ₂ H ₅ O) ₃ P) and tris (2-ethylhexyl) phosphite ((CH ₃ CH ₂ CH ₂ CH ₂ CH (CH)). ₂ CH ₃ ) CH ₂ O) ₃ P), _{Tridecyl phosphite ((C 10} H ₂₁ O) ₃ P), Trilauryl phosphite ((C ₁₂ H ₂₅ O) ₃ P), 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 diphos Fight (C ₁₈ H ₃₇ OP (OCH ₂ ) ₂ C (CH ₂ O) ₂ POC ₁₈ H ₃₇ ), Phosphorus Phosphorus A-Pentaerythritol Phosphite Polymer (Formula "-(OC ₆ H ₁₂ C (CH ₃ )) _2" C ₆ H ₁₂ OP (OCH ₂ ) ₂ C (CH ₂ O) ₂ P)-”is a polymer having a repeating unit) and the like.

In the adhesive composition, the ratio of the content of the phosphorus-based antioxidant (z) to the total content of all components other than the solvent (that is, phosphorus to the total mass of the film-like adhesive in the film-like adhesive). The content ratio 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. It is more preferably%. When the ratio is at least the lower limit value, the effect of using the phosphorus-based antioxidant (z) can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the phosphorus-based antioxidant (z) is suppressed.

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

<Phenol 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 in combination, these combinations function as an epoxy-based thermosetting resin. In the present embodiment, such an epoxy-based thermosetting resin may be referred to as "epoxy-based thermosetting resin (b)".

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

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

The phenol resin (b2) may have an unsaturated hydrocarbon group.
Examples of the other phenol resin (b2) having an unsaturated hydrocarbon group include a compound having a structure in which some of the hydroxyl groups of the phenol resin are substituted with a group having an unsaturated hydrocarbon group, and an aromatic ring of the phenol 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 above-mentioned epoxy compound having an unsaturated hydrocarbon group.

The phenol resin (b2) preferably has a high softening point or glass transition temperature because it is easy to adjust the adhesive force of the film-like adhesive.

The number average molecular weight of the phenol resin (b2) is preferably 300 to 30,000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

The phenol resin (b2) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the phenol resin (b2) is used, the ratio of the content of the phenol resin (b2) to the total content of all the components other than the solvent in the adhesive composition (that is, the film-like adhesive in the film-like adhesive). The ratio of the content of the phenol resin (b2) to the total mass of the above 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 not more than the upper limit value, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.) becomes higher.
That is, as an example of the preferable film-like adhesive containing the phenol resin (b2), the ratio of the content of the phenol resin (b2) to the total mass of the film-like adhesive in the film-like adhesive is. Those having a weight of 10% by mass or less can be mentioned.

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

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 even more preferable.

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

<Curing accelerator (c)>
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition and the film-like 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 and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Tetraphenylborone salts such as tetraphenylborate; inclusion compounds having the imidazoles as guest compounds can be mentioned.

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-like 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 at least the lower limit value, the effect of using the curing accelerator (c) is more remarkable. When the content of the curing accelerator (c) is not more than the above upper limit value, for example, the highly polar curing accelerator (c) is attached to the adherend in the film-like 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-like 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)>
By containing the filler (d), the film-like adhesive makes it easy to adjust its coefficient of thermal expansion, and by optimizing this coefficient of thermal expansion for the object to which the film-like adhesive is attached, the film The reliability of the package obtained by using the state adhesive is further improved. Further, when the film-like adhesive contains the filler (d), it is possible to reduce the hygroscopicity of the cured product of the film-like adhesive and improve the heat dissipation.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; 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 even more preferably 10 to 60 nm. When the average particle size of the filler (d) is not more than the upper limit value, the turbidity of the film-like adhesive is highly suppressed, and the straight line before heating of the light (400 to 800 nm) of the film-like adhesive. The permeability and the linear permeability after heating are improved, and as a result, the image recognition of the film-like adhesive before and after heating becomes higher. When the average particle size of the filler (d) is at least the above lower limit value, the effect of using the filler (d) can be obtained more remarkably.
In the present specification, the "average particle size" means the value _{of the particle size (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-like adhesive may be of only one type, of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all the components other than the solvent in the adhesive composition (that is, the film-like adhesive in the film-like 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 to have. When the content of the filler (d) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.

<Coupling agent (e)>
By containing the coupling agent (e) in the film-like adhesive, the adhesiveness and adhesion to the adherend are improved. Further, when the film-like 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 a functional group of an acrylic resin (a), an epoxy thermosetting resin (b), or the like, and is a silane coupling agent. Is more preferable.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (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. ..

The coupling agent (e) is preferably an aliphatic compound.
By containing the aliphatic compound as the coupling agent (e) in the adhesive composition and the film-like adhesive, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.). By containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-mentioned effect of suppressing coloring is remarkably increased.

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 to be treated.
The adhesive composition and the film-like adhesive contain the coupling agent (e) having no such bond or group, so that the film-like adhesive is heated (for example, heated at 260 ° C.). The effect of suppressing coloring becomes higher, and by containing only those having no such bond or group (in other words, not containing those having these bonds or groups), the above-mentioned effect of suppressing coloring becomes significantly higher. ..

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.
The adhesive composition and the film-like adhesive contain the aliphatic compound having no bond or group as the coupling agent (e) to heat the film-like 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 bonds or groups), the above-mentioned The effect of suppressing coloring is remarkably increased.

Among the coupling agents (e), as the aliphatic compound (aliphatic coupling agent), more specifically, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-Glysidyloxypropyltriethoxysilane, 3-Glysidyloxymethyldiethoxysilane, 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.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is the total of the acrylic resin (a) and the epoxy-based 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, the adhesiveness of the film-like adhesive to the adherend is improved, and the like. , The effect of using the coupling agent (e) is more remarkable. When the content of the coupling agent (e) is not more than the upper limit value, the generation of outgas is further suppressed.

<Crosslinking agent (f)>
When the acrylic resin (a) has 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 that can be bonded to the other compounds described above, the adhesive composition is used. The product and the film-like adhesive may contain a cross-linking agent (f) for bonding the functional group with another compound to cross-link. By cross-linking with the cross-linking agent (f), the initial adhesive force and the cohesive force of the film-like adhesive can be adjusted.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound and the like". (May be abbreviated); trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the like with a polyol compound. And so on. The "adduct" includes the aromatic polyvalent isocyanate compound, the aliphatic polyhydric isocyanate compound, or the alicyclic polyvalent isocyanate compound, and low ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like. It means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct are the xylylene diisocyanate adduct of trimethylolpropane, the isophorone diisocyanate adduct of trimethylolpropane, the tolylene diisocyanate adduct of trimethylolpropane, and the hexamethylene diisocyanate adduct of trimethylolpropane. And so on. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

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

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking 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, the cross-linking structure is simplified into a film-like adhesive by the reaction between the cross-linking agent (f) and the acrylic resin (a). Can be introduced in.

The cross-linking agent (f) is preferably an aliphatic compound.
By containing the aliphatic compound as the cross-linking agent (f) in the adhesive composition and the film-like adhesive, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.) can be obtained. Further, by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-mentioned effect of suppressing coloring is remarkably increased.

The cross-linking agent (f) is selected from the group consisting of triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C = C), cyano groups (-C≡N) and aromatic groups. It is preferable not to have one kind or two or more kinds.
The adhesive composition and the film-like adhesive contain the cross-linking agent (f) that does not have these bonds or groups, so that the film-like adhesive is colored after heating (for example, heating at 260 ° C.). The effect of suppressing the above-mentioned coloring is remarkably increased by containing only those having no such bond or group (in other words, not containing the one having these bonds or groups).

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.
The adhesive composition and the film-like adhesive contain the aliphatic compound having no bond or group as the cross-linking agent (f) to heat the film-like adhesive (for example, heating at 260 ° C.). The effect of suppressing the subsequent coloring becomes higher, and the above coloring is performed by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bonds or groups). The suppressive effect of is significantly increased.

The cross-linking agent (f) is an aliphatic organic polyhydric isocyanate compound (aliphatic polyvalent isocyanate cross-linking agent) in that the above-mentioned effect of suppressing coloration is particularly high and the cross-linking agent has excellent properties as a cross-linking agent. Is preferable.
More specifically, as the aliphatic polyhydric isocyanate cross-linking agent, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-. Diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; A compound in which one or more of tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are added to all or some hydroxyl groups of a polyol such as trimethylolpropane. ; Lysine diisocyanate and the like can be mentioned.

When focusing on the acrylic resin (a) and the cross-linking agent (f), the film-like adhesive can be used as the cross-linking agent (f) in that it has a particularly high effect of suppressing coloring and has excellent properties. It is preferable that the aliphatic polyvalent isocyanate cross-linking agent is contained and the acrylic resin (a) contains 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-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition and the film-like adhesive is 0.3 to 0.3 to 100 parts by mass with respect to 100 parts by mass of the content of the acrylic resin (a). It is preferably 12 parts by mass, more preferably 0.3 to 3.5 parts by mass, and even 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 remarkably. Further, when the content of the cross-linking agent (f) is not more than the upper limit value, the excessive use of the cross-linking agent (f) is suppressed.

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

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

Examples of the acrylate-based compound include trimethylolpropantri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (dipentaerythritol monohydroxypenta). Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylates, dipentaerythritol hexa (meth) acrylates, 1,4-butylene glycol di (meth) acrylates, and 1,6-hexanediol di (meth) acrylates; Cyclic aliphatic skeleton-containing (meth) acrylate such as cyclopentanyldi (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Oligoester (meth) acrylate; Urethane (meth) acrylate oligomer ; Epoxy-modified (meth) acrylate; polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomer and the like.

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

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

When the energy ray-curable resin (g) is used, the ratio of the content of the energy ray-curable resin (g) to the total mass 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-like adhesive contain the energy ray-curable resin (g), the photopolymerization initiator (h) is used in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (g). It may be contained.

Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; Acetphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol such as 1-hydroxycyclohexylphenylketone Compounds; azo compounds such as azobisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1, 2-Diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.
Further, examples of the photopolymerization initiator (h) include a photosensitizer such as amine.

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

The photopolymerization initiator (h) consists of 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 species.
After heating (for example, heating at 260 ° C.) of the film-like adhesive by containing the adhesive composition and the film-like adhesive as the photopolymerization initiator (h) having no bond or group thereof. The effect of suppressing coloration is higher, and the effect of suppressing coloration is remarkably high by containing only those having no such bond or group (in other words, not containing those having these bonds or groups). 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).
The adhesive composition and the film-like adhesive contain the aliphatic compound having no bond or group as the photopolymerization initiator (h), whereby the film-like adhesive is heated (for example, at 260 ° C.). The effect of suppressing coloring after heating) 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 bonds or groups), the above The effect of suppressing the coloring of the compound is remarkably increased.

Among the photopolymerization initiators (h), as the aliphatic compound (aliphatic photopolymerization initiator), more specifically, for example, an acylphosphine oxide compound; a sulfide compound such as tetramethylthium monosulfide; an azo; Examples thereof include azo compounds such as bisisobutyronitrile; peroxide compounds; diketone compounds such as diacetyl; and photosensitizers such as amine.
Among the compounds exemplified here, it 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). Examples of the photopolymerization initiator (h) not having one or more selected from the group consisting of azobisisobutyronitrile include compounds other than azobisisobutyronitrile.

The photopolymerization initiator (h) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrarily selected. 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 content of the energy ray-curable resin (g). It is preferably ~ 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

<Other antioxidants (y)>
The adhesive composition and the film-like adhesive may contain the other antioxidant (y) as long as the effects of the present invention are 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 either an organic compound or an inorganic compound.

The other antioxidants (y) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and if there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.

When another antioxidant (y) is used, the content of the other antioxidant (y) in the adhesive composition and the film-like adhesive is 100 parts by mass of the content 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, and further 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-like adhesive before and after heating is further suppressed.

The adhesive composition and the film-like adhesive preferably do not contain another antioxidant (y).

<Thermoplastic resin (x)>
The adhesive composition and the film-like 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 picking up, the chip provided with the film-like adhesive can be easily separated from the dicing sheet described later, or the film can be formed on the uneven surface of the adherend. The shape adhesive can easily follow, and the generation of voids and the like between the adherend and the film-like 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 1000 to 100,000, more preferably 3000 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-like adhesive may be of only one type, of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

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

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

<General-purpose additive (i)>
The general-purpose additive (i) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited. Preferred general-purpose additives (I) include, for example, plasticizers, antistatic agents, colorants (dye, pigment), gettering agents and the like.

When the general-purpose additive (i) is an organic compound, such a general-purpose additive (i) (abbreviated as "organic general-purpose additive" in the present specification) is preferably an aliphatic compound. ..
When the adhesive composition and the film-like adhesive contain an aliphatic compound as an organic general-purpose additive, the effect of suppressing coloring of the film-like adhesive after heating (for example, heating at 260 ° C.) is further improved. By increasing the amount and containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-mentioned effect of suppressing coloring is remarkably increased.

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.
By containing the adhesive composition and the film-like adhesive as organic general-purpose additives that do not have these bonds or groups, the film-like adhesive can be colored after heating (for example, heating at 260 ° C.). The inhibitory effect is further enhanced, and by containing only those having no of these bonds or groups (in other words, not containing those having these bonds or groups), the inhibitory effect of the above-mentioned coloring is remarkably 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 heating the film-like adhesive (for example, heating at 260 ° C.), the adhesive composition and the film-like adhesive contain an aliphatic compound having no bond or group as an organic general-purpose additive. The effect of suppressing the coloring of the above-mentioned coloring becomes higher, and the above-mentioned coloring is carried out by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bonds or groups). The inhibitory effect is significantly increased.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..
The content of the general-purpose additive (i) in the adhesive composition and the film-like adhesive is not particularly limited and may be appropriately selected depending on the intended 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 preferred ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof 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 type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The 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.

<< Manufacturing method of adhesive composition >>
The adhesive composition is obtained by blending each component for constituting the adhesive composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or diluting any of the compounding components other than the solvent in advance. You may use it by mixing the solvent with these compounding components without leaving it.

The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of 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 cross-sectional view schematically showing a film-like adhesive according to an embodiment of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio and the like of each component are the same as the actual ones. Is not always the case.

The film-like adhesive 13 shown here has a first release film 151 on one surface (sometimes referred to as a “first surface” in the present specification) 13a, and is referred to as the first surface 13a. A second release film 152 is provided on the other surface (sometimes referred to as the "second surface" in the present specification) 13b on the opposite side. Here, reference numeral 109 is attached to a laminated sheet in which the first release film 151, the film-like adhesive 13, and the second release film 152 are laminated 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, for example, a roll.

The film-like 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-like adhesive 13 _{satisfies the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate.
The thickness of the film-like adhesive 13 is preferably 10 to 40 μm.
The film-like adhesive 13 can be formed by using the above-mentioned adhesive composition.

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

In the film-like adhesive 13 shown in FIG. 1, either one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the surface to be attached to the object to be attached. Here, examples of the object to be attached include the above-mentioned chip and the like. In the case of the chip, the sticking surface of the film-like adhesive 13 is the circuit forming surface thereof.

One preferred embodiment of the film-like adhesive is, for example, a film-like adhesive for bonding a circuit-forming surface of a chip and a light-transmitting cover.
One surface of the film-like adhesive before heating at 260 ° C. was analyzed by X-ray photoelectron spectroscopy, the phosphorus concentration V ₁ was measured, the V ₁ was measured, and 10 at 260 ° C. Of the film-like adhesive after heating for a minute, _{the surface on which V 1} was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, V ₁ was 0.1 atomic. % Or more, and the reduction rate of the phosphorus concentration calculated from _{V 1} and V _{2 is 25% or less.}
Using the 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 , 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-like adhesive and the silicon chip are aligned. On the aligned side surface of the test piece under a temperature condition of 23 ° C., for both the film-like adhesive and the silicon chip, the other of the film-like adhesive. A force is applied at a rate of 200 μm / s in a direction parallel to the surface, and the maximum value of the force applied until the film-like adhesive is broken is the shear strength (N) of the film-like adhesive. When it is set to / 2 mm □), the shear strength is 20 N / 2 mm □ or more.

One preferred embodiment of the film-like adhesive is, for example, a film-like adhesive for bonding a circuit-forming surface of a chip and a light-transmitting cover.
One surface of the film-like adhesive before heating at 260 ° C. was analyzed by X-ray photoelectron spectroscopy, the phosphorus concentration V ₁ was measured, the V ₁ was measured, and 10 at 260 ° C. Of the film-like adhesive after heating for a minute, _{the surface on which V 1} was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, V ₁ was 0.1 atomic. % Or more, and the reduction rate of the phosphorus concentration calculated from _{V 1} and V _{2 is 25% or less.}
The film-like adhesive contains a phosphorus-based antioxidant (z) and contains
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. Alternatively, those having no two or more types can be mentioned.

One preferred embodiment of the film-like adhesive is, for example, a film-like adhesive for bonding a circuit-forming surface of a chip and a light-transmitting cover.
One surface of the film-like adhesive before heating at 260 ° C. was analyzed by X-ray photoelectron spectroscopy, the phosphorus concentration V ₁ was measured, the V ₁ was measured, and 10 at 260 ° C. Of the film-like adhesive after heating for a minute, _{the surface on which V 1} was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, V ₁ was 0.1 atomic. % Or more, and the reduction rate of the phosphorus concentration calculated from _{V 1} and V _{2 is 25% or less.}
The film-like adhesive contains an epoxy compound (b1) and contains
One or two types of the epoxy compound (b1) selected from the group consisting of an aliphatic compound and a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above can be mentioned.

One preferred embodiment of the film-like adhesive is, for example, a film-like adhesive for bonding a circuit-forming surface of a chip and a light-transmitting cover.
One surface of the film-like adhesive before heating at 260 ° C. was analyzed by X-ray photoelectron spectroscopy, the phosphorus concentration V ₁ was measured, the V ₁ was measured, and 10 at 260 ° C. Of the film-like adhesive after heating for a minute, _{the surface on which V 1} was measured was analyzed by X-ray photoelectron spectroscopy, and when the phosphorus concentration V ₂ was measured, V ₁ was 0.1 atomic. % Or more, and the reduction rate of the phosphorus concentration calculated from _{V 1} and V _{2 is 25% or less.}
The film-like adhesive contains an acrylic resin (a) and a cross-linking agent (f).
The acrylic resin (a) has a functional group capable of binding to the cross-linking agent (f).
One or two types of the cross-linking agent (f) selected from the group consisting of an aliphatic compound and a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above can be mentioned.

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

◇ Laminated Sheet and Composite Sheet The laminated sheet according to the embodiment of the present invention includes the film-like adhesive and a resin film provided on one surface of the film-like adhesive. ..
Further, the composite sheet according to the embodiment of the present invention includes the film-like adhesive and a dying sheet provided on one surface of the film-like adhesive, and the dying sheet is a base. A material and a pressure-sensitive adhesive layer provided on one surface of the base material are provided, and the pressure-sensitive adhesive layer is arranged between the base material and the film-like adhesive.

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

When the resin films are provided on both sides of the film-like adhesive in the laminated sheet, the 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), 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 plurality of 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 the main constituent material.

Examples of the resin which is a constituent material of the resin film include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, and polymethylpentene. Polyethylene 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, etc. System-based copolymer (polymer obtained by using ethylene as a monomer); vinyl chloride-based resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer); polystyrene; Polycycloolefins; polymers such as polyethylene terephthalates, polyethylene naphthalates, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalenedicarboxylates, all aromatic polyesters in which all constituent units have aromatic cyclic groups; Polymers of two or more of the polyesters; poly (meth) acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyether ketone and the like. Be done.
Further, examples of the resin 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 preferably has a relatively small amount of the resin other than the polyester.
Further, as the resin, for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

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

Examples of the release film include those composed of a plurality of layers including a resin layer and a release-treated layer provided on one surface of the resin layer.

The release film can be produced by peeling one surface of the resin layer.
The resin layer can be produced by molding or coating a resin composition containing a resin and drying it if necessary.

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

The resin layer may be composed of one layer (single layer), 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 multiple layers is not particularly limited.

Examples of the laminated sheet formed by providing the release film as a resin film on both sides of the film-like adhesive include the laminated sheet 109 shown in FIG.

Examples of the laminated sheet formed by providing the resin film only on one side of the film-like adhesive include the laminated sheet 108 shown in FIG.
In the drawings after FIG. 2, the same components as those shown in the already explained figures are designated by the same reference numerals as those in the already explained figures, and detailed description thereof will be omitted.

The laminated sheet 108 shown here is configured by providing the resin film 19 on the first surface 13a of the film-like adhesive 13.
The resin film 19 is the above-mentioned one, 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 part of the laminated sheet shown in FIG. 2 has been changed or deleted without impairing the effect of the present invention, and has been described so far. Other configurations may be added to the above. More specifically, it is as follows.

For example, the laminated sheet of the present embodiment does not have to have anything on the second surface of the film-like adhesive, but the laminated sheet is provided in a region of the second surface of the film-like adhesive near the peripheral edge. A jig adhesive layer for fixing to a jig such as a ring frame may be provided.
The adhesive layer for jigs may be, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may be.

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

FIG. 3 is a cross-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-like adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film-like adhesive 13, and the dicing sheet 10 includes a base material 11 and a base material 11. A pressure-sensitive adhesive layer 12 provided on one surface (sometimes referred to as a "first surface" in the present specification) 11a of the base material 11 is provided, and the pressure-sensitive adhesive layer 12 is a base material. It is arranged and configured between 11 and the film-like adhesive 13.
In other words, the composite sheet 101 is configured by laminating the base material 11, the pressure-sensitive adhesive layer 12, and the film-like adhesive 13 in this order in the thickness direction.
The surface of the dicing sheet 10 on the film-like adhesive 13 side (sometimes referred to as the "first surface" in the present specification) 10a is the surface of the pressure-sensitive adhesive layer 12 opposite to the base material 11 side (the present). In the specification, it is the same as 12a) (sometimes referred to as "first surface").

The composite sheet 101 further includes a release film 15 on the film-like 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-like adhesive 13 is laminated on the entire surface or almost the entire surface 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 13a 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 described in order.

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

The resin constituting the base material may be of only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The base material may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these multiple layers are the same or different from each other. The combination of these plurality of layers may be 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 within such a range, the flexibility of the composite sheet 101 and the stickability to the sticking object 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 the layers constituting the base material. means.

It is preferable that the base material 11 has high thickness accuracy, that is, the base material 11 has a thickness variation suppressed regardless of the site. Among the above-mentioned constituent materials, as a material that can be used to construct a base material having such a high accuracy of thickness, for example, polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer and the like are used. Can be mentioned.

In addition to the main constituent materials such as the resin, the base material 11 contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). May be.

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

In order to improve the adhesion of the base material 11 to other layers (adhesive layer 12 in this case) provided on the base material 11, the base material 11 is subjected to a sandblasting treatment, an unevenness treatment such as a solvent treatment, a corona discharge treatment, and an electron beam. The surface may be subjected to oxidation treatment such as irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and the like.
Further, the surface of the base material 11 may be subjected to a primer treatment.
Further, the base material 11 is an antistatic coat layer; a layer that prevents the base material 11 from adhering to other sheets and the base material 11 from adhering to the adsorption table when the composite sheets are superposed and stored. And the like.

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

The pressure-sensitive adhesive layer 12 in the dicing sheet 10 is in the form of a sheet or a film and contains a pressure-sensitive adhesive.
Examples of the pressure-sensitive 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, the "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only the resin itself having adhesiveness, but also a resin exhibiting adhesiveness when used in combination with other components such as additives, and adhesiveness due to the presence of a trigger such as heat or water. Also included are resins and the like.

The pressure-sensitive adhesive layer 12 may be composed of one layer (single layer), may be composed of a plurality of layers of two or more layers, and when the pressure-sensitive adhesive layer 12 is composed of a plurality of layers, the plurality of layers may be the same as each other. It may be different, and the combination of these plurality of 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 entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

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

The pressure-sensitive adhesive layer 12 can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer 12 can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the pressure-sensitive adhesive layer 12 and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer 12. In the present specification, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The pressure-sensitive adhesive composition may be applied 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, and a screen coater. , 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 onto the base material 11 and dried as necessary to provide 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 onto 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 the exposed surface of the pressure-sensitive adhesive layer 12 and bonding it to one surface of the base material 11 (here, the first surface 11a). good. The release film in this case may be removed at any timing of 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 includes, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, "sticky resin (I)". -1a) ”) and an energy ray-curable compound (adhesive composition (I-1); an unsaturated group is contained in the side chain of the adhesive resin (I-1a). Adhesive composition (I-2) containing the introduced energy ray-curable adhesive resin (I-2a) (hereinafter, may be abbreviated as "adhesive resin (I-2a)"); Examples thereof include a pressure-sensitive adhesive composition (I-3) containing a pressure-sensitive 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 includes, for example, the pressure-sensitive adhesive composition (I-4) containing the pressure-sensitive adhesive resin (I-1a). And so on.

The film-like 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-like adhesive 13 _{satisfies the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate.
The thickness of the film-like adhesive 13 is preferably 10 to 40 μm.
The film-like adhesive 13 can be formed by using the above-mentioned adhesive composition.

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

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 an arbitrary configuration, and the composite sheet of the present embodiment includes a release film. It may or may not be provided.

The composite sheet 101 is used by attaching an object (for example, a circuit forming surface of a chip) to the first surface 13a of the film-like 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 composite sheet shown in FIG. 3 has been changed or deleted without impairing the effect of the present invention, and has been described so far. Other configurations may be added to the above. More specifically, it is as follows.

Up to this point, the composite sheet including the dicing sheet formed 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 composed of only the base material. .. That is, the composite sheet includes a base material and a film-like adhesive provided on one surface of the base material, and an adhesive layer is formed between the base material and the film-like adhesive. It may be configured without being arranged. Examples of such a composite sheet include those in which the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3) in the laminated sheet 108 shown in FIG.

Up to this point, the composite sheet including the dicing sheet formed 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. A configured dicing sheet may be provided. Such a dicing sheet is provided, for example, on 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. There is an intermediate layer, and the one provided with. When such a dicing sheet is used, in the composite sheet, an intermediate layer is arranged between the pressure-sensitive adhesive layer and the film-like adhesive.

For example, the composite sheet of the present embodiment may include only the release film on the first surface of the film-like adhesive, but the first surface of the film-like adhesive may be formed in a 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 adhesive layer for the jig in this case is the same as that described above.

For example, when the composite sheet is viewed from above on the film-like adhesive side or the dicing sheet side and viewed in a plan view, the surface areas of the film-like adhesive and the dicing sheet may be the same or almost the same. In the composite sheet of the form, the surface area of the film-like adhesive may be smaller than the surface area of the dicing sheet, and a part of the dicing sheet (for example, the pressure-sensitive adhesive layer) may be exposed. In that case, for example, at least the peripheral edge portion in the width direction of the dicing sheet may be exposed without being covered with the film-like adhesive. Such a composite sheet may be provided with the above-mentioned adhesive layer for jigs on the exposed surface of the dicing sheet.

Up to this point, the base material, the pressure-sensitive adhesive layer, the intermediate layer, the film-like adhesive, the adhesive layer for jigs, and the release film have been shown as constituting the composite sheet. It may have other layers that do not fall under any of these.
When the composite sheet includes the other layer, the arrangement position thereof is not particularly limited.

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

◇ How to use laminated sheet (film-like adhesive) << Laminated body and its manufacturing method >>
The film-like adhesive in the laminated sheet of the present embodiment can be used, for example, as a film for adhering a light-transmitting cover to a circuit-forming surface of a chip such as a sensor.
More specifically, by using the film-like adhesive, the chip, the film-like adhesive provided on the circuit forming surface of the chip, and the surface of the film-like adhesive on the side opposite to the chip side. A laminate configured with a light transmissive cover provided above can be manufactured. In the laminated body, either one or both of the surface of the film-like adhesive on the chip side and the surface on the light transmissive cover side _{satisfy the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate. It is preferable that both satisfy the conditions of the above-mentioned V ₁ , V ₂ and P concentration reduction rates.

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

In the laminated body 801, the opposite surfaces of the chip 8 and the film-like adhesive 13, that is, the circuit forming surface 8a of the chip 8 and the surface (second surface) 13b of the film-like adhesive 13 on the chip 8 side. , Are in direct contact. Further, the opposing surfaces of the film-like adhesive 13 and the light-transmitting cover 7, that is, the first surface 13a of the film-like adhesive 13 and the surface of the light-transmitting cover 7 on the film-like adhesive 13 side (the present). In the specification, it is in direct contact with 7b) (sometimes referred to as the "second surface").
In this way, in the laminated body 801 the chip 8, the film-like adhesive 13, and the light-transmitting cover 7 are laminated in this order in the thickness direction, and the circuit forming surface 8a of the chip 8 is in the form of a film. It is arranged and configured on the adhesive 13 side.

The film-like 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 have been removed, or the laminated sheet 108 shown in FIG. The resin film 19 is removed.
In the laminated body 801, either one or both of the first surface 13a and the second surface 13b of the film-like adhesive 13 _{satisfies the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate, and both of them are described above. It is preferable to satisfy the conditions of V ₁ , V _{2 and P concentration reduction rate.}

Note that in FIG. 4, the circuit of the chip 8 is not shown. Further, reference numeral 7a indicates a surface of the light transmissive cover 7 opposite to the second surface 7b (in the present specification, it may be referred to as a “first surface”).

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-like 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 via the light transmitting cover 7 and the film-like adhesive 13 (through the light transmitting cover 7 and the film-like adhesive 13). However, it is visible.
Further, as described above, the film-like adhesive 13 has high light transmission before and after heating, and coloring is suppressed. Therefore, the laminated body 801 can stably visually recognize the visual information on the chip 8 with high accuracy.

As the chip 8, for example, a fingerprint sensor can be used, in which case the laminate 801 can be used as a fingerprint sensor module.

The laminate using the film-like adhesive is not limited to the one shown in FIG. 4, and a part of the one shown in FIG. 4 has been changed or deleted as long as the effect of the present invention is not impaired. , Other configurations may be added to those described so far.

In the laminate, for example, the circuit forming surface of the chip is bonded to one surface (second surface) of the film-like adhesive, and light is transmitted to the other surface (first surface) of the film-like adhesive. It can be manufactured by attaching a sex cover.

◇ How to use the composite sheet << Laminated body and its manufacturing method >>
The composite sheet of the present embodiment can be used in the same manner as in the case of a known composite sheet.
FIG. 5 is a cross-sectional view for schematically explaining an example of how to use the composite sheet of the present embodiment. 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-like adhesive 13 to the circuit forming surface 8a of the chip 8.

After the composite sheet 101 is attached to the chip 8, for example, the chip 8 is diced and individualized, and the film-like adhesive 13 is cut along the outer periphery of the individualized chip 8. At this time, the chip 8 can be fragmented and the film-like adhesive 13 can be cut by a known method. For example, these may be performed at the same time, or the chip 8 may be fragmented and then separately. , The film-like adhesive 13 may be cut.

Next, the individualized chips 8 are separated from the dicing sheet 10 and picked up together with the cut film-like adhesive 13. When the pressure-sensitive adhesive layer 12 is energy ray-curable, the pressure-sensitive adhesive layer 12 is energy-ray-cured to reduce the adhesive force to the film-like adhesive 13, and then the adhesive layer 12 is picked up more easily. It can be carried out.

Next, the laminated body (for example, the laminated body 801 shown in FIG. 4) can be manufactured by attaching a light-transmitting cover to the second surface of the film-like adhesive 13 after cutting and picking up.
In the laminated body, either one or both of the first surface and the second surface of the film-like adhesive _{satisfy the above-mentioned conditions of V 1} , V ₂ and P concentration reduction rate, and both of them satisfy the above-mentioned 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 attached to the chip, and after the chip is individualized and after the film-like adhesive is cut, the film-like adhesive after cutting is provided with a light-transmitting cover. Although the case of bonding has been described, the order of bonding the chip and the light-transmitting cover to the film-like adhesive may be reversed. That is, after the first surface of the film-like adhesive is attached to the second surface of the light-transmitting cover, the light-transmitting cover is die-cut into individual pieces, the film-like adhesive is cut, and if necessary. After the pressure-sensitive adhesive layer is energy ray-cured, the light-transmitting cover after individualization is picked up together with the film-like adhesive after cutting from the dying sheet, and then the film-like adhesive after cutting and picking up is picked up. The laminate (for example, the laminate 801 shown in FIG. 4) can also be manufactured by attaching the 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 shown below.

<Raw materials for manufacturing adhesive compositions>
In this example and comparative example, the raw materials used for producing the adhesive composition 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: Cresol novolac type epoxy resin to which an acryloyl group is added (“CNA147” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 518 g / eq, number average molecular weight 2100, unsaturated group content and epoxy group content Is the same amount)
(B1) -2: Hydrogenated bisphenol A type epoxy resin ("Epolite 4000" manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 310-340 g / eq)
[Phenol resin (b2)]
(B2) -1: Aralkyl type phenol resin (“HE100C-10” manufactured by Air Water Chemical Inc.)
[Curing accelerator (c)]
(C) -1: Triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd.)
[Filler (d)]
(D) -1: Spherical silica modified with a methacrylic group (“YA050C-MJE” manufactured by Admatex, average particle size 50 nm)
(D) -2: Spherical silica modified with an epoxy group ("YA050C-MKK" manufactured by Admatex, average particle size 50 nm)
(D) -3: Silica filler modified with an epoxy group (“SC2050MA” manufactured by Admatex, average particle size 500 nm)
[Crosslinking agent (f)]
(F) -1: Trimerizing isocyanate 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.)
[Phosphorus-based antioxidant (z)]
(Z) -1: Bis (decyl) pentaerythritol diphosphite ("JPE-10" manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite ester)

[Example 1]
<< Manufacture of film-like adhesive >>
<Manufacturing of adhesive composition>
Acrylic resin (a) -1 (57.2 parts by mass), epoxy compound (b1) -1 (18 parts by mass), phenol resin (b2) -1 (3 parts by mass), curing accelerator (c) -1 (0.5 parts by mass), filler (d) -1 (20 parts by mass), cross-linking agent (f) -1 (0.5 parts by mass) and phosphorus-based antioxidant (z) -1 (0.8 parts by mass) By dissolving or dispersing (part by mass) in methyl ethyl ketone and stirring at 23 ° C., an adhesive composition having a total concentration of all components other than methyl ethyl ketone of 32% by mass was obtained. The blending amounts of the components other than the methyl ethyl ketone shown here are all the blending amounts of the target product containing no solvent component.

<Manufacturing of film-like adhesive>
A release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate (PET) film is peeled by a silicone treatment is used, and the adhesion obtained above is applied to the peeled surface. The agent composition is applied and dried by heating at 100 ° C. for 2 minutes to form a film-like adhesive having a thickness of 20 μm, and the release film and the film-like adhesive are laminated in these thickness directions. The constructed adhesive sheet was obtained.

<< Evaluation of film-like adhesive >>
<Measurement of shear strength>
Using a tape mounter (Lintec's "Adwill RAD2500 m / 12"), a dicing sheet (Lintec's "Adwill D-678") was placed on a 6-inch silicon wafer (with a sticking temperature of 23 ° C and a sticking 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 the ring frame.
Next, using a dicing device ("DFD6362" manufactured by DISCO), dicing is performed by a dicing blade ("NBC-ZH2050-SE27HECC" manufactured by DISCO) under the conditions of a blade rotation speed of 30,000 rpm and a cutting speed of 40 mm / s, and the size is increased. A plurality of 2 mm × 2 mm silicon chips (hereinafter, may be referred to as “silicon chip group”) were obtained. The above dicing sheet is formed by laminating a base material and an adhesive layer, and is used for dicing. Occasionally, a dicing blade cut into a region of 20 μm in depth of the substrate in the dicing sheet.

Next, the adhesive sheet obtained above was attached to the silicon chip group obtained above with a film-like adhesive therein while heating at 60 ° C. At this time, the adhesive sheet was attached to the surface (exposed surface) of the silicon chips in the silicon chip group opposite to the side to which the dicing sheet was attached. Then, the adhesive sheet after the attachment was cut along the outer circumference 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.

Next, the release film is removed from the film-like adhesive in the laminate, and the exposed surface of the newly generated film-like adhesive is exposed to a size of 30 mm × 30 mm and a thickness of 300 μm using a manual die bonder. It was affixed to the surface of a copper plate. At this time, the film-like adhesive was attached by applying a force of 2.45 N (250 gf) and pressing it against the copper plate while heating at 125 ° C. Further, these bonded products were heated at 175 ° C. for 5 hours to obtain a test piece.

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

<Measurement of linear transmittance of light (400 to 800 nm) before heating>
The film-like adhesive obtained above was attached to one surface of a glass preparation (thickness 0.9 mm) while heating at 40 ° C. The film-like adhesive was not heat-treated immediately after its production until its application.
Next, the portion of the film-like adhesive after application that protrudes from the glass preparation is cut, and the film-like adhesive and the glass preparation of the same size are in a state where the positions of their peripheral edges are the same. A test piece (hereinafter, referred to as "pre-heating test piece") configured by being laminated in these thickness directions was obtained.

Regarding the glass preparation used for producing the preheating test piece, a straight line of light (400 to 800 nm) was used in advance using a spectrophotometer (“UV-3101PC” manufactured by Shimadzu) before the preparation of the preheating test piece. The transmittance (hereinafter referred to as "reference linear transmittance") was measured.
For the preheating test piece obtained above, the linear transmittance of light (400 to 800 nm) was measured 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 obtained from the film before heating. It was adopted as the linear transmittance of light (400 to 800 nm) of the state adhesive (that is, the linear transmittance before heating). The results are shown in Table 1.

<Measurement of linear transmittance after heating light (400-800 nm)>
Using an electric furnace, the test piece after measuring the linear transmittance of the above light (400 to 800 nm) before heating was heated at 260 ° C. for 10 minutes.
Then, the test piece after heating was allowed to cool to the same temperature as room temperature.
Next, with respect to the test piece after heating and cooling (hereinafter referred to as "test piece after heating"), the linear transmittance of light (400 to 800 nm) is measured by the same method as in the case of the test piece before heating described above. bottom.
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 is obtained from the film after heating. It was adopted as the linear transmittance of light (400 to 800 nm) of the state adhesive (that is, the linear transmittance after heating). The results are shown in Table 1.

<Evaluation of fingerprint recognition before heating by RGB>
A digital camera (Canon's "IXY650") is placed in front of the pad of the left index finger, and the distance between the surface of the pad of the left index finger and the surface of the camera lens is adjusted to 50 mm, and in this state. The imaging data of the fingerprint of the index finger of the left hand (hereinafter referred to as "reference imaging data") was acquired in the macro mode.
While maintaining the arrangement relationship between the left index finger and the digital camera, the preheating test piece was further arranged between the pad of the left index finger and the digital camera. At this time, the straight line connecting the pad of the index finger of the left hand and the digital camera is relative to the exposed surface of the glass preparation in the preheating test piece (that is, the surface opposite to the surface to which the film-like adhesive is attached). The preheating test piece was arranged so as to be orthogonal to each other and the exposed surface was on the digital camera side. Under this condition, the fingerprint imaging data of the index finger of the left hand (hereinafter referred to as "pre-heating transmission imaging data") was acquired in the macro mode by the same method as when the reference imaging data was acquired.

Using graphic software (Microsoft's "Paint"), the reference imaging data and pre-heating transmission imaging data obtained above are expanded, and the colors of the peaks and valleys of the fingerprint are extracted from each data. It was digitized in RGB.
The value obtained by subtracting the R value of the fingerprint peak acquired from the reference imaging data from the R value of the fingerprint peak acquired from the pre-heating transmission imaging data is the R value of the fingerprint peak obtained during the pre-heating evaluation. Adopted as a value. By the same method as this, the G value and the B value of the peak part of the fingerprint at the time of evaluation before heating were obtained.
In the same method as above, the value obtained by subtracting the R value of the fingerprint valley acquired from the reference imaging data from the R value of the fingerprint valley acquired from the pre-heating transmission imaging data is obtained during the pre-heating evaluation. It was adopted as the R value of the valley of the fingerprint. By the same method as this, the G value and the B value of the valley portion of the fingerprint at the time of evaluation before heating were obtained.
Further, the absolute value of the difference between the R value of the mountain portion and the R value of the valley portion (hereinafter, may be referred to as “absolute value ΔR”) is calculated, and the G value of the peak portion and the valley portion are calculated. The absolute value of the difference from the G value of the above (hereinafter, may be referred to as "absolute value ΔG") is calculated, and 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. It may be described as "absolute value ΔB").

Based on these calculated values, the fingerprint recognition property of the film-like 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: The absolute value ΔR, the absolute value ΔG, and the absolute value ΔB are all less than 5.

<Evaluation of fingerprint recognition after heating by RGB>
Fingerprints of the film-like adhesive after heating by RGB by the same method as in the case of "evaluation of fingerprint recognition before heating" except that the test piece after heating was used instead of the test piece before heating. Recognition was evaluated.
More specifically, at the time of this evaluation, "transmissive imaging data after heating" was acquired instead of the transmission imaging data before heating. Further, using this post-heating transmission imaging data, instead of the R value, G value and B value of the fingerprint peak during the pre-heating evaluation, the R value, G value and the fingerprint peak during the post-heating evaluation are used. The B value was obtained, and instead of the R value, G value and B value of the fingerprint valley portion at the time of pre-heating evaluation, the R value, G value and B value of the fingerprint valley portion at the time of post-heating evaluation 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 pre-heating evaluation, the absolute value ΔR, absolute value ΔG and absolute value ΔB at the time of post-heating evaluation Was calculated. The results are shown in Table 1.

<Visual evaluation of fingerprint recognition before heating>
Five observers were randomly selected, and the fingerprints were visually observed one by one by the method shown below.
That is, one observer is placed in front of the pad of the left index finger, and the distance between the surface of the pad of the left index finger and the observer's eyes is adjusted to 150 mm. The fingerprint was directly observed visually.
While maintaining the arrangement relationship between the left index finger and the observer, the preheating test piece was further arranged between the pad of the left index finger and the observer. The arrangement form of the preheating test piece at this time was the same as that of the preheating test piece at the time of the above-mentioned "evaluation of fingerprint recognition before heating by RGB". Under this condition, the fingerprint of the index finger of the left hand was visually observed through the preheating test piece in the same manner as in the case of direct visual observation as described above.

By this method, all five observers visually observe the fingerprint directly and through the preheating test piece, and the appearance of the fingerprint through the preheating test piece and the appearance of the fingerprint directly through the test piece. , The fingerprint recognition of the film-like adhesive before heating was visually evaluated according to the following criteria. 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) who judged that there was no difference in the appearance of fingerprints".
A: All five observers judged that there was no difference in the appearance of fingerprints.
B: Four out of five observers determined that there was no difference in the appearance of fingerprints.
C: Two or more of the five observers determined that the fingerprint colors were different from each other and the appearance was different.

<Visual evaluation of fingerprint recognition after heating>
A film-like adhesive after heating visually in the same manner as in the case of "visual evaluation of fingerprint recognition before heating" except that the test piece after heating was used instead of the test piece before heating. Fingerprint recognition 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), 0 of one surface of the film-like adhesive (hereinafter referred to as “pre-heated film-like adhesive”) obtained above. an area of .1mm × 1mm, measuring angles 45 °, by survey scan by the beam diameter 18 [mu] m, performs XPS analysis to determine the P concentration _{V 1} of the this plane. At this time, the peak detected in the binding energy range of 123 to 143 eV was determined to be a P2p spectrum. Aluminum was used as the X-ray source. The film-like adhesive was not heat-treated immediately after its production until this measurement. The results are shown in Table 1.

<Measurement of _{V 2>}
Using an electric furnace, before heating after measuring V ₁ of the above film-like adhesive was heated for 10 minutes at 260 ° C..
The heated film-like adhesive was then allowed to cool to the same temperature as room temperature.
Then, the heating and film-like adhesive after cooling (hereinafter, referred to as "post-film adhesive heating") among the measurement surface of the V _1, same as in the heating before film-like adhesive described above in the method, it carried out XPS analysis to determine the P concentration _{V 2.} The results are shown in Table 1.

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

<< Manufacture and evaluation of film-like adhesives >>
[Examples 2 to 5]
The point that either one or both of the types and amounts of the compounding components were changed at the time of manufacturing the adhesive composition so that the types and contents of the components contained in the adhesive composition were as shown in Table 1. A film-like 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 1-2]
The point that either one or both of the types and amounts of the compounding components were changed at the time of manufacturing the adhesive composition so that the types and contents of the components contained in the adhesive composition were as shown in Table 2. Except for the above, an attempt was made to produce and evaluate a film-like adhesive by the same method as in Example 1. 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 evaluation result column in Tables 1 and 2 means that the item could not be evaluated (when the data could not be acquired and the data was less than the detection limit). Including the case) or it means that the data could not be calculated.

As is clear from the above results, in Examples 1 to 5, the film-like adhesives before and after heating at 260 ° C. had high light transmittance, suppressed coloring, and high fingerprint recognition. In Examples 1 to 5, the linear transmittance of the light (400 to 800 nm) of the film-like adhesive before heating at 260 ° C. is 95% or more (95 to 97%), and the film-like adhesive after heating at 260 ° C. The linear transmittance of the 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-like adhesive was 48 N / 2 mm □ or more (48 to 95 N / 2 mm □), and the adhesive strength of the film-like adhesive was sufficiently strong.

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

On the other hand, in Comparative Example 1, the film-like adhesive before heating at 260 ° C. had high light transmittance and the coloring was suppressed, but the film-like adhesive after heating at 260 ° C. was light-transmitting. The property was low, coloring was not suppressed, and fingerprint recognition was low.
In Comparative Example 1, it was presumed that the film-like adhesive did not contain an antioxidant, so that the coloring due to heating was not suppressed.
In Comparative Example 1, naturally, V ₁ and V ₂ were below the detection limit, and the P concentration reduction rate could not be calculated.

In Comparative Example 2, the film-like adhesive at the stage before heating at 260 ° C. had already low light transmittance, was white and turbid, and had low fingerprint recognition. Therefore, the film-like adhesive after heating at 260 ° C. also remained white and turbid, and the fingerprint recognition property was low.
In Comparative Example 2, since the filler (d) -3 having a large average particle size was used, it was presumed that the film-like adhesive became cloudy white. This is clear from the comparison between the film-like adhesive of Example 4 and the film-like adhesive of Comparative Example 2, which are very similar in composition to each other, 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 by heating due to the influence of this turbidity, but since the film-like adhesive does not contain an antioxidant, naturally coloring by heating is not suppressed. It was speculated.
In Comparative Example 2, naturally, V ₁ and V ₂ were below the detection limit, and the P concentration reduction rate could not be calculated.

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

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

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

Claims (9)

A film-like adhesive for bonding the circuit forming surface of a chip and a light-transmitting cover.
For one side of the front of the film adhesive is heated at 260 ° C., it was analyzed by X-ray photoelectron spectroscopy to measure the concentration V ₁ of the phosphorus,
Of the film-like 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 When measuring
The V ₁ is 0.1 atomic% or more,
A film-like adhesive having a phosphorus concentration reduction rate of 25% or less calculated from _{V 1} and V _2. The linear transmittance of light having a wavelength of 400 to 800 nm of the film-like 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-like 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-like adhesive according to claim 1 or 2, wherein the film-like adhesive contains an aliphatic epoxy compound. The film-like adhesive contains a phenol resin (b2) and contains
The method according to any one of claims 1 to 3, wherein the ratio of the content of the phenol resin (b2) to the total mass of the film-like adhesive in the film-like adhesive is 10% by mass or less. Film-like adhesive. The film-like adhesive according to any one of claims 1 to 4, wherein the film-like adhesive contains an aliphatic phosphite ester as an antioxidant. The film-like adhesive contains an acrylic resin and an aliphatic multivalent isocyanate-based cross-linking agent.
The film-like adhesive according to any one of claims 1 to 5, wherein the acrylic resin has a functional group capable of binding to the cross-linking agent. A laminated sheet comprising the film-like adhesive according to any one of claims 1 to 6 and a resin film provided on one surface of the film-like adhesive. The 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 are provided.
The dicing sheet includes a base material and an adhesive layer provided on one surface of the base material.
A composite sheet in which the pressure-sensitive adhesive layer is arranged between the base material and the film-like adhesive. The circuit-forming surface of the chip is attached to one surface of the film-like adhesive according to any one of claims 1 to 6, and the light-transmitting cover is attached to the other surface of the film-like adhesive. A method for producing a laminated body, wherein the chip, the film-like adhesive, and the light-transmitting cover are laminated in this order to obtain a laminated body.

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