KR20200133717A - Film adhesive and sheet for semiconductor processing - Google Patents

Abstract

A film adhesive having the following characteristics: (I) The initial detection temperature of the melt viscosity of this film adhesive after storage at 40°C for 168 hours is T ₁₆₈ , and the initial detection temperature of the melt viscosity of this film adhesive before this storage a when the T _0, the T ₁₆₈ and this is the difference △ T ₁₆₈ of T ₀ is less than 10 ℃, also (II) is, when the gel fraction prior to preserve the adhesive film at 40 ℃ as W _0, W ₀ is 15% or less film adhesive.

Description

Film adhesive and sheet for semiconductor processing

The present invention relates to a film adhesive and a sheet for semiconductor processing.

This application claims priority based on Japanese Patent Application No. 2018-057006 for which it applied to Japan on March 23, 2018, and uses the content here.

The semiconductor chip is usually die-bonded to the circuit formation surface of the substrate with a film-like adhesive affixed on the back surface thereof. Then, a semiconductor package is produced using the obtained one, and finally, a target semiconductor device is produced using the semiconductor package.

A semiconductor chip provided with a film adhesive on the back surface is produced, for example, by dividing (cutting) a semiconductor wafer provided with a film adhesive on the back surface together with a film adhesive. As described above, as a method of dividing a semiconductor wafer into semiconductor chips, for example, a method of dicing a semiconductor wafer into a film adhesive using a dicing blade is known. In this case, the film-like adhesive before dividing (cutting) is laminated on a dicing sheet used to fix a semiconductor wafer during dicing, and is sometimes used as an integrated dicing die bonding sheet.

As a film adhesive, various things have been disclosed so far depending on the purpose.

For example, heat containing 5 to 15% by weight of a thermoplastic resin component and 45 to 55% by weight of a thermosetting resin component as main components, and a melt viscosity at 100°C before thermosetting of 400 Pa·s or more and 2500 Pa·s or less. A curable die-bonding film is disclosed (see Patent Document 1).

This thermosetting die-bonding film is said to be excellent in adhesion to an adherend, and to prevent contamination of a substrate or a semiconductor chip due to bleeding of the adhesive.

In addition, the gel fraction in the organic component after heat curing by heat treatment at 120°C for 1 hour is within the range of 20% by weight or less, and the organic component after heat curing by heat treatment at 175°C for 1 hour A thermosetting die-bonding film in which the gel fraction is in the range of 10 to 30% by weight is disclosed (refer to Patent Document 2). It is said that this thermosetting die-bonding film suppresses curing shrinkage after die bonding, thereby preventing the occurrence of warpage on the adherend.

Japanese Patent Laid-Open Publication No. 2008-244464 Japanese Unexamined Patent Publication No. 2011-103440

The properties of the film-like adhesive may change by reacting the crosslinkable or curable component, which is a component thereof, during storage until use. As described above, the film-like adhesive, which is easily changed in properties and has low storage stability, may not be able to sufficiently exhibit its intended action at the time of use. In addition, the reliability of a semiconductor package manufactured using such a film adhesive and a semiconductor chip may be deteriorated.

On the other hand, as described above, the thermosetting die-bonding film (film adhesive) described in Patent Document 1 has a melt viscosity at 100°C before heat curing within a specific range, but the melt viscosity before and after storage is stable. It is not clear whether or not.

In the thermosetting die-bonding film (film adhesive) described in Patent Document 2, the gel fraction in the organic component after heat curing falls within a specific range, but it is not clear whether the gel fraction before and after storage is stable.

As described above, it is not clear whether or not the thermosetting die-bonding film (film adhesive) described in Patent Documents 1 to 2 has high storage stability and whether or not a highly reliable semiconductor package can be manufactured.

It is an object of the present invention to provide a film adhesive capable of producing a semiconductor package having high storage stability and high reliability based on this, and a sheet for semiconductor processing provided with the film adhesive.

In order to solve the above problem, the present invention is the above-described case where the storage time is 168 hours when the film adhesive is stored at 40°C and the initial detection temperature of the melt viscosity is determined for the film adhesive before and after storage. the initial detected temperature T is less than _168, and the initial detected temperature T ₀ difference △ T ₁₆₈ of the 10 ℃ before storage, less gel fraction W ₀ of the said film adhesive prior to preserve the adhesive the film at 40 ℃ 15% Provides a film-like adhesive.

In the present invention, when the film adhesive is stored at 40°C and the gel fraction is measured for the film adhesive before and after storage, the gel fraction W ₁₆₈ when the storage time is 168 hours, and the above before storage There is provided a film adhesive having a change rate RW ₁₆₈ of the gel fraction determined from the gel fraction W ₀ , when the storage time is 168 hours, 200% or less, and the gel fraction W ₀ 15% or less.

Further, in the present invention, when the film adhesive is stored at 40°C, and the elongation at break is measured in accordance with JIS K7161:1994 for the film adhesive before and after storage, the above fracture when the storage time is 168 hours. The film before storage of the film-like adhesive at 40° C. where the reduction ratio RF ₁₆₈ of the breaking elongation when the storage time is 168 hours is less than 30%, determined from the elongation F ₁₆₈ and the breaking elongation F ₀ before storage. A film adhesive having a gel fraction W ₀ of 15% or less of the upper adhesive is provided.

Further, the present invention provides a sheet for semiconductor processing provided with a support sheet and provided with the film-like adhesive on the support sheet.

That is, the present invention includes the following aspects.

[1] A film adhesive having the following properties:

(I) When the initial detection temperature of the melt viscosity of the film adhesive after storage at 40°C for 168 hours is T ₁₆₈ and the initial detection temperature of the melt viscosity before storage of the film adhesive is T ₀ , the T _{The difference between 168} and T ₀ ΔT ₁₆₈ is less than 10°C, and

(II) When the gel fraction before storing the film-like adhesive at 40° C. is W ₀ , the W ₀ is 15% or less.

[2] A film adhesive having the following properties:

(I') When the gel fraction of the film adhesive after storage at 40°C for 168 hours is W ₁₆₈ , and the gel fraction before storage of the film adhesive is W ₀ , it is determined from W ₁₆₈ and W ₀ The rate of change of the gel fraction RW ₁₆₈ is 200% or less, and (II') W ₀ is 15% or less.

[3] A film adhesive having the following properties:

(I") The elongation at break measured according to JIS K7161:1994 after storage at 40°C for 168 hours of the film adhesive was F ₁₆₈ , and measured according to JIS K7161:1994 before storage of the film adhesive. When the elongation at break is F ₀ , the rate of decrease in breaking elongation RF ₁₆₈ obtained from F ₁₆₈ and F ₀ is less than 30%, and (II") the film form before storage of the film-like adhesive at 40°C When the gel fraction of the adhesive is W ₀ , the W ₀ is 15% or less.

[4] a supporting sheet,

A sheet for semiconductor processing comprising the film adhesive according to any one of [1] to [3] provided on the support sheet.

[5] The film adhesive according to [1], further having the following properties:

(III) When the gel fraction of the film adhesive after storage at 40°C for 168 hours is W ₁₆₈ , and the gel fraction before storage of the film adhesive is W ₀ , it is determined from the W ₁₆₈ and the W ₀ The rate of change of the gel fraction RW ₁₆₈ is 200% or less.

[6] The film adhesive according to any one of [1] to [3], further having the following characteristics:

(IV) Fracture elongation measured in accordance with JIS K7161:1994 after storage at 40°C for 168 hours of the film adhesive is F ₁₆₈ , and fracture measured in accordance with JIS K7161:1994 before storage of the film adhesive When the elongation is F ₀ , the reduction ratio RF ₁₆₈ of the fracture elongation determined from the F ₁₆₈ and F ₀ is less than 30%.

According to the present invention, there are provided a film adhesive capable of producing a semiconductor package having high storage stability and high reliability based on this, and a sheet for semiconductor processing provided with the film adhesive.

1 is a cross-sectional view schematically showing a film adhesive according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing an embodiment of the sheet for semiconductor processing of the present invention.
3 is a cross-sectional view schematically showing another embodiment of the sheet for semiconductor processing of the present invention.
4 is a cross-sectional view schematically showing still another embodiment of the sheet for semiconductor processing of the present invention.
5 is a cross-sectional view schematically showing another embodiment of the sheet for semiconductor processing of the present invention.

◇Film adhesive

<<1st Embodiment>>

The film adhesive according to the first embodiment of the present invention has a storage time of 168 hours when the film adhesive is stored at 40°C and the initial detection temperature of the melt viscosity is determined for the film adhesive before and after storage. If the initial detected temperature is T _168, and is the initial detected temperature is lower than the difference △ T ₁₆₈ is 10 ℃ of T ₀ before storage, the gel fraction W ₀ of the film-like adhesive prior to preserve the adhesive the film at 40 ℃ It is 15% or less.

That is, the film-like adhesive according to the first embodiment of the present invention has the following properties:

(I) When the initial detection temperature of the melt viscosity of the film adhesive after storage at 40°C for 168 hours is T ₁₆₈ and the initial detection temperature of the melt viscosity before storage of the film adhesive is T ₀ , the T _{The difference between 168} and T ₀ ΔT ₁₆₈ is less than 10°C, and

(II) When the gel fraction before storing the film-like adhesive at 40° C. is W ₀ , the W ₀ is 15% or less.

The film adhesive of the first embodiment has curability, preferably has thermosetting, and preferably has pressure-sensitive adhesiveness. The film-like adhesive having both thermosetting and pressure-sensitive adhesive properties can be adhered by lightly pressing on various adherends in an uncured state.

Further, the film-like adhesive may be heated and softened to be affixed to various adherends. By curing, the film-like adhesive eventually becomes a cured product having high impact resistance, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

As described above, the film adhesive of the first embodiment has a small ΔT ₁₆₈ (=T ₁₆₈ -T ₀ ), and even when stored at 40°C for 168 hours, a change in melt viscosity is suppressed, and storage stability is high. A film-like adhesive that satisfies these conditions is not limited to these storage conditions, and has high storage stability throughout the storage conditions that are usually applied, suppresses changes in properties during storage, and sufficiently exhibits the intended action at the time of use. It is possible to indicate. And, by using such a film-like adhesive, a highly reliable semiconductor package can be manufactured.

Further, the film-like adhesive of the first embodiment has a small W ₀ , and makes it possible to manufacture a highly reliable semiconductor package regardless of the presence or absence of the storage.

In the film adhesive of the first embodiment, as described above, ΔT ₁₆₈ is less than 10°C, preferably 9.5°C or less, more preferably 9°C or less, even more preferably 8°C or less, for example , 6°C or less and 3°C or less may be used.

In the film adhesive of the first embodiment, the lower limit of ΔT ₁₆₈ is not particularly limited, but is usually 0°C. That is, in the film adhesive of the first embodiment, ΔT ₁₆₈ is preferably 0°C or higher.

In the film adhesive of the first embodiment, ΔT ₁₆₈ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower and upper limits. For example, ΔT ₁₆₈ is preferably 0°C or more and less than 10°C, more preferably 0 to 9.5°C, still more preferably 0 to 9°C, particularly preferably 0 to 8°C, for example, Any of 0 to 6°C and 0 to 3°C may be used. As another aspect, ΔT ₁₆₈ may be 0 to 7°C. However, these are examples of ΔT ₁₆₈ .

In the film adhesive of the first embodiment, T ₀ is not particularly limited, but it is preferably 35 to 100°C, more preferably 40 to 90°C, and particularly preferably 45 to 80°C. As another aspect, T ₀ may be 59 to 71°C. When T ₀ is equal to or greater than the above lower limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. When T ₀ is equal to or less than the above upper limit, the handleability of the film-like adhesive is further improved.

The film-like adhesive according to the first embodiment, T ₁₆₈ is not particularly limited, it is preferable that the 35~109.5 ℃, more preferably 40~99.5 ℃, that the 45~89.5 ℃ is particularly preferred. Further, as another aspect, T is ₁₆₈ or may be 59~78 ℃. When T ₁₆₈ is equal to or greater than the above lower limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher.

When T ₁₆₈ is equal to or less than the above upper limit, the handleability of the film adhesive is further improved.

The initial detection temperature T _t of the melt viscosity of the film adhesive according to the present embodiment is a known method for the film adhesive having a storage time at 40° C. of t time (t is a number of 0 or more). It is obtained by measuring with That is, using a capillary rheometer, a film-like adhesive to be measured is set in the cylinder (capillary), and while contacting the inner wall of the cylinder, along the inner wall, the longitudinal direction of the cylinder (in other words, the central axis With a piston that can move in the direction), a certain amount of force is applied to the film-like adhesive in this cylinder to maintain the state (loaded state, for example, 5.10 N), while raising the temperature of the film-like adhesive (for example, , The temperature was raised from 50 to 120°C at 10°C/min). Then, extrusion of the film-like adhesive to the outside of the cylinder from the hole formed in the tip of the cylinder (the tip of the film-like adhesive in the direction in which the force is applied) (for example, a hole with a diameter of 0.5 mm and a height of 1.0 mm) The temperature of the film adhesive when it is started, that is, when detection of the melt viscosity of the film adhesive is started, is adopted as the initial detection temperature T _t (°C) of the film adhesive. By this method, T ₁₆₈ and T ₀ are obtained. The size and shape of the film-like adhesive provided for measurement can be appropriately adjusted in consideration of the size of the cylinder and the like. For example, a cylindrical test piece having a diameter of 10 mm and a height of 20 mm is preferable.

In addition, in this specification, "melt viscosity" means a melt viscosity measured by the above-described method unless otherwise specified.

When storing the film adhesive which is a measurement object of T _t at 40 degreeC, it is preferable to store in an air atmosphere, it is preferable to stand still, and it is preferable to store in a dark place. And, it is more preferable to store so as to satisfy these two or more conditions, and it is particularly preferable to store so as to satisfy all of the conditions.

When storing the film adhesive which is a measurement object of T _t at 40 degreeC, it is preferable to start storage immediately after preparation of this film adhesive.

In the film adhesive of the first embodiment, as described above, the gel fraction W ₀ is 15% or less, preferably 13% or less, more preferably 11% or less, and particularly preferably 9% or less. When W ₀ is equal to or less than the above upper limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher.

In the film adhesive of 1st Embodiment, the lower limit of W ₀ is not specifically limited.

In the film adhesive of 1st Embodiment, it is preferable that it is 3% or more, and, as for W ₀ , it is more preferable that it is 5% or more. When W ₀ is equal to or greater than the above lower limit, the handleability of the film-like adhesive is improved, and the sticking of the film-like adhesive to the semiconductor wafer becomes easier. Further, even if the layer adjacent to the film-like adhesive such as a substrate has an uneven surface, the followability of the film-like adhesive with respect to this uneven surface is improved.

In the film adhesive of the first embodiment, W ₀ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, in one embodiment, W ₀ is preferably 3 to 15%, more preferably 3 to 13%, still more preferably 3 to 11%, and particularly preferably 3 to 9%. Further, as another aspect, W ₀ is preferably 5 to 15%, more preferably 5 to 13%, further preferably 5 to 11%, and particularly preferably 5 to 9%. As another aspect, W ₀ may be 3 to 8% or 5 to 8%. However, these are examples of W ₀ .

In this embodiment, the gel fraction W ₀ can be measured by a known method.

For example, 0.5 g of a test piece of a sheet-like film adhesive having a size of 2.5 cm×4.0 cm×600 μm was wrapped with a polyester mesh, and the test piece in this state was placed in methyl ethyl ketone (300 ml) at 23°C. After immersing for 24 hours, drying the test piece after immersion (for example, drying at 120°C for 1 hour), and then storing the dried test piece in an environment of 23°C and 50% relative humidity for 24 hours, the mass of the test piece Measure. From the measured value of the test piece and the mass of the test piece before immersion, W ₀ (%) can be calculated by the following equation.

The melt viscosity of the film-like adhesive of the first embodiment, T _t such as T ₀ or T ₁₆₈ , and ΔT ₁₆₈ and W ₀ (hereinafter, encompassing these, may be referred to as ``melt viscosity, etc.'') All can be suitably adjusted, for example, by adjusting the kind and amount of components contained in the film adhesive. For example, the type and content ratio of the constituent units in the polymer component (a) described later, which are components of the film adhesive, the constituent components of the epoxy resin (b1), the three-dimensional structure of the thermosetting agent (b2), and curing By controlling the reactivity of the accelerator (c) and the average particle diameter of the filler (d), the above-described melt viscosity and the like can be appropriately adjusted. However, these are only an example of a method for controlling the melt viscosity and the like described above.

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

On the other hand, in the present specification, it is not limited to the case of a film adhesive, and "the multiple layers may be the same or different from each other" means "all the layers may be the same, all layers may be different, and only some of the layers are the same. It means "may be good", and "the multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer are different from each other".

The thickness of the film-like adhesive of the first embodiment is not particularly limited, but it is preferably 1 to 50 µm, more preferably 3 to 40 µm, and particularly preferably 5 to 30 µm. When the thickness of the film-like adhesive is more than the above lower limit, the adhesion of the film-like adhesive to the adherend (semiconductor wafer, semiconductor chip) becomes higher. When the thickness of the film-like adhesive is less than or equal to the above upper limit, the film-like adhesive can be more easily cut in the manufacturing process of a semiconductor chip to be described later, and the amount of cut pieces derived from the film-like adhesive can be further reduced. have.

Here, the "thickness of the film adhesive" means the thickness of the entire film adhesive, for example, the thickness of the film adhesive consisting of multiple layers means the total thickness of all layers constituting the film adhesive. do.

In addition, in this specification, "thickness" means a value measured with a static pressure thickness meter.

The film-like adhesive can be formed from an adhesive composition containing the constituent material. For example, a film adhesive can be formed on a target site by coating an adhesive composition on a surface to be formed of a film adhesive and drying as necessary.

In the adhesive composition, the ratio of the content between the components that do not vaporize at room temperature is usually the same as the ratio of the content between the components of the film adhesive. In addition, in this specification, "normal temperature" means a temperature which is not specifically cooled or heated, that is, a normal temperature, and a temperature of 15-25 degreeC etc. are mentioned, for example.

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

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 containing the solvent is preferably dried at 70 to 130°C for 10 seconds to 5 minutes, for example.

<<2nd embodiment>>

In the film adhesive according to the second embodiment of the present invention, when the film adhesive is stored at 40°C and the gel fraction is measured for the film adhesive before and after storage, the gel when the storage time is 168 hours. The rate of change RW ₁₆₈ of the gel fraction when the storage time is 168 hours, determined from the fraction W ₁₆₈ and the gel fraction W ₀ before storage, is 200% or less, and the gel fraction W ₀ is 15% or less. .

As another aspect, the film-like adhesive according to the second embodiment of the present invention has the following properties:

(I') When the gel fraction of the film adhesive after storage at 40°C for 168 hours is W ₁₆₈ , and the gel fraction before storage of the film adhesive is W ₀ , it is determined from W ₁₆₈ and W ₀ The change rate RW ₁₆₈ of the paper gel fraction is 200% or less, and

(II') W ₀ is 15% or less.

As described above, the film-like adhesive of the second embodiment has a small RW ₁₆₈ , and even when stored at 40° C. for 168 hours, the change in the gel fraction is suppressed, and storage stability is high. A film-like adhesive that satisfies these conditions is not limited to these storage conditions, and has high storage stability over the storage conditions that are usually applied. And, by using such a film-like adhesive, a highly reliable semiconductor package can be manufactured.

In addition, the film-like adhesive of the second embodiment has a small W ₀ , and makes it possible to manufacture a highly reliable semiconductor package regardless of the presence or absence of the storage.

In the film adhesive of the second embodiment, as above, RW ₁₆₈ is 200% or less, preferably 185% or less, more preferably 170% or less, even more preferably 155% or less, as described above, for example, Any of 140% or less and 125% or less may be used.

In the film adhesive of the second embodiment, the lower limit of RW ₁₆₈ is not particularly limited, but is usually 100%. That is, in the film adhesive of 2nd Embodiment, it is preferable that _RW168 is 100% or more. A film-like adhesive having these properties can be produced more easily.

In the film adhesive of the second embodiment, RW ₁₆₈ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, RW ₁₆₈ is preferably 100 to 200%, more preferably 100 to 185%, still more preferably 100 to 170%, particularly preferably 100 to 155%, for example 100 to 140 Any of% and 100 to 125% may be used. As another aspect, 113-150% may be sufficient. However, these are examples of RW ₁₆₈ .

In the film adhesive of the second embodiment, as described above, W ₀ is 15% or less, preferably 13% or less, more preferably 11% or less, and particularly preferably 9% or less. When W ₀ is equal to or less than the above upper limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher.

In the film adhesive of 2nd Embodiment, the lower limit of W ₀ is not specifically limited.

In the film adhesive of 2nd Embodiment, it is preferable that it is 3% or more, and, as for W ₀ , it is more preferable that it is 5% or more. When W ₀ is equal to or greater than the above lower limit, the handleability of the film-like adhesive is improved, and the sticking of the film-like adhesive to the semiconductor wafer becomes easier. Further, even if the layer adjacent to the film-like adhesive such as a substrate has an uneven surface, the followability of the film-like adhesive with respect to this uneven surface is improved.

In the film adhesive of the second embodiment, W ₀ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, in one embodiment, W ₀ is preferably 3 to 15%, more preferably 3 to 13%, still more preferably 3 to 11%, and particularly preferably 3 to 9%. Further, as another aspect, W ₀ is preferably 5 to 15%, more preferably 5 to 13%, further preferably 5 to 11%, and particularly preferably 5 to 9%. As another aspect, W ₀ may be 3 to 8% or 5 to 8%. However, these are examples of W ₀ .

Article according to the adhesive film of the second embodiment, W ₁₆₈ is not particularly limited, it is preferably 4-16% and, more preferably 5 to 15%, which is 6-14% are especially preferred. As another aspect, W ₁₆₈ it is or may be 9-12%. When W ₁₆₈ is equal to or less than the above upper limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. When W ₁₆₈ is equal to or more than the above lower limit, the handleability of the film-like adhesive is improved, and affixing of the film-like adhesive to the semiconductor wafer becomes easier. Further, even if the layer adjacent to the film-like adhesive such as a substrate has an uneven surface, the followability of the film-like adhesive with respect to this uneven surface is improved.

In this embodiment, the gel fraction W _t of the film-like adhesive stored at 40° C. for t hours (t is a number greater than or equal to 0) can be measured by a known method.

For example, 0.5 g of a test piece of a sheet-like film adhesive having a size of 2.5 cm×4.0 cm×600 μm was prepared from a film adhesive stored at 40° C. for t hours, and wrapped with a polyester mesh, in this state The test piece of was immersed in methyl ethyl ketone (300 ml) at 23°C for 24 hours, the test piece after immersion was dried (eg, dried at 120°C for 1 hour), and the dried test piece was dried at 23°C and 50% relative humidity. After standing still for 24 hours in an environment, the mass of this test piece is measured. The gel fraction W _t (%) can be calculated from the measured value of the test piece and the mass of the test piece before immersion. By this method, W ₁₆₈ and W ₀ are obtained.

In addition, the measuring method of W ₀ in this embodiment is the same as the measuring method of W ₀ in the 1st embodiment mentioned above.

In addition, in this specification, "gel fraction" means a gel fraction measured by the above-described method unless otherwise specified.

The conditions for storing the film-like adhesive as an object for obtaining W _t at 40° C. are the same as those for obtaining T _t described above.

When storing the film adhesive which is the measurement object of W _t at 40 degreeC, it is preferable to start storage immediately after preparation of this film adhesive.

RW ₁₆₈ can be calculated according to the following formula (i).

RW ₁₆₈ (%)＝W ₁₆₈ ／W ₀ ×100 (i)

The film adhesive of the second embodiment is the same as the film adhesive of the first embodiment described above except that RW ₁₆₈ is 200% or less as an essential configuration, and ΔT ₁₆₈ is not required to be less than 10°C. .

For example, the film-like adhesive of the second embodiment, like the film-like adhesive of the first embodiment, has curability, preferably has thermosetting, preferably has pressure-sensitive adhesive, and thermosetting and pressure-sensitive You may have adhesiveness together. The film-like adhesive of the second embodiment also finally becomes a cured product having high impact resistance by curing, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

In addition, the film adhesive of the second embodiment may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers, similarly to the film adhesive of the first embodiment.

In addition, the thickness of the film adhesive of 2nd Embodiment is the same as the thickness of the film adhesive of 1st Embodiment.

In addition, the film adhesive of 2nd Embodiment can be manufactured by the same method as the case of the film adhesive of 1st Embodiment.

W _t of the film adhesive of the second embodiment, such as W ₀ or W ₁₆₈ , and RW ₁₆₈ (hereinafter, these are encompassed and may be referred to as ``W ₀ and the like'') are, for example, film adhesives By adjusting the kind and amount of the components contained in the, it can be appropriately adjusted. For example, the type and content ratio of the constituent units in the polymer component (a) described later, which are components of the film adhesive, the constituent components of the epoxy resin (b1), the three-dimensional structure of the thermosetting agent (b2), and curing By adjusting the reactivity of the accelerator (c) and the average particle diameter of the filler (d), the above-described W ₀ and the like can be appropriately adjusted. However, these are only examples of the above-described control method such as W ₀ .

<<3rd embodiment>>

In the film adhesive according to the third embodiment of the present invention, when the film adhesive is stored at 40°C and the elongation at break is measured according to JIS K7161:1994 for the film adhesive before and after storage, the storage time this is below the 30% rate of decrease RF ₁₆₈ of the elongation at break in case the elongation at break F _168, and, retention time determined from the rupture elongation F ₀ before storage is a 168 times in the case of 168 hours, the the adhesive the film The gel fraction W ₀ of the film adhesive before storage at 40°C is 15% or less.

As another aspect, the film-like adhesive according to the third embodiment of the present invention has the following properties:

(I") The elongation at break measured according to JIS K7161:1994 after storage at 40°C for 168 hours of the film adhesive was F ₁₆₈ , and measured according to JIS K7161:1994 before storage of the film adhesive. when the elongation at break as F _0, F is the rate of decrease of RF ₁₆₈ and ₁₆₈ of the elongation at break obtained from the F ₀ is less than 30%, and

(II") When the gel fraction of the film adhesive before storing the film adhesive at 40°C is W ₀ , the W ₀ is 15% or less.

In this way, the film-like adhesive of the third embodiment has a small RF ₁₆₈ , and even when stored at 40°C for 168 hours, the change in breaking elongation is suppressed, and storage stability is high. A film-like adhesive that satisfies these conditions is not limited to these storage conditions, and has high storage stability over the storage conditions that are usually applied. And, by using such a film-like adhesive, a highly reliable semiconductor package can be manufactured.

In addition, the film-like adhesive of the third embodiment has a small W ₀ , and makes it possible to manufacture a highly reliable semiconductor package regardless of the storage or not.

In the film adhesive of the third embodiment, as described above, RF ₁₆₈ is less than 30%, preferably 29.5% or less, more preferably 28% or less, still more preferably 26% or less, and 24% or less as described above. It is particularly preferred.

In the film adhesive of the third embodiment, the lower limit of RF ₁₆₈ is not particularly limited, but it is usually 0%. That is, the film-like adhesive according to the third embodiment, RF ₁₆₈ is preferably not less than 0%, and for example, may be 5% or more.

In the film adhesive of the third embodiment, RF ₁₆₈ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower and upper limits. For example, in one embodiment, RF ₁₆₈ is preferably 0% or more and less than 30%, more preferably 0 to 29.5%, still more preferably 0 to 28%, particularly preferably 0 to 26%, Most preferably, it is 0 to 24%. Further, as another aspect, RF ₁₆₈ is preferably 5% or more and less than 30%, more preferably 5 to 29.5%, still more preferably 5 to 28%, particularly preferably 5 to 26%, most preferably Is 5 to 24%. As another aspect, RF ₁₆₈ may be 0 to 23%, or 5 to 23%. However, these are examples of RF ₁₆₈ .

In the film adhesive of the third embodiment, F ₀ is not particularly limited, but it is preferably 550 to 950%, more preferably 600 to 900%, and particularly preferably 650 to 850%. As another aspect, F ₀ may be 700 to 800%. When F ₀ is equal to or less than the above upper limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. When F ₀ is more than the above lower limit, the handling property of the film-like adhesive is further improved.

Article according to the adhesive film of the third embodiment, F ₁₆₈ is not particularly limited, it is preferably 550-850% and, more preferably 550-800%, which is 550-750% is particularly preferred. As another aspect, F ₁₆₈ is even 560-700%. When F ₁₆₈ is equal to or less than the above upper limit, it becomes difficult to generate a void portion between the film-like adhesive and the object to be pasted, and the embedding property to the object to be pasted is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. When F ₁₆₈ is more than the above lower limit, the handling property of the film-like adhesive is further improved.

In this embodiment, for a film-like adhesive whose storage time at 40°C is t time (t is a number greater than or equal to 0), the elongation at break F _t can be measured according to JIS K7161:1994. For example, F ₁₆₈ and F ₀ degree, JIS K7161: 1994 can be measured in accordance with.

In addition, in this specification, "breaking elongation" means the breaking elongation measured in conformity with JIS K7161:1994 (ISO 527-1:1993) unless otherwise specified.

Conditions for storing the film-like adhesive as a measurement object of F _t at 40° C. are the same as those for obtaining T _t described above.

When preserving the film-like adhesive to obtain the target F _t in 40 ℃, immediately after production of the film-like adhesive, it is preferred to start the storage.

As an aspect, the elongation at break F _t of the film-like adhesive whose storage time at 40°C is t hours (t is a number greater than or equal to 0) is obtained by placing the film-like adhesive immediately after creation in a dark place in an air atmosphere, and at 40°C. It is obtained by standing still for t hours, and then immediately producing a test piece in accordance with JIS K7161:1994, and measuring the elongation at break of the test piece.

In addition, as an aspect, the breaking elongation F ₀ is obtained by immediately producing a test piece from the film-like adhesive immediately after preparation, and measuring the breaking elongation with respect to the test piece immediately after preparation according to JIS K7161:1994.

RF ₁₆₈ can be calculated according to the following formula (ii).

RF ₁₆₈ (%)＝(F ₀ －F ₁₆₈ )／F ₀ ×100 (ii)

As described above, the film adhesive of the third embodiment has an RF ₁₆₈ of less than 30% as an essential configuration, and ΔT ₁₆₈ is not required to be less than 10°C, except that the film-like adhesive of the first embodiment described above Same as adhesive.

For example, the film adhesive of the third embodiment has curability, like the film adhesive of the first embodiment, preferably has a thermosetting property, preferably has a pressure-sensitive adhesive property, and thermosetting and reduced pressure You may have adhesiveness together. The film adhesive of the third embodiment also finally becomes a cured product having high impact resistance by curing, and this cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

In addition, the film adhesive of 3rd embodiment may consist of one layer (single layer), similarly to the film adhesive of 1st Embodiment, and may consist of multiple layers of two or more layers.

In addition, the thickness of the film adhesive of 3rd embodiment is the same as the thickness of the film adhesive of 1st embodiment.

Further, the W ₀ of the film-like adhesive of the third embodiment is the same as W ₀ of the film-like adhesive of the first embodiment.

In addition, the film adhesive of 3rd embodiment can be manufactured by the same method as the case of the film adhesive of 1st embodiment.

F _t such as F ₀ or F ₁₆₈ of the film-like adhesive of the third embodiment, RF ₁₆₈ and W ₀ (hereinafter, these are encompassed and may be referred to as ``F ₀ and the like'') are all, for example. , By adjusting the kind and amount of the components contained in the film-like adhesive, it can be appropriately adjusted. For example, the type and content ratio of the constituent units in the polymer component (a) described later, which are components of the film adhesive, the constituent components of the epoxy resin (b1), the three-dimensional structure of the thermosetting agent (b2), and curing By controlling the reactivity of the accelerator (c) and the average particle diameter of the filler (d), the above-described F ₀ and the like can be appropriately adjusted. However, these are only examples of the above-described adjustment method such as F ₀ .

The film adhesive of the present invention may have the characteristics of any two or more (two or three) embodiments of the first embodiment, the second embodiment, and the third embodiment described above.

That is, as an embodiment of the film-like adhesive, for example, ΔT ₁₆₈ is less than 10°C, RW ₁₆₈ is 200% or less, and W ₀ is 15% or less.

Moreover, as an embodiment of the said film adhesive, what is ΔT ₁₆₈ is less than 10 _degreeC , W ₀ is 15% or less, and RF ₁₆₈ is less than 30% is mentioned, for example.

Moreover, as an embodiment of the said film adhesive, what is 200% or less of RW ₁₆₈ , 15% or less of W ₀ , and RF ₁₆₈ less than 30% is mentioned, for example.

In addition, in one embodiment of the film adhesive, for example, ΔT ₁₆₈ is less than 10°C, RW ₁₆₈ is 200% or less, W ₀ is 15% or less, and RF ₁₆₈ What is less than this 30% is mentioned.

In these film adhesives, T ₀ , T ₁₆₈ , ΔT ₁₆₈ , W ₀ , W ₁₆₈ , RW ₁₆₈ , F ₀ , F ₁₆₈ , and RF ₁₆₈ are all as previously described.

1 is a cross-sectional view schematically showing a film adhesive according to an embodiment of the present invention. Meanwhile, in the drawings used in the following description, for convenience, in order to make it easier to understand the features of the present invention, there are cases where the main part is enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality. Does not.

The film-like adhesive 13 shown here is provided with a 1st peeling film 151 on one side (in this specification, it may be called a ``first side'') 13a, and the said 1st side The second release film 152 is provided on the other side opposite to the (13a) side (in this specification, it may be referred to as the “second side”) 13b.

This film-like adhesive 13 is suitable for storage in a roll shape, for example.

The film adhesive 13 has the characteristics of any one or two or more of the above-described first, second, and third embodiments.

The film adhesive 13 can be formed from an adhesive composition described later.

The first release film 151 and the second release film 152 may all be known.

The first release film 151 and the second release film 152 may be the same as each other, for example, when peeling from the film-like adhesive 13, the required peeling force may be different from each other, and may be different from each other. .

In the film-like adhesive 13 shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed to the exposed surface formed by removing either of the 1st peeling film 151 and the 2nd peeling film 152. And the exposed surface formed by removing the other side of the 1st peeling film 151 and the 2nd peeling film 152 becomes the affixing surface of the support sheet mentioned later.

<<adhesive composition>>

As a preferable adhesive composition, a thermosetting adhesive composition is mentioned.

As a thermosetting adhesive composition, what contains a polymer component (a) and an epoxy thermosetting resin (b) is mentioned, for example. Hereinafter, each component is demonstrated.

(Polymer component (a))

The polymer component (a) is a component that can be considered to have been formed by a polymerization reaction of a polymerizable compound, and provides film-forming properties or flexibility to the film-like adhesive, as well as adhesion to an object to be adhered such as a semiconductor chip. It is a polymer component to improve the property). In addition, the polymer component (a) is also a component that does not correspond to the epoxy resin (b1) and the thermosetting agent (b2) described later. That is, the polymer component (a) excludes components corresponding to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The number of polymer components (a) contained in the adhesive composition and the film-like adhesive may be one or two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

Examples of the polymer component (a) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, thermosetting polyimides, and acrylic resins.

As said acrylic resin in the polymer component (a), a well-known acrylic polymer is mentioned.

It is preferable that it is 10000-2000000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000-150,000. When the weight average molecular weight of the acrylic resin is in such a range, it becomes easy to adjust the adhesive force between the film-like adhesive and the adherend to a preferable range.

On the other hand, when the weight average molecular weight of the acrylic resin is more than the above lower limit, the shape stability (stability with time at storage) of the film adhesive is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above upper limit, the film-like adhesive easily follows the uneven surface of the adherend, and generation of voids or the like between the adherend and the film-like adhesive is more suppressed.

In addition, in this specification, a "weight average molecular weight" is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

It is preferable that it is -60 to 70 degreeC, and, as for the glass transition temperature (Tg) of an acrylic resin, it is more preferable that it is -30 to 50 degreeC. When the Tg of the acrylic resin is more than the above lower limit, the adhesive force between the film adhesive and the adherend is suppressed, and during pickup, the semiconductor chip on which the film adhesive is formed becomes easier to separate from the support sheet described later. In this specification, the "semiconductor chip in which a film adhesive was formed" means "a semiconductor chip provided with a film adhesive on the back surface". When the Tg of the acrylic resin is equal to or less than the above upper limit, the adhesive strength between the film adhesive and the semiconductor chip is improved.

Examples of the (meth)acrylic acid ester constituting the acrylic resin include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n (meth)acrylate. -Butyl, (meth) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate, (meth) hexyl acrylate, (meth) heptyl acrylate, (meth) acrylate 2- Ethylhexyl, (meth) acrylate isooctyl, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate, (meth) Dodecyl acrylate (also referred to as (meth) lauryl acrylate), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristol (meth) acrylate), pentadecyl (meth) acrylate, hexa (meth) acrylate The alkyl groups constituting the alkyl ester, such as decyl (also referred to as palmityl ((meth)acrylate)), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also referred to as stearyl (meth)acrylate), have 1 to (Meth)acrylate alkyl ester having a chain structure of 18;

Cycloalkyl esters of (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

(Meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate;

Imide (meth)acrylate;

Glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate;

Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylate;

And substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate. Here, the "substituted amino group" means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

In addition, in this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic acid.

The acrylic resin is, for example, in addition to the (meth)acrylic acid ester, one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide. May be obtained by copolymerization.

The number of monomers constituting the acrylic resin may be only one, or may be two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

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

In the acrylic resin, the ratio (content) of the amount of the structural unit derived from the glycidyl group-containing monomer to the total content (total mass) of the structural units constituting the acrylic resin is preferably 15% by mass or less, 12 It is more preferable that it is mass% or less, and it is especially preferable that it is 9 mass% or less. When the ratio (content) is less than or equal to the upper limit, the storage stability of the film-like adhesive becomes higher. In addition, the said glycidyl group-containing monomer means a monomer which has a glycidyl group, such as the said glycidyl group-containing (meth)acrylic acid ester.

In the acrylic resin, the lower limit of the ratio (content) of the amount of the structural unit derived from the glycidyl group-containing monomer with respect to the total content (total mass) of the structural units constituting it is not particularly limited.

In the acrylic resin, the ratio (content of the structural unit derived from the glycidyl group-containing monomer) may be 0% by mass or more, for example, if it is 2% by mass or more, the effect of using a glycidyl group-containing monomer Is obtained more clearly.

In the acrylic resin, the ratio (content) of the amount of the constituent unit derived from the glycidyl group-containing monomer to the total content (total mass) of the constituent units constituting it is set by arbitrarily combining the above-described preferred lower and upper limits It can be properly adjusted within the range. For example, in one embodiment, the ratio is preferably 0 to 15% by mass, more preferably 0 to 12% by mass, and particularly preferably 0 to 9% by mass. As another aspect, the ratio is preferably 2 to 15% by mass, more preferably 2 to 12% by mass, particularly preferably 2 to 9% by mass, and may be 2 to 5% by mass. However, these are examples of the above ratio.

In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter, simply abbreviated as "thermoplastic resin" may be used alone) without using an acrylic resin, and an acrylic resin and You may use it together. By using the thermoplastic resin, it becomes easier to separate the semiconductor chip on which the film adhesive is formed from the support sheet to be described later at the time of pickup, or the film adhesive easily follows the uneven surface of the adherend. The occurrence of voids or the like between the complex and the film-like adhesive may be more suppressed.

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

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

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The thermoplastic resins contained in the adhesive composition and the film adhesive may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the adhesive composition, the ratio of the content of the polymer component (a) to the total content (total mass) of all components other than the solvent (that is, the content of the polymer component (a) of the film adhesive) is the polymer component (a) Regardless of the kind of, it is preferably 5 to 20 mass%, more preferably 6 to 16 mass%, and may be 7 to 12 mass% or the like.

In the adhesive composition and the film adhesive, the ratio of the content of the acrylic resin to the total content (total mass) of the polymer component (a) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass. And, it is more preferable that it is 90-100 mass %, and for example, it may be 95-100 mass %. When the ratio of the content is equal to or greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

(Epoxy thermosetting resin (b))

The epoxy-based thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2).

The epoxy-based thermosetting resin (b) contained in the adhesive composition and the film-like adhesive may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

Epoxy resin (b1)

Examples of the epoxy resin (b1) include known ones, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ethers and their hydrogenated products, orthocresol novolac epoxy resins, dicyclopenta Diene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher epoxy compounds.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group. In addition, in the present specification, "derivative" means that at least one group of the original compound is substituted with a group (substituent) other than that unless otherwise specified. Here, "group" shall include not only an atomic group formed by bonding of a plurality of atoms, but also one atom.

Further, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin, for example.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (also called vinyl group), 2-propenyl group (also called allyl group), (meth)acryloyl group, (meth)acrylamide group, etc. And acryloyl groups are preferred.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but in terms of the curability of the film-like adhesive, and the strength and heat resistance of the film-like adhesive after curing, it is preferably 300 to 30,000, more preferably 400 to 10000. And it is particularly preferably 500 to 3000.

In the present specification, "number average molecular weight" means a number average molecular weight represented by a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise noted.

It is preferable that it is 100-1000 g/eq, and, as for the epoxy equivalent of the epoxy resin (b1), it is more preferable that it is 150-800 g/eq.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 equivalent of an epoxy group, and can be measured according to the method of JIS K7236:2001.

The number of the epoxy resins (b1) contained in the adhesive composition and the film-like adhesive may be one, or may be two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

As one aspect, the epoxy resin (b1) is selected from the group consisting of a bisphenol A type epoxy resin, a polyfunctional aromatic type (triphenylene type) epoxy resin, a bisphenol F type epoxy resin, and a dicyclopentadiene type epoxy resin. At least one is preferred.

Commercially available products of the epoxy resin (b1) include acrylic resin fine particles (fine acrylic resin), but in the present invention, it is preferable to use an epoxy resin (b1) that does not contain acrylic resin fine particles. By doing in this way, even when a polymer component (a) that is easy to agglomerate acrylic resin fine particles due to interaction with the acrylic resin fine particles is used, such agglomeration of acrylic resin fine particles is suppressed. Thereby, the storage stability of the film-like adhesive becomes higher.

For example, in the adhesive composition, the ratio of the content of the acrylic resin fine particles to the total content (total mass) of all components other than the solvent (that is, the content of the acrylic resin fine particles of the film adhesive) is Regardless of origin, it is preferably 0 to 5% by mass, and more preferably 0 to 3% by mass.

·Heat curing agent (b2)

The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).

Examples of the thermosetting agent (b2) include a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or an acid group is preferably an anhydride group, It is more preferable that it is a sexual hydroxyl group or an amino group.

Among the thermal curing agents (b2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, aralkyl type phenol resins, etc. Can be lifted.

Among the thermal curing agents (b2), examples of the amine curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as DICY) and the like.

The thermosetting agent (b2) may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (b2) having an unsaturated hydrocarbon group include, for example, a compound obtained by substituting a group having an unsaturated hydrocarbon group in a part of the hydroxyl group of a phenol resin, or a compound obtained by directly bonding a group having an unsaturated hydrocarbon group to the aromatic ring of the phenol resin. And the like.

The unsaturated hydrocarbon group in the thermosetting agent (b2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the above-described unsaturated hydrocarbon group.

In the case of using a phenolic curing agent as the thermal curing agent (b2), it is preferable that the thermal curing agent (b2) has a high softening point or glass transition temperature from the viewpoint of being easy to adjust the adhesive force of the film-like adhesive.

Among the thermal curing agents (b2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30000. , It is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Among the thermosetting agents (b2), the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but, for example, it is preferably 60 to 500.

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the thermosetting agent (b2), a substituent such as an alkyl group is bonded to a carbon atom to which a phenolic hydroxyl group is bonded and a carbon atom adjacent to each other (that is, a carbon atom constituting a benzene ring skeleton) in the phenol resin, Those having a steric hindrance in the vicinity of the phenolic hydroxyl group (in this specification, it may be abbreviated as "sterically hindered phenol resin") is preferred. Examples of such hindered phenol resin include o-cresol-type novolac resin.

In the adhesive composition and the film adhesive, the content of the thermosetting agent (b2) is preferably 10 to 200 parts by mass, more preferably 15 to 160 parts by mass, and 20 parts by mass based on 100 parts by mass of the epoxy resin (b1). It is more preferable that it is -120 mass parts, and it is especially preferable that it is 25-80 mass parts. When the content of the thermosetting agent (b2) is equal to or greater than the lower limit, curing of the film-like adhesive is more likely to proceed. When the content of the thermosetting agent (b2) is less than or equal to the upper limit, the moisture absorption rate of the film adhesive is reduced, and the reliability of the package obtained by using the film adhesive is further improved.

In the adhesive composition and the film adhesive, the content of the epoxy-based thermosetting resin (b) (the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is 400 based on 100 parts by mass of the content of the polymer component (a). It is preferable that it is -1200 mass parts, it is more preferable that it is 500-1100 mass parts, It is still more preferable that it is 600-1000 mass parts, For example, any of 600-900 mass parts and 800-1000 mass parts may be sufficient. When the content of the epoxy-based thermosetting resin (b) is in such a range, it becomes easier to adjust the adhesive force between the film-like adhesive and the support sheet described later.

In the adhesive composition and the film adhesive, the ratio of the content of the sterically hindered phenol resin to the total content (total mass) of the thermosetting agent (b2) is preferably 80 to 100% by mass, and 85 to 100% by mass. It is more preferable that it is 90-100 mass %, and, for example, it may be 95-100 mass %. When the ratio of the content is equal to or greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

In addition, since the storage stability of the film adhesive is further increased, in the adhesive composition and the film adhesive, the ratio of the content of the o-cresol type novolac resin to the total content of the thermosetting agent (b2) is 80 to 100 mass. It is preferable that it is %, it is more preferable that it is 85-100 mass %, It is still more preferable that it is 90-100 mass %, For example, it may be 95-100 mass %.

In order to improve the various physical properties of the film-like adhesive, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components that do not correspond to these may further be contained as needed.

Other components contained in the film adhesive include, for example, a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), and a photopolymerization initiator (h ), a general-purpose additive (i), and the like. Among these, preferable other components include a curing accelerator (c), a filler (d), a coupling agent (e), and a general-purpose additive (i).

In the present invention, the term "energy ray" means having both energy in an electromagnetic wave or a charged particle ray, 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, or an LED lamp as an ultraviolet source. The electron beam can be irradiated with what is generated by an electron beam accelerator or the like.

In the present invention, "energy ray curability" means a property that is hardened by irradiation with energy rays, and "non-energy ray curability" means a property that does not cure even when irradiated with energy rays.

(Hardening accelerator (c))

The curing accelerator (c) is a component for controlling the curing speed of the adhesive composition.

Preferred curing accelerators (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 Imidazoles such as hydroxymethylimidazole (that is, imidazole in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); Organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (ie, phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; Inclusion compounds using the above imidazoles as a guest compound, etc. are mentioned.

The number of curing accelerators (c) contained in the adhesive composition and the film-like adhesive may be one or two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

When using the curing accelerator (c), in the adhesive composition and film adhesive, the content of the curing accelerator (c) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the epoxy-based thermosetting resin (b), It is more preferable that it is 0.1-2 mass parts. When the content of the curing accelerator (c) is more than the lower limit, the effect of using the curing accelerator (c) is more remarkably obtained. When the content of the curing accelerator (c) is less than or equal to the above upper limit, for example, the high polarity curing accelerator (c) is prevented from moving to the side of the adhesion interface with the adherend and segregation in the film-like adhesive under conditions of high temperature and high humidity. The resulting effect increases, and the reliability of the package obtained by using the film-like adhesive is further improved.

Among the above, the curing accelerator (c) is preferably an inclusion compound containing the imidazoles as a guest compound. In such a curing accelerator (c), imidazoles, which are active ingredients, are encapsulated by the host compound. For this reason, it is estimated that the reaction site|part of imidazoles is not exposed except at the time of reaction, or the degree of exposure is suppressed. As a result, it is estimated that the storage stability of the film adhesive becomes higher by suppressing the progress of the reaction other than the purpose of the curing accelerator (c) during storage of the film adhesive.

Examples of the clathrate compound include imidazoles as a guest compound and carboxylic acid as a host compound.

The carboxylic acid as the host compound is preferably an aromatic carboxylic acid.

The aromatic carboxylic acid may be a monocyclic aromatic carboxylic acid or a polycyclic aromatic carboxylic acid.

The aromatic carboxylic acid is any of a carboxylic acid having only an aromatic hydrocarbon ring as a ring skeleton, a carboxylic acid having only an aromatic heterocycle as a ring skeleton, and a carboxylic acid having both an aromatic hydrocarbon ring and an aromatic heterocycle as a ring skeleton. It may be.

It is preferable that the aromatic carboxylic acid is an aromatic hydroxycarboxylic acid.

The aromatic hydroxycarboxylic acid is not particularly limited as long as it is an aromatic carboxylic acid having a hydroxyl group and a carboxyl group in one molecule, but is preferably a carboxylic acid having a structure in which a hydroxyl group and a carboxyl group are bonded together to an aromatic ring skeleton.

Preferred as the inclusion compound is, for example, the imidazoles are 2-phenyl-4-methyl-5-hydroxymethylimidazole (in this specification, it may be abbreviated as "2P4MHZ"). , An inclusion compound in which the carboxylic acid is 5-hydroxyisophthalic acid (in this specification, it may be abbreviated as "HIPA"), and 1 molecule is composed of 2 molecules of 2P4MHZ and 1 molecule of HIPA. It is more preferable that it is the inclusion compound which has become.

In the adhesive composition and film adhesive, the ratio of the content of the clathrate compound to the total content (total mass) of the curing accelerator (c) is preferably 80 to 100% by mass, more preferably 85 to 100% by mass. And, it is more preferable that it is 90-100 mass %, and for example, it may be 95-100 mass %. When the ratio of the content is equal to or greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

And, since the storage stability of the film adhesive is further increased, in the adhesive composition and the film adhesive, the ratio of the content of the clathrate compound composed of 2P4MHZ and HIPA to the total content of the curing accelerator (c) is It is preferable that it is 80-100 mass %, it is more preferable that it is 85-100 mass %, It is still more preferable that it is 90-100 mass %, For example, it may be 95-100 mass %.

(Filling material (d))

When the film-like adhesive contains the filler (d), it becomes 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 adhered, the reliability of the package obtained using the film-like adhesive is further improved. . In addition, when the film adhesive contains the filler (d), the moisture absorption rate of the film adhesive after curing can be reduced or the heat dissipation property can be improved.

The filler (d) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide and boron nitride; Beads in which these inorganic fillers are spheroidized; Surface modified products of these inorganic fillers; Single crystal fibers of these inorganic fillers; Glass fiber, etc. are mentioned.

Among these, the inorganic filler is preferably silica or alumina.

The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 to 150 µm, more preferably 0.1 to 125 µm, even more preferably 0.5 to 100 µm, and particularly 1 to 75 µm. desirable. As another aspect, the average particle diameter of the filler (d) may be 0.01 to 0.05 µm. When the average particle diameter of the filler (d) is in such a range, while the effect of using the filler (d) is sufficiently obtained, storage stability of the film-like adhesive is further improved.

In addition, in this specification, the "average particle diameter" means the value of the particle diameter (D ₅₀ ) at the integrated value 50% in the particle size distribution curve calculated by the laser diffraction scattering method, unless otherwise noted. .

The number of fillers (d) contained in the adhesive composition and the film-like adhesive may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using the filler (d), in the adhesive composition, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent (that is, the content of the filler (d) of the film adhesive ) Is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and particularly preferably 15 to 30% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

In the adhesive composition and the film adhesive, the ratio of the content of the filler (d) having an average particle diameter of 0.01 to 150 µm to the total content (total mass) of the filler (d) is preferably 80 to 100% by mass, , 85 to 100% by mass is more preferable, 90 to 100% by mass is still more preferable, and for example, 95 to 100% by mass may be used. When the ratio of the content is equal to or greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

(Coupling agent (e))

When the film-like adhesive contains the coupling agent (e), the adhesion and adhesion to the adherend are improved. In addition, when the film-like adhesive contains the coupling agent (e), the cured product does not impair heat resistance and improves water 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 possessed by the polymer component (a), an epoxy-based thermosetting resin (b), and the like, and more preferably a silane coupling agent.

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-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyl Triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, oligomeric or polymeric organosiloxane, and the like.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

As an aspect, as the coupling agent (e), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and an oligomeric silane coupling agent having an epoxy group, a methyl group, and a methoxy group. It is preferably at least one member selected from the group consisting of.

When a coupling agent (e) is used, in the adhesive composition and film adhesive, the content of the coupling agent (e) is 0.03 based on 100 parts by mass of the total content of the polymer component (a) and the epoxy-based thermosetting resin (b). It is preferable that it is -20 mass parts, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts.

When the content of the coupling agent (e) is greater than or equal to the lower limit, the effect of using the coupling agent (e), such as improving the dispersibility of the filler (d) in the resin, and improving the adhesion of the film-like adhesive to the adherend, etc. Is obtained more remarkably. When the content of the coupling agent (e) is less than or equal to the upper limit, the outgassing is further suppressed.

Among the above, the coupling agent (e) is preferably an oligomeric or polymeric organosiloxane. The oligomeric or polymeric organosiloxane is an organosiloxane having an oligomeric structure or a polymeric structure, which can be considered to be formed by a polymerization reaction of a polymerizable compound. By using such an oligomeric or polymeric organosiloxane, the effect of using the coupling agent (e) is sufficiently obtained, and the storage stability of the film-like adhesive is further improved.

In the adhesive composition and film adhesive, the ratio of the content of the oligomeric or polymeric organosiloxane to the total content of the coupling agent (e) is preferably 80 to 100% by mass, and 85 to 100% by mass. It is more preferable, and it is still more preferable that it is 90-100 mass %, and for example, it may be 95-100 mass %. When the ratio of the content is equal to or greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

(Crosslinking agent (f))

When using a polymer component (a) having a functional group such as a vinyl group, (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc. that can be bonded to other compounds, such as an acrylic resin described above, is used, an adhesive composition and The film adhesive may contain a crosslinking agent (f) for crosslinking by bonding the functional group with another compound. By crosslinking using the crosslinking agent (f), the initial adhesion and cohesive strength of the film-like adhesive can be controlled.

As the crosslinking agent (f), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate type crosslinking agent (i.e., a crosslinking agent having a metal chelate structure), an aziridine type crosslinking agent (ie, a crosslinking agent having an aziridinyl group), etc. Can be lifted.

As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be included and abbreviated as ``aromatic polyvalent isocyanate compound, etc.'' in some cases) ; Trimers, isocyanurates, and adducts such as the above aromatic polyvalent isocyanate compounds; And a terminal isocyanate urethane prepolymer obtained by reacting the above aromatic polyvalent isocyanate compound and the like with a polyol compound. The ``adduct body'' is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Means reactant. Examples of the adduct body include a xylylene diisocyanate adduct of trimethylolpropane described later, and the like. In addition, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

As the organic polyvalent isocyanate compound, more specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or part of the hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate, etc. are mentioned.

As the organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate , Tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxyamide)triethylene melamine, and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinking structure can be easily introduced into the film-like adhesive by reaction of the crosslinking agent (f) and the polymer component (a).

The number of crosslinking agents (f) contained in the adhesive composition and the film-like adhesive may be one, or two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The content of the crosslinking agent (f) is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, still more preferably 0 to 1 parts by mass, based on 100 parts by mass of the polymer component (a), It is particularly preferable that it is 0 parts by mass, that is, that the adhesive composition and the film-like adhesive do not contain a crosslinking agent (f). When the content of the crosslinking agent (f) is not less than the lower limit, the effect of using the crosslinking agent (f) is more remarkably obtained. When the content of the crosslinking agent (f) is equal to or less than the upper limit, the storage stability of the film-like adhesive becomes higher.

(Energy ray curable resin (g))

Since the film-like adhesive contains the energy ray-curable resin (g), its properties can be changed by irradiation with energy rays.

The energy ray-curable resin (g) is obtained by polymerizing (curing) an energy ray-curable compound.

Examples of the energy ray-curable compound include a compound having at least one polymerizable double bond in a molecule, and an acrylate compound having a (meth)acryloyl group is preferable.

Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol monohydroxypenta (meth)acrylate, dipentaerythritol hexa (meth)acrylate, 1,4-butylene glycol di (meth)acrylate, 1,6-hexanedioldi (meth)acrylate Chain aliphatic skeleton-containing (meth)acrylates such as; Cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyldi(meth)acrylate; Polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; Oligoester (meth)acrylate; Urethane (meth)acrylate oligomers; Epoxy modified (meth)acrylate; Polyether (meth)acrylate other than the polyalkylene glycol (meth)acrylate; Itaconic acid oligomer, etc. are mentioned.

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the energy ray-curable resin (g), it is more preferable that it is 300-10000.

The energy ray-curable resin (g) contained in the adhesive composition may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using an energy ray-curable resin (g), the content of the energy ray-curable resin (g) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, with respect to the total mass of the adhesive composition. , It is particularly preferably 10 to 85% by mass.

(Photopolymerization initiator (h))

When the adhesive composition contains the energy ray-curable resin (g), in order to efficiently advance the polymerization reaction of the energy ray-curable resin (g), it may contain a photoinitiator (h).

As the photoinitiator (h) in the adhesive composition, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, Benzoin compounds such as benzoin dimethyl ketal; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; Benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; And quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Moreover, as a photoinitiator (h), photosensitizers, such as an amine, etc. are also mentioned, for example.

The photopolymerization initiator (h) contained in the adhesive composition may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the case of using a photoinitiator (h), in the adhesive composition, the content of the photoinitiator (h) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the energy ray-curable resin (g), and 1 to It is more preferable that it is 10 mass parts, and it is especially preferable that it is 2-5 mass parts.

(Universal Additive (i))

The general-purpose additive (i) may be any known one, and may be arbitrarily selected according to the purpose, and is not particularly limited. As a preferable general-purpose additive (i), a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent, etc. are mentioned, for example.

The general-purpose additives (i) contained in the adhesive composition and the film-like adhesive may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The content of the adhesive composition and the general-purpose additive (i) of the film adhesive is not particularly limited, and may be appropriately selected according to the purpose.

(menstruum)

It is preferable that the adhesive composition further contains a solvent. The adhesive composition containing a solvent becomes good handling property.

The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; And amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The solvent contained in the adhesive composition may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

<<the manufacturing method of an adhesive composition>>

The adhesive composition is obtained by blending each component for constituting it.

The order of addition at the time of compounding each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be used by diluting it in advance, and the solvent is not previously diluted with any of the compounding components other than the solvent. You may use by mixing with.

The method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Semiconductor processing sheet

The sheet for semiconductor processing of the present invention is provided with a support sheet, and the film-like adhesive is provided on the support sheet. That is, the sheet for semiconductor processing of the present invention includes a support sheet and the film-like adhesive provided on the support sheet.

The sheet for semiconductor processing is preferable as, for example, a dicing die bonding sheet.

As described above, the film-like adhesive has high storage stability, suppresses a change in properties during storage, and can sufficiently exhibit a target action at the time of use. Therefore, a semiconductor package formed by using the sheet for semiconductor processing and including the film-like adhesive has high reliability. In addition, in the semiconductor package formed with such a film-like adhesive having high storage stability, the change in properties due to the change in the properties of the film-like adhesive is suppressed even during storage. Therefore, also in this respect, the semiconductor package has high reliability.

<<support sheet>>

The support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the supporting sheet is made of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited unless the effect of the present invention is impaired.

Preferred supporting sheets include, for example, those made of only a substrate; It includes a base material, and includes an intermediate layer on the base material.

That is, the support sheet according to the present invention may be a support sheet composed of only a base material; A support sheet including a substrate and an intermediate layer provided on the substrate may be used.

The support sheet composed of only a base material is preferable as a carrier sheet or a dicing sheet. The sheet for semiconductor processing provided with a supporting sheet composed of only such a base material is a side opposite to the side provided with the supporting sheet (i.e., base material) of a film-like adhesive (in this specification, it may be referred to as a ``first side''). ) Is affixed to the side opposite to the side on which the circuit of the semiconductor wafer is formed (in this specification, it may be referred to as "the back side") and used.

On the other hand, the support sheet having a substrate and having an intermediate layer on the substrate is preferable as a dicing sheet. In the semiconductor processing sheet provided with such a support sheet, the side opposite to the side (first side) provided with the support sheet of the film-like adhesive is on the side opposite to the side (the back side) on which the circuit of the semiconductor wafer is formed. It is attached and used.

The method of using the sheet for semiconductor processing will be described in detail later.

Hereinafter, each layer constituting the support sheet will be described.

<Description>

The substrate is in the form of a sheet or a film, and examples of the constituent material include various resins.

Examples of the resin include polyethylene such as low density polyethylene (some abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), and high density polyethylene (some abbreviated as HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (i.e., copolymer obtained using ethylene as a monomer) coalescence); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (that is, resins obtained using vinyl chloride as a monomer); polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all structural units have an aromatic ring group; A copolymer of two or more of the above polyesters; Poly(meth)acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; Polyether ketone, etc. are mentioned.

Moreover, as said resin, polymer alloys, such as a mixture of said polyester and resin other than that, are also mentioned, for example. It is preferable that the polymer alloy of the polyester and other resins has a relatively small amount of resin other than polyester.

Further, as the resin, for example, a crosslinked resin in which one or two or more of the resins exemplified so far is crosslinked; Modified resins such as ionomers using one or two or more of the resins exemplified so far can also be mentioned.

The number of resins constituting the base material may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The base material may consist of one layer (single layer), may consist of a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited. Does not.

The thickness of the substrate is preferably 50 to 300 µm, more preferably 60 to 150 µm. When the thickness of the substrate is within such a range, the flexibility of the sheet for semiconductor processing and the adhesion to the semiconductor wafer or semiconductor chip are further improved.

Here, "thickness of a base material" means the thickness of the whole base material, and for example, the thickness of a base material consisting of a plurality of layers means the total thickness of all layers constituting the base material.

It is preferable that the substrate has high accuracy in thickness, that is, the variation in thickness is suppressed regardless of the portion. Among the above-described constituent materials, examples of materials that can be used to construct a substrate with such a high accuracy in thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), in addition to the main constituent materials such as the resin.

The substrate may be transparent or opaque, may be colored depending on the purpose, or may be deposited with another layer.

In order to improve adhesion with other layers such as an intermediate layer formed thereon, the substrate is uneven treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, etc. The surface may be subjected to oxidation treatment such as treatment, chromic acid treatment, or hot air treatment.

In addition, the base material may have been subjected to a primer treatment on the surface.

In addition, the base material is an antistatic coating layer; When the sheet for semiconductor processing is superimposed and stored, the substrate may be adhered to another sheet, or may have a layer that prevents the substrate from adhering to the adsorption table.

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

<Middle floor>

The intermediate layer is not particularly limited as long as it is disposed between the substrate and the film-like adhesive and exhibits its function.

As the intermediate layer, more specifically, for example, a peelability improving layer in which one side is subjected to a peeling treatment is mentioned.

○ Peelability improvement layer

The peelability improving layer is in the form of a sheet or a film.

Examples of the peelability improving layer include a resin layer and a layer comprising a plurality of layers comprising a peeling treatment layer formed on the resin layer. In the sheet for semiconductor processing, as for the peelability improvement layer, the peeling treatment layer is disposed toward the film-like adhesive side.

Among the peelability improving layers, the resin layer can be produced by molding a resin composition containing a resin.

And the peelability improvement layer can be manufactured by peeling-processing one side of the said resin layer.

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, or wax-based, for example.

From the viewpoint of having heat resistance, the release agent is preferably an alkyd-based, silicone-based, or fluorine-based release agent.

The resin which is the constituent material of the resin layer may be appropriately selected depending on the purpose, and is not particularly limited.

Preferred examples of the resin include polyethylene terephthalate (some abbreviated as PET), polyethylene naphthalate (sometimes abbreviated as PEN), and polybutylene terephthalate (some abbreviated as PBT). ), polyethylene (some abbreviated as PE), polypropylene (some abbreviated as PP), and the like.

The resin layer may be composed of one layer (single layer), may be composed of a plurality of layers 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, and a combination of these plurality of layers is particularly Not limited.

The thickness of the peelability improving layer (the total thickness of the resin layer and the peeling treatment layer) is preferably 10 to 2000 nm, more preferably 25 to 1500 nm, and particularly preferably 50 to 1200 nm. When the thickness of the peelability improvement layer is more than the above lower limit, the effect of the peelability improvement layer becomes more remarkable, and the effect of suppressing breakage such as cutting of the peelability improvement layer becomes higher. When the thickness of the peelability improvement layer is less than or equal to the above upper limit, when picking up a semiconductor chip with a film-like adhesive to be described later, the pushing force is easily transmitted to the semiconductor chip on which the film-like adhesive is formed, and pickup can be performed more easily. have.

Next, an example of the sheet for semiconductor processing of the present invention will be described for each type of support sheet, with reference to the drawings.

2 is a cross-sectional view schematically showing an embodiment of the sheet for semiconductor processing of the present invention.

On the other hand, in the drawings after FIG. 2, the same components as those shown in the previously described drawings are denoted by the same reference numerals as those in the illustrated drawings, and detailed descriptions thereof are omitted.

The sheet 1A for semiconductor processing shown here is provided with the support sheet 10, and the film-like adhesive 13 is provided on the support sheet 10. The support sheet 10 consists of only the substrate 11, and the semiconductor processing sheet 1A is, in other words, one side of the substrate 11 (in this specification, it may be referred to as the ``first surface'') 11a ) On the film-like adhesive 13 has a laminated configuration. Moreover, the sheet|seat 1A for semiconductor processing is equipped with the peeling film 15 on the film adhesive 13 further.

In the semiconductor processing sheet 1A, a film adhesive 13 is laminated on the first surface 11a of the substrate 11, and the side of the film adhesive 13 provided with the substrate 11 is A jig adhesive layer 16 is laminated on a part of the opposite side (in this specification, it may be referred to as the ``first surface'') 13a, that is, in the area near the periphery, and the film-like adhesive 13 Of the first surface 13a, a surface on which the jig adhesive layer 16 is not laminated, and of the jig adhesive layer 16, a surface 16a that is not in contact with the film adhesive 13 (the upper surface and The release film 15 is laminated on the side surface).

Here, the first surface 11a of the base material 11 is also referred to as the first surface 10a of the support sheet 10.

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

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a multilayer structure in which layers containing an adhesive component are laminated on both surfaces of a sheet serving as a core material.

In the semiconductor processing sheet 1A, with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is affixed to the first surface 13a of the film-like adhesive 13, and the jig adhesive layer Among the surfaces 16a of (16), the upper surface is attached to a jig such as a ring frame and used.

3 is a cross-sectional view schematically showing another embodiment of the sheet for semiconductor processing of the present invention.

The sheet 1B for semiconductor processing shown here is the same as the sheet 1A for semiconductor processing shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the sheet 1B for semiconductor processing, the film adhesive 13 is laminated on the first surface 11a of the substrate 11 (the first surface 10a of the support sheet 10), and the film adhesive The release film 15 is laminated on the entire surface of the first surface 13a of (13).

In other words, in the sheet 1B for semiconductor processing, the substrate 11, the film-like adhesive 13, and the release film 15 are laminated in this order in the thickness direction thereof.

The sheet 1B for semiconductor processing shown in FIG. 3 is similar to the case of the sheet 1A for semiconductor processing shown in FIG. 2, with the release film 15 removed, and the first surface 13a of the film-like adhesive 13 ), the rear surface of the semiconductor wafer (not shown) is affixed to a partial region on the center side, and the region near the periphery of the film-like adhesive 13 is affixed to a jig such as a ring frame and used.

4 is a cross-sectional view schematically showing still another embodiment of the sheet for semiconductor processing of the present invention.

The sheet 1C for semiconductor processing shown here is the same as the sheet 1A for semiconductor processing shown in FIG. 2 except that an intermediate layer 12 is additionally provided between the substrate 11 and the film-like adhesive 13 Do. The support sheet 10 is a laminate of the substrate 11 and the intermediate layer 12, and the sheet for semiconductor processing 1C is also laminated with a film-like adhesive 13 on the first surface 10a of the support sheet 10 Has a configuration.

In the semiconductor processing sheet 1C, the intermediate layer 12 is laminated on the first surface 11a of the substrate 11, and the surface of the intermediate layer 12 on the opposite side to the substrate 11 side (in this specification, The film-like adhesive 13 is laminated on the entire surface of 12a, and a part of the first surface 13a of the film-like adhesive 13, that is, a region near the periphery The jig adhesive layer 16 is laminated on the first surface 13a of the film adhesive 13, the surface on which the jig adhesive layer 16 is not laminated, and the jig adhesive layer 16 , The release film 15 is laminated on the surface 16a (the upper surface and the side surface) that is not in contact with the film-like adhesive 13.

In the semiconductor processing sheet 1C, when the intermediate layer 12 is the above-described peelability improving layer, for example, the layer on the side of the substrate 11 of the intermediate layer 12 becomes the resin layer (not shown), The layer on the side of the film-like adhesive 13 of the intermediate layer 12 becomes the above-described peeling treatment layer (not shown). Accordingly, in this case, the first surface 12a of the intermediate layer 12 becomes a peeling treatment surface. This intermediate layer 12 is easily peeled off of the film-like adhesive (the film-like adhesive 13 in Fig. 4 is cut off) at the time of pickup of the semiconductor chip on which the film-like adhesive described later is formed.

In the semiconductor processing sheet 1C shown in Fig. 4, the back surface of a semiconductor wafer (not shown) is affixed to the first surface 13a of the film-like adhesive 13, with the release film 15 removed, and further for a jig. The upper surface of the surface 16a of the adhesive layer 16 is attached to a jig such as a ring frame and used.

5 is a cross-sectional view schematically showing another embodiment of the sheet for semiconductor processing of the present invention.

The sheet 1D for semiconductor processing shown here is the same as the sheet 1C for semiconductor processing shown in FIG. 4 except that the jig adhesive layer 16 is not provided and the shape of the film-like adhesive is different. That is, the sheet 1D for semiconductor processing is provided with the base material 11, the intermediate layer 12 is provided on the base material 11, and the film adhesive 23 is provided on the intermediate layer 12. The support sheet 10 is a laminate of the substrate 11 and the intermediate layer 12, and the sheet for semiconductor processing 1D is also laminated with a film adhesive 23 on the first surface 10a of the support sheet 10 Has a configuration.

In the semiconductor processing sheet 1D, the intermediate layer 12 is laminated on the first surface 11a of the substrate 11, and a part of the first surface 12a of the intermediate layer 12, that is, a film on the center side region. The upper adhesive 23 is laminated. And, of the first surface 12a of the intermediate layer 12, a region in which the film adhesive 23 is not laminated, and of the film adhesive 23, a surface 23a that is not in contact with the intermediate layer 12 The release film 15 is laminated on (upper surface and side surface).

When the semiconductor processing sheet 1D is viewed from above and viewed in a plan view, the film adhesive 23 has a smaller surface area than the intermediate layer 12, and has a shape such as a circle shape.

In the sheet 1D for semiconductor processing shown in FIG. 5, with the release film 15 removed, the back surface of a semiconductor wafer (not shown) is affixed on the upper surface of the surfaces 23a of the film-like adhesive 23, and Of the first surface 12a of the intermediate layer 12, a region in which the film-like adhesive 23 is not laminated is affixed to a jig such as a ring frame and used.

On the other hand, in the semiconductor processing sheet 1D shown in FIG. 5, in the region in which the film-like adhesive 23 is not laminated, among the first surface 12a of the intermediate layer 12, as shown in FIGS. 2 and 4 Similarly, a jig adhesive layer may be laminated (not shown). The semiconductor processing sheet 1D provided with such a jig adhesive layer is used with the upper surface of the surface of the jig adhesive layer affixed to a jig such as a ring frame, as in the case of the semiconductor processing sheet shown in FIGS. 2 and 4. do.

As described above, the sheet for semiconductor processing may have any form of the supporting sheet and the film-like adhesive or provided with a jig adhesive layer. However, usually as shown in Figs. 2 and 4, as a sheet for semiconductor processing provided with a jig adhesive layer, it is preferable that a jig adhesive layer is provided on a film adhesive.

The sheet for semiconductor processing of the present invention is not limited to the ones shown in Figs. 2 to 5, and parts of the configurations shown in Figs. 2 to 5 have been changed or deleted within the range that does not impair the effects of the present invention. Another configuration may be added to the one described above.

For example, in the sheet for semiconductor processing shown in Figs. 2 to 5, a base material, an intermediate layer, a film-like adhesive, and a layer other than a release film may be formed at arbitrary locations.

In addition, in the sheet for semiconductor processing, a partial gap may be formed between the release film and the layer in direct contact with the release film.

In addition, in the sheet for semiconductor processing, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

◇How to use film adhesive and semiconductor processing sheet

The film adhesive and the semiconductor processing sheet of the present invention can be used to manufacture a semiconductor package and a semiconductor device through the production of a semiconductor chip on which the film adhesive is formed.

After the film-like adhesive without the supporting sheet is affixed to the back surface of the semiconductor wafer, for example, the release film is removed as necessary, and the exposed surface (that is, the side opposite to the side affixed to the semiconductor wafer. In this specification, a dicing sheet is affixed to (may be referred to as a "second surface"). The thus obtained dicing sheet, film adhesive, and semiconductor wafer are laminated in this order in their thickness direction, and a laminated structure is then subjected to a known dicing step. On the other hand, the laminated structure of a dicing sheet and a film adhesive can be regarded as a dicing die bonding sheet.

By performing the dicing process, the semiconductor wafer is divided into a plurality of semiconductor chips, and the film adhesive is also cut along the outer periphery of the semiconductor chip, and the semiconductor chip (film adhesive is It may be referred to as a formed semiconductor chip).

On the other hand, the sheet for semiconductor processing already has a structure as a dicing die bonding sheet. Therefore, in the step in which the semiconductor processing sheet is affixed to the back surface of the semiconductor wafer, after the semiconductor processing sheet (dicing sheet, film-like adhesive) and the semiconductor wafer are obtained in this order, a laminated structure stacked in their thickness direction. As described above, a semiconductor chip with a film adhesive is obtained in the same manner as when a dicing sheet is affixed to the second surface using a film adhesive not provided with a support sheet.

The dicing method of the semiconductor wafer may be any known method, and is not particularly limited.

Preferred dicing methods for semiconductor wafers include, for example, a method using a blade (ie, blade dicing), a method performed by laser irradiation (ie, laser dicing), and a method performed by spraying water containing an abrasive. A method of cutting a semiconductor wafer, such as (that is, water dicing), is mentioned.

Even when either a film adhesive or a semiconductor processing sheet is used, the semiconductor chip on which the obtained film adhesive is formed is then separated from the dicing sheet (picked up) and die-bonded to the circuit formation surface of the substrate by the film adhesive. do. Thereafter, a semiconductor package and a semiconductor device are manufactured in the same manner as in the conventional method.

For example, if necessary, at least one semiconductor chip is further laminated on the die-bonded semiconductor chip, wire bonding is performed, and then the entire obtained product is sealed with a resin to produce a semiconductor package. And using this semiconductor package, a target semiconductor device is manufactured.

By using the film-like adhesive of the present invention, the obtained semiconductor package becomes highly reliable.

In one aspect, the film adhesive of the present invention is a film adhesive having the following properties:

(I-1) When the initial detection temperature of the melt viscosity of the film adhesive after storage at 40°C for 168 hours is T ₁₆₈ , and the initial detection temperature of the melt viscosity before storage of the film adhesive is T ₀ ,

The T ₁₆₈ is 50 to 78°C,

The T ₀ is 59 to 71°C,

The difference between the T ₁₆₈ and the T ₀ △ T ₁₆₈ is 0~7 ℃ and;

(II-1) When the gel fraction of the film adhesive after storage at 40°C for 168 hours is W ₁₆₈ , and the gel fraction before storage of the film adhesive is W ₀ ,

W ₁₆₈ is 9 to 12%,

W ₀ is 3 to 8% or 5 to 8%,

The rate of change RW ₁₆₈ of the gel fraction determined from W ₁₆₈ and W ₀ is 113 to 150%; In addition

(III-1) The elongation at break measured according to JIS K7161:1994 after storage at 40° C. for 168 hours of the film adhesive is F ₁₆₈ , and measurement according to JIS K7161:1994 before storage of the film adhesive. When one breaking elongation is F ₀ ,

F ₁₆₈ is 0 to 23%, or 5 to 23%,

The F ₀ is 700 to 800%,

The reduction ratio RF ₁₆₈ of the breaking elongation calculated from F ₁₆₈ and F ₀ is 560 to 700%.

In addition, the film adhesive is formed of a film adhesive composition,

The film adhesive composition contains a polymer component (a), an epoxy-based thermosetting resin (b), a curing accelerator (c), a filler (d), and a coupling agent (e);

The polymer component (a) is

N-butyl acrylate (preferably 10 to 15 parts by mass per 100 parts by mass of the polymer component (a)), methyl acrylate (preferably 70 to 80 parts by mass per 100 parts by mass of the polymer component (a)) ), glycidyl methacrylate (preferably 2 to 5 parts by mass per 100 parts by mass of the polymer component (a)), and 2-hydroxyethyl acrylate (with respect to 100 parts by mass of the polymer component (a)) , Preferably 15 to 20 parts by mass) of an acrylic resin obtained by copolymerization, or

N-butyl acrylate (with respect to 100 parts by mass of the polymer component (a), preferably 40 to 50 parts by mass), ethyl acrylate (with respect to 100 parts by mass of the polymer component (a), preferably 20 to 30 parts by mass) ), acrylonitrile (with respect to 100 parts by mass of the polymer component (a), preferably 20 to 40 parts by mass), and glycidyl methacrylate (with respect to 100 parts by mass of the polymer component (a), preferably Is an acrylic resin obtained by copolymerizing 2 to 5 parts by mass);

The epoxy-based thermosetting resin (b) is composed of an epoxy resin (b1) and a thermosetting agent (b2);

The epoxy resin (b1) is

Bisphenol A type epoxy resin and polyfunctional aromatic type (triphenylene type) epoxy resin, or bisphenol F type epoxy resin and dicyclopentadiene type epoxy resin;

The thermosetting agent (b2) is an o-cresol-type novolac resin;

The curing accelerator (c) is

Inclusion compound of 1 molecule of 5-hydroxyisophthalic acid (HIPA) and 2 molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), or 2-phenyl-4,5-dihydroxymethyl Imidazole;

The filler (d) is spherical silica (preferably, the average particle diameter is 0.01 to 0.05 μm); In addition

The coupling agent (e) is an oligomeric silane coupling agent having an epoxy group, a methyl group, and a methoxy group, or an oligomeric silane coupling agent having an epoxy group, a methyl group, and a methoxy group, and 3-glycidoxypropyltrimethoxysilane and Glycidoxypropyltriethoxysilane phosphorus

It may be a film adhesive.

In addition, the film-like adhesive

The content of the polymer component (a) is 7 to 12% by mass with respect to the total content of all components constituting the film-like adhesive composition (that is, the total mass of the film-like adhesive composition);

The ratio of the content of the structural unit derived from glycidyl methacrylate is 2 to 5% by mass with respect to the total amount of the structural unit constituting the polymer component (a);

The content of the epoxy-based thermosetting resin (b) is 600 to 1000 parts by mass based on 100 parts by mass of the polymer component (a);

The content of the curing accelerator (c) is 0.1 to 2 parts by mass based on 100 parts by mass of the epoxy-based thermosetting resin (b);

The content of the filler (d) is 15 to 30% by mass with respect to the total content of all components constituting the film-like adhesive composition (that is, the total mass of the film-like adhesive composition); In addition

The content of the coupling agent (e) is 0.1 to 5 parts by mass based on 100 parts by mass of the total content of the polymer component (a) and the epoxy-based thermosetting resin (b).

It may be a film adhesive.

Example

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

<Monomer>

In the present Examples and Comparative Examples, the official names of the abbreviated monomers are shown below.

BA: n-butyl acrylate

MA: methyl acrylate

HEA: 2-hydroxyethyl acrylate

GMA: Glycidyl methacrylate

EA: ethyl acrylate

AN: Acrylonitrile

<Materials for manufacturing adhesive composition>

In the present Examples and Comparative Examples, the raw materials used for producing the adhesive composition are shown below.

[Polymer component (a)]

(a)-1: Acrylic resin (weight average molecular weight 350000, glass transition temperature) obtained by copolymerizing BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass), and HEA (15 parts by mass)- 1℃)

(a)-2: Acrylic resin obtained by copolymerization of BA (40 parts by mass), EA (25 parts by mass), AN (30 parts by mass), and GMA (5 parts by mass) (weight average molecular weight 700000, glass transition temperature- 14℃)

(a)-3: Acrylic resin obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass), and HEA (15 parts by mass) (weight average molecular weight 800000, glass transition temperature- 28℃)

(a)-4: Thermoplastic resin, polyester (Toyobo Corporation "Vylon 220", weight average molecular weight 35000, glass transition temperature 53 degreeC)

[Epoxy resin (b1)]

(b1)-1: Bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g/eq)

(b1)-2: Polyfunctional aromatic type (triphenylene type) epoxy resin ("EPPN-502H" manufactured by Nippon Explosives Co., Ltd., epoxy equivalent 167 g/eq, softening point 54°C, weight average molecular weight 1200)

(b1)-3: Bisphenol F-type epoxy resin ("YL983U" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170 g/eq)

(b1)-4: Dicyclopentadiene type epoxy resin ("XD-1000-L" manufactured by Nippon Explosives Co., Ltd., epoxy equivalent 248 g/eq)

(b1)-5: A mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles ("BPA328" manufactured by Nippon Explosives Co., Ltd., epoxy equivalent 235 g/eq)

(b1)-6: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC, epoxy equivalent 255 to 260 g/eq)

[Thermal Curing Agent (b2)]

(b2)-1: o-cresol-type novolac resin ("Phenolite KA-1160" manufactured by DIC)

(b2)-2: novolac-type phenolic resin (novolac resin other than o-cresol-type, Showa Electric Corporation ``BRG-556'')

(b2)-3: Dicyandiamide ("Adeka Hardener EH-3636AS" manufactured by ADEKA, solid dispersion type latent curing agent, active hydrogen amount 21 g/eq)

[Hardening accelerator (c)]

(c)-1: Inclusion compound of 1 molecule of 5-hydroxyisophthalic acid (HIPA) and 2 molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) (manufactured by Nippon Soda Corporation ``HIPA- 2P4MHZ」)

(c)-2: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Industry Co., Ltd. "Curesol 2PHZ-PW")

[Filling material (d)]

(d)-1: spherical silica modified with an epoxy group ("Admanano YA050C-MKK" manufactured by Admatex, average particle diameter 50 nm)

(d)-2: Silica filler ("SC2050MA" manufactured by Admatex, a silica filler surface-modified with an epoxy compound, an average particle diameter of 500 nm)

[Coupling agent (e)]

(e)-1: 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 12.7 mmol/g, molecular weight 236.3)

(e)-2: 3-glycidoxypropyltriethoxysilane ("KBE-403" manufactured by Shin-Etsu Silicone Co., Ltd., silane coupling agent, methoxy equivalent 8.1 mmol/g, molecular weight 278.4)

(e)-3: An oligomeric silane coupling agent having an epoxy group, a methyl group, and a methoxy group ("X-41-1056" manufactured by Shin-Etsu Silicone Co., Ltd., epoxy equivalent 280 g/eq)

(e)-4: Trimethoxy[3-(phenylamino)propyl]silane ("SZ6083" manufactured by Toray Dow, silane coupling agent)

(e)-5: Silicate compound to which 3-glycidoxypropyltrimethoxysilane was added ("MKC silicate MSEP2" manufactured by Mitsubishi Chemical Corporation))

[Crosslinking agent (f)]

(f)-1: Tolylene diisocyanate trimer adduct of trimethylolpropane ("BHS8515" manufactured by Toyo Chem)

[Energy ray curable resin (g)]

(g)-1: Tricyclodecanedimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Explosives, UV-curable resin, molecular weight 304)

[Photopolymerization initiator (h)]

(h)-1: 1-hydroxycyclohexylphenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF)

(h)-2: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE (registered trademark) 369" manufactured by BASF))

[Example 1]

<<Manufacture of film adhesive>>

<Preparation of adhesive composition>

Polymer component ((a)-1) (10 parts by mass), epoxy resin ((b1)-1) (20 parts by mass), epoxy resin ((b1)-2) (25 parts by mass), thermosetting agent ((b2) )-1) (25 parts by mass), curing accelerator ((c)-1) (0.3 parts by mass), filler ((d)-1) (20 parts by mass), coupling agent ((e)-1) (0.3 Parts by mass), coupling agent ((e)-2) (0.4 parts by mass), and coupling agent ((e)-3) (0.5 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23°C, An adhesive composition having a solid content concentration of 55% by mass was obtained. On the other hand, the blending amounts of components other than methyl ethyl ketone shown here are all values in terms of solid content.

<Production of film adhesive>

One side of a polyethylene terephthalate (PET) film was peeled off by a silicone treatment, on the peeling-treated side of a release film (“SP-PET381031H” manufactured by Lintec, a thickness of 38 μm) It was coated and dried by heating at 100° C. for 2 minutes to form a film-like adhesive having a thickness of 20 μm.

<Production of sheet for semiconductor processing>

By bonding a polyethylene film (thickness 100 μm) as a base material to the surface (exposed surface) of the film adhesive obtained above, opposite to the side provided with the release film, the base material, the film adhesive and the release film are in this order. As a result, a sheet for semiconductor processing was obtained by laminating in these thickness directions.

<<Evaluation of film adhesive>>

<Calculation of the initial detected temperature difference △ T ₁₆₈ of melt viscosity>

From the film-like adhesive obtained above, a columnar test piece having a diameter of 10 mm and a height of 20 mm was produced immediately.

At the measuring point of the capillary rheometer ("CFT-100D" manufactured by Shimadzu Corporation), the test piece immediately after this production was set, and while applying a force of 5.10 N (50 kgf) to the test piece, the test piece was heated at a heating rate of 10°C/ The temperature was raised from 50°C to 120°C in min. Then, the temperature at which the detection of the melt viscosity of the test piece was started (initial detection temperature T ₀ ) (° C.) was obtained when extrusion of the test piece was started from the hole formed in the die with a diameter of 0.5 mm and a height of 1.0 mm. Table 1 shows the results.

Separately, the film-like adhesive obtained above was placed in a dark place in an air atmosphere immediately after its production, and left still at 40°C for 168 hours (1 week).

From the film-like adhesive after storage, the same columnar test piece as described above was immediately produced.

And, in the same manner as in the case of the test piece produced from the film-like adhesive immediately after the production, for the test piece produced from the film-like adhesive after storage, the temperature at which the detection of the melt viscosity was started (initial detection temperature T ₁₆₈ ) (° C.) Saved. Further, the difference ΔT ₁₆₈ (°C) between T ₁₆₈ and T ₀ was calculated. Table 1 shows these results.

<Calculation of the change rate RW ₁₆₈ of the gel fraction>

From the film-like adhesive obtained above, a sheet-like test piece (0.5 g) having a size of 2.5 cm x 4.0 cm x 600 µm was produced immediately.

The test piece immediately after this production was wrapped with a polyester #200 mesh, and the test piece in this state was immersed in methyl ethyl ketone (300 ml) at 23°C for 24 hours.

Next, the test piece was taken out together with the mesh in methyl ethyl ketone, and the test piece from which the mesh was removed was dried at 120° C. for 1 hour.

After the dried test piece was allowed to stand still for 24 hours in an environment of 23°C and 50% relative humidity, the mass of the test piece was measured. And the gel fraction W ₀ (%) was calculated from this measured value and the mass (0.5 g) of the test piece before immersion. Table 1 shows the results.

Separately, the film-like adhesive obtained above was placed in a dark place in an air atmosphere immediately after its production, and left still at 40°C for 168 hours (1 week).

From the film-like adhesive after storage, a sheet-like test piece similar to the above was produced immediately. And the gel fraction W ₁₆₈ (%) was calculated for the test piece produced from the film-like adhesive after storage in the same manner as in the case of the test piece produced from the film-like adhesive immediately after the above production. Further, according to the above formula (i), the rate of change RW ₁₆₈ (%) of the gel fraction of the test piece was calculated. Table 1 shows these results.

<Calculation of RF ₁₆₈ , the rate of decrease in elongation at break>

According to JIS K7161:1994, a test piece was immediately produced from the film-like adhesive obtained above, and the elongation at break F ₀ (%) was measured for the test piece immediately after the production. Table 1 shows the results.

Separately, the film-like adhesive obtained above was placed in a dark place in an air atmosphere immediately after its production, and left still at 40°C for 168 hours (1 week).

Subsequently, immediately, according to JIS K7161:1994 (ISO 527-1:1993), a test piece was prepared from the film-like adhesive after storage, and the elongation at break F ₁₆₈ (%) was measured for this test piece. Further, according to the above formula (ii), the decrease rate RF ₁₆₈ (%) of the fracture elongation of the test piece was calculated. Table 1 shows these results.

<Evaluation of reliability of semiconductor package>

(Manufacture of semiconductor chips with film-like adhesives)

A surface protection tape ("Adwill E-3125KN" manufactured by Lintec) was affixed to the mirror surface of an 8-inch silicon mirror wafer (720 µm in thickness) at room temperature using a tape bonding apparatus ("RAD3510" manufactured by Lintec). Then, using a grinder ("DFG8760" manufactured by DISCO Corporation), the side surface (that is, the back surface) of the silicon wafer opposite to the surface to which this surface protection tape was affixed was ground. Grinding at this time was performed until the thickness of the silicon wafer became 50 µm, and the grinding surface was made into a dry polish finish.

Next, in the sheet for semiconductor processing obtained above, the release film was removed. Then, the sheet for semiconductor processing was affixed to the grinding surface (back surface) of this silicon mirror wafer using a laminating apparatus ("VA-400" manufactured by Taisei Laminator) with the film-like adhesive. At this time, the sheet for semiconductor processing was heated at 60°C, and affixed under the conditions of an affixing speed of 0.6 m/min and an affixing pressure of 0.5 MPa.

Next, in the sheet for semiconductor processing after affixing to the silicon mirror wafer, the substrate was removed from the film-like adhesive. Then, an expanded tape ("ADWILL DG889SO5" manufactured by Lintec) was affixed to the exposed surface of the newly formed film-like adhesive using a laminating device ("VA-400" manufactured by Taisei Laminator). At this time, the expanded tape was affixed under the conditions of an affixing speed of 0.6 m/min and an affixing pressure of 0.5 MPa under normal temperature.

Next, a double-sided tape for fixing a ring frame ("ADWILL G-01DF*" manufactured by Lintec) was affixed to the exposed surface of the expand tape in the vicinity of the peripheral portion not adhered to the film-like adhesive. Then, the expanded tape, the film-like adhesive, and the silicon mirror wafer were laminated in this order in the thickness direction thereof, and the first laminated structure was fixed to the ring frame by this double-sided tape.

Subsequently, the surface protection tape is removed from the mirror surface of the silicon mirror wafer and diced using a dicing device ("DFD6361" manufactured by Disco) to divide the silicon mirror wafer and cut the film adhesive. Thus, a silicon chip having a size of 8 mm x 8 mm was obtained. In this case, dicing is performed with the dicing blade moving speed of 50 mm/sec and the rotation speed of the dicing blade at 40000 rpm. For the expanded tape, dicing to a depth of 20 μm from the affixed surface of the film-like adhesive. It was done by cutting with a blade.

As described above, a plurality of silicon chips (that is, a silicon chip on which a plurality of film-like adhesives are formed) having a film-like adhesive after cutting on the back surface is fixed in a state aligned on the expand tape by the film-like adhesive. A second laminated structure was obtained.

(Manufacture of semiconductor package)

As a substrate, a circuit pattern was formed on a copper foil (18 µm thick) of a copper foil-clad laminate ("HL832NX-A" manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a solder resist ("PSR-4000 AUS308 manufactured by Taiyo Ink Co., Ltd." The substrate on which the layer was formed ("LN001E-001 PCB (Au) AUS308" manufactured by Shima Electronics Co., Ltd.) was prepared.

On the other hand, the second laminated structure obtained above was installed in the expand unit of the pickup die bonding apparatus ("BESTEM D02" manufactured by Canon Machinery Co., Ltd.).

Subsequently, the second laminated structure was pushed up from the expand tape side under conditions of a push-up speed of 300 mm/min and a push-up amount of 200 µm using five pins, and a collet having a size of 8 mm×8 mm Using, the silicon chip on which the film-like adhesive was formed was picked up by separating it from the expand tape.

Next, the silicon chip on which the picked up film-like adhesive was formed was bonded to the substrate. Bonding at this time was performed by applying a force of 2.45 N (250 gf) for 0.5 seconds to the silicon chip on which the film adhesive was formed heated at 120°C.

Next, a layer made of a sealing resin ("KE-G1250" manufactured by Kyocera Chemical) was formed on the silicon chip after bonding using a sealing device ("MPC-06M TriAl Press" manufactured by Apic Yamada). Then, this sealing resin was cured and a sealing layer having a thickness of 400 µm was formed to obtain a sealing substrate. The curing of the sealing resin at this time was performed by applying a pressure of 7 MPa to the sealing resin heated at 175°C for 2 minutes.

Next, a dicing tape ("adwill D-510T" manufactured by Lintec Co., Ltd.) was affixed to this sealing substrate, and the rotation speed of the dicing blade was set to 4000 rpm using a dicing device ("DFD6361" manufactured by Disco Corporation), By dicing this sealing substrate, a semiconductor package having a size of 15 mm x 15 mm was obtained.

(Evaluation of reliability of semiconductor package)

With respect to the semiconductor package obtained above, IR reflow was performed three times immediately by heating for 1 minute at a maximum temperature of 260°C. IR reflow at this time was performed using a tabletop reflow oven ("STR-2010N2M" manufactured by Senju Metal Industries, Ltd.).

Next, the semiconductor package after this IR reflow was observed using an ultrasonic microscope ("D-9600" manufactured by Sonoscan), and the presence or absence of lifting of the joint, the presence or absence of peeling of the joint, and the presence or absence of a package crack were confirmed. In addition, when lifting of the bonding portion, peeling of the bonding portion, and all of the package cracks were not confirmed, it was determined as "A", and when one or more of them were confirmed, it was determined as "B". Table 1 shows the results.

Separately, in accordance with JEDEC Level 2, the semiconductor package obtained above was subjected to moisture absorption by standing still for 168 hours (1 week) under moist heat conditions at 85°C and 60% relative humidity.

Then, immediately, the semiconductor package after moisture absorption was subjected to IR reflow three times in the same manner as in the case of the semiconductor package immediately after the above-described manufacturing, and the semiconductor package after IR reflow was evaluated. Table 1 shows the results.

<Production of film adhesives and sheets for semiconductor processing, and evaluation of film adhesives>

[Example 2, Comparative Examples 1 to 2]

Except for changing either or both of the type and amount of the compounded component at the time of manufacture of the adhesive composition so that the type and content of the components contained in the adhesive composition are as shown in Table 1, the same as in Example 1 In the same manner, a film adhesive and a sheet for semiconductor processing were produced, and the film adhesive was evaluated. Table 1 shows the results.

As is clear from the above results, in Examples 1 to 2, ΔT ₁₆₈ was 7°C or less (0-7°C), and during storage of the film-like adhesive, the melt viscosity was stable. In addition, W ₀ was 8%, RW ₁₆₈ was 150% or less (113 to 150%), the gel fraction before storage of the film adhesive was low, and the gel fraction was stable during storage of the film adhesive. . Further, RF ₁₆₈ was 22.8% or less (22.2 to 22.8%), and the elongation at break was stable during storage of the film-like adhesive.

In this way, the film adhesives of Examples 1 to 2 had stable melt viscosity, gel fraction, and elongation at break during storage, and the storage stability of the film adhesive was high.

And reflecting these results, in Examples 1 to 2, the reliability of the semiconductor package was high both immediately after manufacture and after moisture absorption.

On the other hand, in Comparative Example 1, ΔT ₁₆₈ was 14°C, and during storage of the film-like adhesive, the melt viscosity was not stable and was remarkably increased. Further, W ₀ was 8%, RW ₁₆₈ was 300%, and the gel fraction before storage of the film adhesive was low, but during storage of the film adhesive, the gel fraction was not stabilized and increased remarkably. In addition, RF ₁₆₈ was 85.4%, and during storage of the film-like adhesive, the elongation at break was not stable and significantly decreased.

Thus, the film adhesive of Comparative Example 1 did not stabilize the melt viscosity, gel fraction, and elongation at break during storage, and the storage stability of the film adhesive was low.

And, in view of these results, in Comparative Example 1, the reliability of the semiconductor package immediately after manufacture was high, but the reliability of the semiconductor package after moisture absorption was all at a low level.

In Comparative Example 2, ΔT ₁₆₈ was 1°C, and during storage of the film-like adhesive, the melt viscosity was stable. On the other hand, W ₀ was 18%, and the gel fraction before storage of the film adhesive was high. RW ₁₆₈ was 117%, and during storage of the film-like adhesive, the gel fraction was stable, but this was merely a state with a high gel fraction. RF ₁₆₈ was 12.5% or less, and the elongation at break was stable during storage of the film-like adhesive.

As described above, the film-like adhesive of Comparative Example 2 had a consistently high gel fraction from the initial stage (right after production), and it could not be determined that the storage stability was high.

And reflecting these results, in Comparative Example 2, either immediately after manufacture or after moisture absorption, the reliability of the semiconductor package was low.

The present invention can provide a film adhesive capable of producing a semiconductor package having high storage stability and high reliability based on this, and a sheet for semiconductor processing provided with the film adhesive, and thus can be used in the manufacture of semiconductor devices. , Very useful in industry.

1A, 1B, 1C, 1D... Sheet for semiconductor processing,
10… Support sheet,
12... Middle floor,
13, 23... Adhesive on film

Claims (4)

A film adhesive having the following properties:
(I) the initial detection temperature of the melt viscosity of the film adhesive after storage at 40° C. for 168 hours is T ₁₆₈ ,
When the initial detection temperature of the melt viscosity of the film-like adhesive before storage is T ₀ ,
And the T ₁₆₈ and T ₀ the difference △ T ₁₆₈ of less than 10 ℃, also
(II) When the gel fraction before storing the said film adhesive at 40 degreeC is W ₀ , the film adhesive which W ₀ is 15% or less. A film adhesive having the following properties:
(I') the gel fraction of the film adhesive after storage at 40°C for 168 hours is W ₁₆₈ ,
When the gel fraction before storage of the film-like adhesive is W ₀ ,
The rate of change RW ₁₆₈ of the gel fraction determined from W ₁₆₈ and W ₀ is 200% or less, and
(II') A film adhesive having the gel fraction W ₀ of 15% or less. A film adhesive having the following properties:
(I") The elongation at break measured in accordance with JIS K7161:1994 after storage at 40°C for 168 hours of the film-like adhesive is F ₁₆₈ ,
When the elongation at break measured in accordance with JIS K7161:1994 of the film-like adhesive before storage was F ₀ ,
The rate of decrease in breaking elongation RF ₁₆₈ obtained from F ₁₆₈ and F ₀ is less than 30%, and
(II") When the gel fraction of the film adhesive before storing the film adhesive at 40°C is W ₀ , the W ₀ is 15% or less. A sheet for semiconductor processing comprising a support sheet and the film adhesive of any one of claims 1 to 3 provided on the support sheet.

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