WO2019182001A1

WO2019182001A1 - Film-like adhesive and sheet for semiconductor processing

Info

Publication number: WO2019182001A1
Application number: PCT/JP2019/011659
Authority: WO
Inventors: 啓示布施
Original assignee: リンテック株式会社
Priority date: 2018-03-23
Filing date: 2019-03-20
Publication date: 2019-09-26
Also published as: JPWO2019182001A1; TWI798390B; CN111670231B; KR20200133717A; JP7282076B2; TW202325809A; CN111670231A; TWI836931B; TW202003735A; KR102637855B1

Abstract

A film-like adhesive having the following characteristics: (I) when an initial detected temperature of the melt viscosity of the film-like adhesive after being stored for 168 hours at 40°C is T₁₆₈, and when the initial detected temperature of the melt viscosity of the film-like adhesive before being stored is T₀, the difference ΔT₁₆₈ between the T₁₆₈ and the T₀ is less than 10°C, and (II) when a gel fraction before the film-like adhesive is stored at 40°C is W₀, W₀ is no more than 15%.

Description

Film adhesive and semiconductor processing sheet

The present invention relates to a film adhesive and a semiconductor processing sheet.
This application claims priority based on Japanese Patent Application No. 2018-057006 filed in Japan on March 23, 2018, the contents of which are incorporated herein by reference.

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

A semiconductor chip having a film-like adhesive on the back surface is produced, for example, by dividing (cutting) a semiconductor wafer having a film-like adhesive on the back surface together with the film-like adhesive. As a method for dividing the semiconductor wafer into semiconductor chips in this manner, for example, a method of dicing the semiconductor wafer together with the film adhesive using a dicing blade is known. In this case, the film adhesive before division (cutting) may be used as a dicing die bonding sheet laminated and integrated on a dicing sheet used for fixing the semiconductor wafer during dicing.

Various film adhesives have been disclosed so far depending on the purpose.
For example, a heat containing a thermoplastic resin component of 5 to 15% by weight and a thermosetting resin component of 45 to 55% by weight as a main component and having a melt viscosity at 100 ° C. of 400 Pa · s to 2500 Pa · s before thermosetting. A curable die-bonding film is disclosed (see Patent Document 1).
This thermosetting die-bonding film is excellent in adhesion to an adherend and is supposed to prevent contamination of the substrate and the semiconductor chip due to bleeding of the adhesive.

The organic fraction after being thermally cured by heat treatment at 120 ° C. for 1 hour has a gel fraction of 20% by weight or less in the organic component after being thermally cured by heat treatment at 175 ° C. for 1 hour. A thermosetting die-bonding film in which the gel fraction in the component is in the range of 10 to 30% by weight is disclosed (see Patent Document 2). This thermosetting die-bonding film is supposed to suppress curing shrinkage after die bonding, thereby preventing warpage of the adherend.

JP 2008-244464 A JP 2011-103440 A

The characteristics of the film adhesive may change due to the reaction of the crosslinkable or curable component that is a component of the film adhesive during storage until it is used. As described above, a film-like adhesive that easily changes its characteristics and has low storage stability may not sufficiently exhibit the intended action during use. Furthermore, the reliability of a semiconductor package manufactured using such a film adhesive and a semiconductor chip may be reduced.

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

The thermosetting die-bonding film (film adhesive) described in Patent Document 2 has a gel fraction in the organic component after thermosetting within a specific range, but is the gel fraction before and after storage stable? It is not certain whether or not.

As described above, the thermosetting die-bonding film (film adhesive) described in Patent Documents 1 and 2 has high storage stability and can manufacture a highly reliable semiconductor package. , Is not certain.

An object of the present invention is to provide a film adhesive capable of producing a semiconductor package having high storage stability and high reliability based thereon, and a semiconductor processing sheet provided with the film adhesive. To do.

In order to solve the above problems, the present invention is a case where the film adhesive is stored at 40 ° C., and when the initial detection temperature of the melt viscosity is obtained for the film adhesive before and after storage, the storage time is 168 hours. The difference ΔT ₁₆₈ between the initial detection temperature T ₁₆₈ and the initial detection temperature T ₀ before storage is less than 10 ° C., and the film adhesive before storing the film adhesive at 40 ° C. A film adhesive having a gel fraction W ₀ of 15% or less is provided.
In addition, the present invention stores the film adhesive at 40 ° C., and when 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, The change rate RW ₁₆₈ of the gel fraction when the storage time is 168 hours, obtained from the gel fraction W ₀ before storage, is 200% or less, and the gel fraction W ₀ is 15 %, The film adhesive is provided.

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, the storage time is 168 hours. The breaking elongation reduction rate RF ₁₆₈ when the storage time is 168 hours, which is obtained from the breaking elongation F ₁₆₈ and the breaking elongation F ₀ before storage, is less than 30%, Provided is a film adhesive in which a gel fraction W ₀ of the film adhesive before storing the film adhesive at 40 ° C. is 15% or less.
Moreover, this invention provides the sheet | seat for semiconductor processing provided with the support sheet and having the said film adhesive on the said support sheet.

That is, the present invention includes the following aspects.
[1] Film adhesive having the following characteristics:
(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 of the film adhesive before storage is T ₀ When the difference ΔT ₁₆₈ between the T ₁₆₈ and the T ₀ is less than 10 ° C. and (II) the gel fraction before storing the film adhesive at 40 ° C. is W ₀ , the W ₀ Is 15% or less.
[2] Film adhesive having the following characteristics:
(I ′) When the gel fraction of the film adhesive after storage for 168 hours at 40 ° C. is W ₁₆₈ and the gel fraction of the film adhesive before storage is W ₀ , the W ₁₆₈ The change rate RW ₁₆₈ of the gel fraction obtained from the W ₀ is 200% or less, and (II ′) the W ₀ is 15% or less.
[3] Film adhesive having the following characteristics:
(I '') JIS after storage the film-like 168 hours at 40 ° C. of the adhesive K7161: elongation at break, determined in accordance with the 1994 and _{F 168,} before the storage of the film-like adhesive JIS K7161: When the elongation at break measured in accordance with 1994 is F ₀ , the decrease rate RF _{168 of} elongation at break 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 defined as W ₀ , the W ₀ is 15% or less.
[4] a support 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], which further has the following characteristics:
(III) When the gel fraction of the film adhesive after storage at 40 ° C. for 168 hours is W _168, and the gel fraction of the film adhesive before storage is W ₀ , the W ₁₆₈ and the above The change rate RW ₁₆₈ of the gel fraction obtained from W ₀ is 200% or less.
[6] The film adhesive according to any one of [1] to [3], which further has the following characteristics:
(IV) the film-like after 168 hours storage at 40 ° C. of the adhesive JIS K7161: elongation at break, determined in accordance with the 1994 and _{F 168,} the film-like adhesive the storage prior to JIS of K7161: 1994 When the elongation at break measured in accordance with F0 is F ₀ , the reduction rate RF _{168 of the} elongation at break obtained from 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 thereon, and a semiconductor processing sheet provided with the film adhesive.

It is sectional drawing which shows typically the film adhesive which concerns on one Embodiment of this invention. It is sectional drawing which shows typically one Embodiment of the sheet | seat for semiconductor processing of this invention. It is sectional drawing which shows typically other embodiment of the sheet | seat for semiconductor processing of this invention. It is sectional drawing which shows typically other embodiment of the sheet | seat for semiconductor processing of this invention. It is sectional drawing which shows typically other embodiment of the sheet | seat for semiconductor processing of this invention.

◇ Film adhesive << First embodiment >>
When the film-like adhesive according to the first embodiment of the present invention stores the film-like adhesive at 40 ° C., and determines the initial detection temperature of the melt viscosity for the film-like adhesive before and after storage, the storage time is The difference ΔT ₁₆₈ between the initial detected temperature T _{168 in} the case of 168 hours and the initial detected temperature T ₀ before storage is less than 10 ° C., and the film adhesive before storing at 40 ° C. The gel fraction W ₀ of the film adhesive is 15% or less.
That is, the film adhesive according to the first embodiment of the present invention has the following characteristics:
(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 of the film adhesive before storage is T ₀ When the difference ΔT ₁₆₈ between the T ₁₆₈ and the T ₀ is less than 10 ° C. and (II) the gel fraction before storing the film adhesive at 40 ° C. is W ₀ , the W ₀ Is 15% or less.

The film-like adhesive of the first embodiment has curability, preferably has thermosetting properties, and preferably has pressure-sensitive adhesive properties. A film adhesive having both thermosetting and pressure-sensitive adhesive properties can be applied by lightly pressing on various adherends in an uncured state.
The film adhesive may be one that can be applied to various adherends by heating and softening. The film adhesive finally becomes a cured product having high impact resistance by curing, and this cured product can retain sufficient adhesive properties even under severe high temperature and high humidity conditions.

The film-like adhesive of the first embodiment thus has a small ΔT ₁₆₈ (= T ₁₆₈ −T ₀ ), and even when stored at 40 ° C. for 168 hours, the change in melt viscosity is suppressed, High storage stability. A film-like adhesive that satisfies such conditions is not limited to such storage conditions, but is generally stable under general storage conditions, and changes in properties during storage are suppressed. Can sufficiently exhibit the intended action. And by using such a film adhesive, a highly reliable semiconductor package can be manufactured.
In addition, the film-like adhesive of the first embodiment has a small W ₀ , and enables production of a highly reliable semiconductor package regardless of whether or not it is stored.

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

In the film adhesive of the first embodiment, the lower limit value 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-like adhesive of the first embodiment, ΔT ₁₆₈ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, ΔT ₁₆₈ is preferably 0 ° C. or more and less than 10 ° C., more preferably 0 to 9.5 ° C., further preferably 0 to 9 ° C., particularly preferably 0 to 8 ° C., for example, 0 to 6 ° C., And any of 0 to 3 ° C. 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 is preferably 35 to 100 ° C., more preferably 40 to 90 ° C., and particularly preferably 45 to 80 ° C. preferable. As another aspect, T ₀ may be 59 to 71 ° C. When T ₀ is equal to or more than the lower limit value, it is difficult for a gap to be formed between the film-like adhesive and the sticking target, and the embedding property to the sticking target is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. T ₀ that it is equal to or less than the upper limit, handling property of the film-like adhesive is further improved.

In the film-like adhesive of the first embodiment, T ₁₆₈ is not particularly limited, but is preferably 35 to 109.5 ° C, more preferably 40 to 99.5 ° C, and 45 to 89.5. It is particularly preferable that the temperature is C. As another aspect, T ₁₆₈ may be 59 to 78 ° C. When T ₁₆₈ is equal to or more than the lower limit value, it is difficult for a void portion to be generated between the film adhesive and the sticking object, and the embedding property to the sticking object is further improved. As a result, the reliability of the obtained semiconductor package becomes higher.
When _T168 is equal to or less than the 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 the melting temperature of the film adhesive whose storage time at 40 ° C. is t hours (t is a number of 0 or more). It is determined by measuring the viscosity by a known method. That is, using a capillary rheometer, set the film-like adhesive to be measured in the cylinder (capillary) and make contact with the inner wall of the cylinder along the inner wall along the longitudinal direction of the cylinder (in other words, the direction of the central axis) ) While maintaining a state in which a certain amount of force is applied to the film-like adhesive in the cylinder (a state where a load is applied, for example, 5.10 N) by the movable piston. The temperature is raised (for example, raised from 50 ° C. to 120 ° C. at 10 ° C./min). Then, from the hole (for example, a hole with a diameter of 0.5 mm and a height of 1.0 mm) provided at the tip of the cylinder (tip in the direction in which a force is applied to the film adhesive), the outside of the cylinder When the extrusion of the film adhesive is started, that is, when the detection of the melt viscosity of the film adhesive is started, the temperature of the film adhesive is set to the initial detection temperature T _t ( ° C). By this method, T ₁₆₈ and T ₀ are determined. The size and shape of the film adhesive used for the 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 the present specification, “melt viscosity” means the melt viscosity measured by the above method unless otherwise specified.

When storing the film-like adhesive, which is the measurement target of _Tt , at 40 ° C., it is preferably stored in an air atmosphere, preferably stored at rest, and preferably stored in a dark place. And it is more preferable to preserve | save so that these 2 or more conditions may be satisfy | filled, and it is especially preferable to preserve | save so that all conditions may be satisfy | filled.

When storing the film-like adhesive which is the measurement target of _Tt at 40 ° C., it is preferable to start the storage immediately after the production of the film-like adhesive.

In the film adhesive of the first embodiment, the Kell fraction W ₀ is 15% or less as described above, preferably 13% or less, more preferably 11% or less, and 9% or less. It is particularly preferred. When W ₀ is equal to or less than the upper limit value, it is difficult for a void portion to be generated between the film adhesive and the sticking target, and the embedding property to the sticking target is further improved. As a result, the reliability of the obtained semiconductor package becomes higher.

In the film adhesive of the first embodiment, the lower limit value of W ₀ is not particularly limited.
In the film-like adhesive of the first embodiment, W ₀ is preferably 3% or more, and more preferably 5% or more. When W ₀ is equal to or more than the lower limit, the handleability of the film adhesive is improved, and the film adhesive can be more easily attached to the semiconductor wafer. Furthermore, even if the layer adjacent to the film adhesive such as the substrate has an uneven surface, the followability of the film adhesive to the uneven surface is improved.

In the film-like adhesive according to the first embodiment, W ₀ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, in one embodiment, W ₀ is preferably 3-15%, more preferably 3-13%, even more preferably 3-11% ° C., and particularly preferably 3-9%. In another aspect, W ₀ is preferably 5 to 15%, more preferably 5 to 13%, still more 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 the present embodiment, the gel fraction W ₀ can be measured by a known method.
For example, 0.5 g of a sheet-like film adhesive test piece having a size of 2.5 cm × 4.0 cm × 600 μm is wrapped with a polyester mesh, and the test piece in this state is subjected to methyl ethyl ketone (23 ° C. (300 mL) for 24 hours, the test piece after immersion was dried (for example, dried at 120 ° C. for 1 hour), and the dried test piece was stored for 24 hours in an environment of 23 ° C. and a relative humidity of 50%. Then, the mass of this test piece is measured. 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 formula.

The melt viscosity of the film-like adhesive of the first embodiment, T _t such as T ₀ and T ₁₆₈ , ΔT ₁₆₈ and W ₀ (hereinafter, these are collectively referred to as “melt viscosity”). Any) can be appropriately adjusted by adjusting, for example, the type and amount of the component of the film adhesive. For example, the component of the film-like adhesive, which is a component of the polymer component (a) described later, and the content ratio thereof, the component 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-mentioned melt viscosity and the like can be adjusted as appropriate. However, these are only examples of methods for adjusting the above-described melt viscosity and the like.

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

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

The thickness of the film-like adhesive of the first embodiment is not particularly limited, but 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 adhesive is equal to or more than the lower limit, the adhesive force of the film adhesive to the adherend (semiconductor wafer, semiconductor chip) is further increased. When the thickness of the film adhesive is equal to or less than the above upper limit value, the film adhesive can be more easily cut in the semiconductor chip manufacturing process described later, and the generation of a cut piece derived from the film adhesive The amount can be further reduced.
Here, the “thickness of the film-like adhesive” means the thickness of the entire film-like adhesive. For example, the thickness of the film-like adhesive composed of a plurality of layers means all of the film-like adhesive. Means the total thickness of the layers.
In the present specification, “thickness” means a value measured by a constant pressure thickness measuring instrument.

The film adhesive can be formed from an adhesive composition containing the constituent materials. For example, a film adhesive can be formed in the target site | part by applying an adhesive composition to the formation object surface of a film adhesive, and making it dry as needed.
In the adhesive composition, the content ratio of components that do not vaporize at normal temperature is usually the same as the content ratio of the components of the film adhesive. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

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

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

<< Second Embodiment >>
When the film adhesive according to the second embodiment of the present invention is stored at 40 ° C. and the gel fraction is measured for the film adhesive before and after storage, the storage time is 168 hours. The change rate RW ₁₆₈ of the gel fraction when the storage time is 168 hours, which is obtained from the gel 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 adhesive according to the second embodiment of the present invention has the following characteristics:
(I ′) When the gel fraction of the film adhesive after storage for 168 hours at 40 ° C. is W ₁₆₈ and the gel fraction of the film adhesive before storage is W ₀ , the W ₁₆₈ The change rate RW ₁₆₈ of the gel fraction obtained from the W ₀ is 200% or less, and (II ′) the W ₀ is 15% or less.

The film-like adhesive of the second embodiment has a small RW _{168 as} described above, and even when stored at 40 ° C. for 168 hours, the change in gel fraction is suppressed and the storage stability is high. A film-like adhesive satisfying such conditions has high storage stability not only in such storage conditions but also in general storage conditions generally applied. And by using such a film 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 enables production of a highly reliable semiconductor package regardless of whether or not it is stored.

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

In the film-like adhesive of the second embodiment, the lower limit value of RW ₁₆₈ is not particularly limited, but is usually 100%. That is, in the film-like adhesive of the second embodiment, RW ₁₆₈ is preferably 100% or more. A film adhesive having such characteristics can be produced more easily.

In the film-like adhesive of the second embodiment, RW ₁₆₈ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, RW ₁₆₈ is preferably 100 to 200%, more preferably 100 to 185%, still more preferably 100 to 170% ° C, particularly preferably 100 to 155%, such as 100 to 140%, and 100 to It may be any of 125%. Another aspect may be 113 to 150%. However, these are examples of RW ₁₆₈ .

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

In the film adhesive of the second embodiment, the lower limit value of W ₀ is not particularly limited.
In the film-like adhesive of the second embodiment, W ₀ is preferably 3% or more, and more preferably 5% or more. When W ₀ is equal to or more than the lower limit, the handleability of the film adhesive is improved, and the film adhesive can be more easily attached to the semiconductor wafer. Furthermore, even if the layer adjacent to the film adhesive such as the substrate has an uneven surface, the followability of the film adhesive to the uneven surface is improved.

In the film-like adhesive of the second embodiment, W ₀ can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, in one embodiment, W ₀ is preferably 3-15%, more preferably 3-13%, even more preferably 3-11% ° C., and particularly preferably 3-9%. In another aspect, W ₀ is preferably 5 to 15%, more preferably 5 to 13%, still more preferably 5 to 11%, and particularly preferably 5 to 9%. As yet another aspect, W ₀ may be 3 to 8% or 5 to 8%. However, these are examples of _{W 0.}

In the film-like adhesive of the second embodiment, W ₁₆₈ is not particularly limited, but is preferably 4 to 16%, more preferably 5 to 15%, and particularly preferably 6 to 14%. preferable. In another aspect, W ₁₆₈ may be _9-12 %. When W ₁₆₈ is less than or equal to the above upper limit value, a void portion is less likely to be generated between the film-like adhesive and the sticking target, and the embedding property to the sticking target 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 lower limit, the handleability of the film adhesive is improved, and the film adhesive can be more easily attached to the semiconductor wafer. Furthermore, even if the layer adjacent to the film adhesive such as the substrate has an uneven surface, the followability of the film adhesive to the uneven surface is improved.

In the present embodiment, the gel fraction W _t of the film adhesive stored at 40 ° C. for t time (t is a number of 0 or more) can be measured by a known method.
For example, a 0.5 g × 4.0 cm × 600 μm sheet-shaped film-shaped adhesive test piece having a size of 2.5 cm × 4.0 cm × 600 μm is prepared from a film-shaped adhesive stored at 40 ° C. for t hours, and then a polyester mesh is used. The test piece in this state is immersed in methyl ethyl ketone (300 mL) at 23 ° C. for 24 hours, and the test piece after immersion is dried (for example, dried at 120 ° C. for 1 hour). After standing still for 24 hours in a 50% humidity environment, the mass of the 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.
The method of measuring the W ₀ in the present embodiment is the same as the measurement method of W ₀ in the first embodiment described above.

In the present specification, “gel fraction” means a gel fraction measured by the above method unless otherwise specified.

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

When saving a W _t measured in the film-like adhesive 40 ° C. from immediately after the production of the film-like adhesive, it is preferable to start saving.

RW ₁₆₈ can be calculated according to the following formula (i).
RW ₁₆₈ (%) = W ₁₆₈ / W ₀ × 100 (i)

The film-like adhesive of the second embodiment has the essential constitution that RW ₁₆₈ is 200% or less, and the film of the first embodiment described above except that ΔT ₁₆₈ does not have to be less than 10 ° C. It is the same as the adhesive.

For example, the film-like adhesive according to the second embodiment has curability like the film-like adhesive according to the first embodiment, and preferably has thermosetting, and has pressure-sensitive adhesiveness. Is preferable, and may have both thermosetting and pressure-sensitive adhesive properties. The film adhesive of the second embodiment also 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.
Moreover, the film adhesive of 2nd Embodiment may consist of 1 layer (single layer) similarly to the film adhesive of 1st Embodiment, and may consist of two or more layers. .
Moreover, the thickness of the film adhesive of 2nd Embodiment is the same as the thickness of the film adhesive of 1st Embodiment.
Moreover, the film adhesive of 2nd Embodiment can be manufactured by the method similar to the case of the film adhesive of 1st Embodiment.

In the film-like adhesive of the second embodiment, W _t such as W ₀ and W ₁₆₈ and RW ₁₆₈ (hereinafter, these may be collectively referred to as “W ₀ etc.”) It can be adjusted as appropriate by adjusting the type and amount of the components contained in the film adhesive. For example, the component of the film-like adhesive, which is a component of the polymer component (a) described later, and the content ratio thereof, the component of the epoxy resin (b1), the three-dimensional structure of the thermosetting agent (b2), and curing By adjusting the reactivity of the accelerator (c), the average particle size of the filler (d), and the like, the above-described W _{0 and the} like can be appropriately adjusted. However, these are only examples of adjusting methods such as the above-described W ₀ .

<< Third Embodiment >>
In the film-like adhesive according to the third embodiment of the present invention, the film-like adhesive was stored at 40 ° C., and the elongation at break was measured according to JIS K7161: 1994 for the film-like adhesive before and after storage. When the storage time is 168 hours, the breaking elongation F ₁₆₈ when the storage time is 168 hours, and the breaking elongation F ₀ before the storage, the decrease rate RF _{168 of the} breaking elongation when the storage time is 168 hours However, it is less than 30%, and the gel fraction W ₀ of the film adhesive before storing the film adhesive at 40 ° C. is 15% or less.
As another aspect, the film adhesive according to the third embodiment of the present invention has the following characteristics:
(I '') JIS after storage the film-like 168 hours at 40 ° C. of the adhesive K7161: elongation at break, determined in accordance with the 1994 and _{F 168,} before the storage of the film-like adhesive JIS K7161: When the elongation at break measured in accordance with 1994 is F ₀ , the decrease rate RF _{168 of} elongation at break 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 defined as W ₀ , the W ₀ is 15% or less.

As described above, 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 elongation at break is suppressed and the storage stability is high. A film-like adhesive satisfying such conditions has high storage stability not only in such storage conditions but also in general storage conditions generally applied. And by using such a film 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 enables production of a highly reliable semiconductor package regardless of whether or not it is stored.

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

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

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

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

In the film adhesive of the third embodiment, F ₁₆₈ is not particularly limited, but is preferably 550 to 850%, more preferably 550 to 800%, and particularly preferably 550 to 750%. preferable. In another aspect, F ₁₆₈ may be 560-700%. When F ₁₆₈ is equal to or less than the upper limit value, it is difficult for a void portion to be generated between the film-like adhesive and the sticking target, and the embedding property to the sticking target is further improved. As a result, the reliability of the obtained semiconductor package becomes higher. The handling property of a film adhesive improves more because _F168 is more than the said lower limit.

In the present embodiment, for a film adhesive having a storage time at 40 ° C. of t hours (t is a number of 0 or more), the elongation at break F _t is measured according to JIS K7161: 1994. it can. For example, F ₁₆₈ and F ₀ can also be measured according to JIS K7161: 1994.

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

The conditions for storing the film-like adhesive, which is the measurement target of F _t , at 40 ° C. are the same as those for obtaining T _t described above.

When storing the film adhesive for which _{Ft is} to be determined at 40 ° C., it is preferable to start the storage immediately after the production of the film adhesive.
As one aspect, the elongation at break F _t of a film-like adhesive having a storage time at 40 ° C. of t hours (t is a number of 0 or more) is that the film-like adhesive immediately after production is subjected to an air atmosphere. In a dark place, the sample is stored at 40 ° C. for t hours, and then a test piece is immediately prepared according to JIS K7161: 1994, and the elongation at break of the test piece is measured.
Moreover, as one aspect, the breaking elongation F ₀ is a JIS K7161: 1994, immediately after preparing a test piece from a film adhesive immediately after the production, measuring the breaking elongation of the test piece immediately after the production Can be obtained.

RF ₁₆₈ can be calculated according to the following equation (ii).
RF ₁₆₈ (%) = (F ₀ -F ₁₆₈ ) / F ₀ × 100 (ii)

As described above, the film-like adhesive according to the third embodiment has an essential configuration that RF ₁₆₈ is less than 30%, and ΔT ₁₆₈ does not have to be less than 10 ° C. This is the same as the film adhesive of one embodiment.

For example, the film-like adhesive of the third embodiment has curability like the film-like adhesive of the first embodiment, and preferably has thermosetting, and has pressure-sensitive adhesiveness. Is preferable, and may have both thermosetting and pressure-sensitive adhesive properties. The film adhesive of the third embodiment also 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.
Moreover, the film adhesive of 3rd Embodiment may consist of 1 layer (single layer) similarly to the film adhesive of 1st Embodiment, and may consist of two or more layers. .
Moreover, the thickness of the film adhesive of 3rd Embodiment is the same as the thickness of the film adhesive of 1st Embodiment.
Further, 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.
Moreover, the film adhesive of 3rd Embodiment can be manufactured by the method similar to the case of the film adhesive of 1st Embodiment.

A third embodiment of a film-like adhesive such as _{F 0} and _{F 168} _{F _t,} the _{RF 168,} _{W 0} (hereinafter, these are generic, may be referred to as _{"F 0,} etc.") are Any of these can be adjusted as appropriate by adjusting, for example, the types and amounts of the components of the film adhesive. For example, the component of the film-like adhesive, which is a component of the polymer component (a) described later, and the content ratio thereof, the component of the epoxy resin (b1), the three-dimensional structure of the thermosetting agent (b2), and curing By adjusting the reactivity of the accelerator (c), the average particle size of the filler (d), and the like, the above-described F _{0 and the} like can be appropriately adjusted. However, these are only examples of the adjusting method such as F ₀ described above.

The film adhesive of the present invention may have both of the characteristics of the above-described first embodiment, second embodiment, and third embodiment in two or more (2 or 3) embodiments.
That is, as one embodiment of the film 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 one embodiment of the film adhesive, for example, ΔT ₁₆₈ is less than 10 ° C., W ₀ is 15% or less, and RF ₁₆₈ is less than 30%. .
Moreover, as one embodiment of the film adhesive, for example, RW ₁₆₈ is 200% or less, W ₀ is 15% or less, and RF ₁₆₈ is less than 30%. .
Further, as 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 is less than 30%.
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 described above.

FIG. 1 is a cross-sectional view schematically showing a film adhesive according to an embodiment of the present invention. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The film-like adhesive 13 shown here includes a first release film 151 on one side (sometimes referred to as a “first side” in this specification) 13a, and the first side 13a is defined as: A second release film 152 is provided on the other surface (which may be referred to as “second surface” in this specification) 13b on the opposite side.
Such a film adhesive 13 is suitable for storing as a roll, for example.

The film adhesive 13 has the characteristics of one or more of the first embodiment, the second embodiment, and the third embodiment described above.
The film adhesive 13 can be formed from an adhesive composition to be described later.

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

1, one of the first release film 151 and the second release film 152 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the resulting exposed surface. And the remaining other of the 1st peeling film 151 and the 2nd peeling film 152 is removed, and the produced exposed surface turns into the sticking surface of the support sheet mentioned later.

<< Adhesive composition >>
A preferable adhesive composition includes a thermosetting adhesive composition.
As a thermosetting adhesive composition, what contains a polymer component (a) and an epoxy-type thermosetting resin (b) is mentioned, for example. Hereinafter, each component will be described.

(Polymer component (a))
The polymer component (a) is a component that can be regarded as formed by polymerization reaction of a polymerizable compound, and imparts film-forming properties, flexibility, etc. to the film adhesive, and is attached to an object to be bonded such as a semiconductor chip. It is a polymer component for improving adhesiveness (sticking property). Moreover, a polymer component (a) is also a component which does not correspond to the epoxy resin (b1) and thermosetting agent (b2) which are mentioned later. That is, the polymer component (a) excludes components corresponding to the epoxy resin (b1) and the thermosetting agent (b2) described later.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected. .

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

As said acrylic resin in a polymer component (a), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is within such a range, it becomes easy to adjust the adhesive force between the film adhesive and the adherend to a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin is equal to or more than the lower limit, the shape stability of the film adhesive (time stability during storage) is improved. Moreover, since the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the film adhesive can easily follow the uneven surface of the adherend, and voids or the like between the adherend and the film adhesive. Occurrence is further suppressed.
In the present specification, “weight average molecular weight” is a polystyrene equivalent value measured by gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. Since the Tg of the acrylic resin is equal to or higher than the lower limit, the adhesive force between the film adhesive and the adherend is suppressed, and the support described later of the semiconductor chip with the film adhesive during pickup is performed. The separation from the sheet becomes easier. In the present specification, the “semiconductor chip with film adhesive” means “semiconductor chip having a film adhesive on the back surface”. When the Tg of the acrylic resin is equal to or less than the upper limit value, the adhesive force between the film adhesive and the semiconductor chip is improved.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid (Also known as uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also known as palmityl (meth) acrylate) The alkyl group constituting the alkyl ester such as heptadecyl (meth) acrylate and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms. (Meth) acrylic acid alkyl ester;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl group-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylate. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.

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

Only one type of monomer constituting the acrylic resin may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a carboxy group, and an isocyanate group in addition to the above-described hydroxyl group. These functional groups including the hydroxyl group of the acrylic resin may be bonded to other compounds via the crosslinking agent (f) described later, or directly bonded to other compounds not via the crosslinking agent (f). You may do it. When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the film 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 15% by mass or less. It is preferably 12% by mass or less, more preferably 9% by mass or less. When the ratio (content) is equal to or less than the upper limit value, the storage stability of the film adhesive is further increased. In addition, the said glycidyl group containing monomer means the monomer which has glycidyl groups, such as the said glycidyl group containing (meth) acrylic acid ester, for example.

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 to the total content (total mass) of the structural units constituting the acrylic resin 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 glycidyl group-containing monomer The effect by using can be obtained more clearly.

In the acrylic resin, 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 this is the above-described preferred lower limit value and upper limit value. It can adjust suitably within the range set combining arbitrarily. 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 ratio.

In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. Alternatively, it may be used in combination with an acrylic resin. By using the thermoplastic resin, at the time of pick-up, the semiconductor chip with the film adhesive can be easily separated from the support sheet described later, or the film adhesive follows the uneven surface of the adherend. It becomes easy and generation | occurrence | production of a void etc. may be suppressed more between a to-be-adhered body and a film adhesive.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.

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

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

1 type may be sufficient as the said thermoplastic resin which an adhesive composition and a film adhesive contain, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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 preferably 5 to 20% by mass, more preferably 6 to 16% by mass, and may be 7 to 12% by mass, regardless of the type of the polymer component (a).

In the adhesive composition and the film adhesive, the ratio of the acrylic resin content to the total content (total mass) of the polymer component (a) is preferably 80 to 100% by mass, 85 to The amount is more preferably 100% by mass, still more preferably 90 to 100% by mass, for example, 95 to 100% by mass. The storage stability of a film adhesive becomes higher because the ratio of the said content is more than the said lower limit.

(Epoxy thermosetting resin (b))
The epoxy 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 adhesive may be only one type, two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

・ Epoxy resin (b1)
Examples of the epoxy resin (b1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the film adhesive is improved by using the epoxy resin having an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound 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 can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. In the present specification, the “derivative” means a compound obtained by substituting at least one group of the original compound with another group (substituent) unless otherwise specified. Here, the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meth) acrylamide groups and the like, and an acryloyl group is preferred.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30000 from the viewpoints of curability of the film adhesive and strength and heat resistance of the cured film adhesive. It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
In the present specification, the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
In the present specification, “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing one equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

As for the epoxy resin (b1) which an adhesive composition and a film adhesive contain, only 1 type may be sufficient and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
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.

As a commercially available product of the epoxy resin (b1), there are those containing acrylic resin fine particles (fine particle acrylic resin). In the present invention, it is preferable to use an epoxy resin (b1) that does not contain the acrylic resin fine particles. . In this way, for example, even when the polymer component (a) is a polymer component (a) that is easy to aggregate the acrylic resin fine particles due to the interaction with the acrylic resin fine particles, Aggregation is suppressed. Thereby, the storage stability of a film adhesive becomes higher.
For example, in the adhesive composition, the ratio of the content of acrylic resin fine particles to the total content (total mass) of all components other than the solvent (that is, the content of acrylic resin fine particles in the film adhesive) is acrylic. Regardless of the origin of the resin fine particles, 0 to 5% by mass is preferable, and 0 to 3% by mass is more preferable.

・ Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b1).
As a thermosetting agent (b2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting 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, and aralkyl type phenol resins. .
Among the thermosetting agents (b2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as DICY).

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

In the case of using a phenolic curing agent as the thermosetting agent (b2), the thermosetting agent (b2) has a high softening point or glass transition temperature because it becomes easy to adjust the adhesive force of the film adhesive. Those are preferred.

Of the thermosetting agent (b2), for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, aralkyl type phenolic resin is preferably 300 to 30000. 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
Among the thermosetting agents (b2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

As for the thermosetting agent (b2) which an adhesive composition and a film adhesive contain, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .

The thermosetting agent (b2) is an alkyl group or the like with respect to the carbon atom adjacent to the carbon atom to which the phenolic hydroxyl group is bonded (that is, the carbon atom constituting the benzene ring skeleton). Those having a steric hindrance in the vicinity of the phenolic hydroxyl group bonded to a substituent (in this specification, sometimes abbreviated as “sterically hindered phenol resin”) are preferable. Examples of such sterically hindered phenol resins include o-cresol type novolac resins.

In the adhesive composition and the film adhesive, the content of the thermosetting agent (b2) is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin (b1), 15 to The amount is more preferably 160 parts by mass, further preferably 20 to 120 parts by mass, and particularly preferably 25 to 80 parts by mass. When the content of the thermosetting agent (b2) is greater than or equal to the lower limit value, the curing of the film adhesive is more likely to proceed. When the content of the thermosetting agent (b2) is equal to or lower than the upper limit, the moisture absorption rate of the film adhesive is reduced, and the reliability of the package obtained using the film adhesive is further improved. .

In the adhesive composition and the film adhesive, the content of the epoxy thermosetting resin (b) (total content of the epoxy resin (b1) and the thermosetting agent (b2)) is the same as that of the polymer component (a). The content is preferably 400 to 1200 parts by mass, more preferably 500 to 1100 parts by mass, still more preferably 600 to 1000 parts by mass, for example, 600 to 900 parts by mass with respect to the content of 100 parts by mass. Part and 800 to 1000 parts by mass. When the content of the epoxy thermosetting resin (b) is in such a range, it becomes easier to adjust the adhesive force between the film adhesive and a 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. 85 to 100% by mass, more preferably 90 to 100% by mass, for example, 95 to 100% by mass. The storage stability of a film adhesive becomes higher because the ratio of the said content is more than the said lower limit.
From the point that the storage stability of the film adhesive is further increased, the content of the o-cresol type novolak resin relative to the total content of the thermosetting agent (b2) in the adhesive composition and the film adhesive is The ratio is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, further preferably 90 to 100% by mass, and may be, for example, 95 to 100% by mass. .

In order to improve the various physical properties, the film adhesive contains, in addition to the polymer component (a) and the epoxy-based thermosetting resin (b), other components not corresponding to these, if necessary. You may have.
Examples of other components contained in the film adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), and an energy ray curable resin (g). , Photopolymerization initiator (h), 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, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present invention, “energy ray curable” means the property of being cured by irradiation with energy rays, and “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .

(Curing accelerator (c))
The curing accelerator (c) is a component for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (ie, at least one hydrogen atom is hydrogen Imidazoles substituted with groups other than atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (ie, phosphines wherein at least one hydrogen atom is replaced with an organic group); Phosphonium tetraphenylborate, tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate; clathrate compounds to the imidazoles guest compound.

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

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film adhesive is based on 100 parts by mass of the epoxy thermosetting resin (b). 0.01 to 5 parts by mass is preferable, and 0.1 to 2 parts by mass is more preferable. The effect by using a hardening accelerator (c) is acquired more notably because the said content of a hardening accelerator (c) is more than the said lower limit. When the content of the curing accelerator (c) is not more than the above upper limit value, for example, the highly polar curing accelerator (c) is in contact with the adherend in the film adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion interface side is enhanced, and the reliability of the package obtained using the film adhesive is further improved.

Among the above, the curing accelerator (c) is preferably an inclusion compound containing the imidazole as a guest compound. In such a curing accelerator (c), an imidazole which is an active ingredient is included by a host compound. Therefore, it is presumed that the reaction site of imidazoles is not exposed or the degree of exposure is suppressed except during the reaction. As a result, it is presumed that the storage stability of the film adhesive is further increased by suppressing the progress of the reaction other than the intended purpose of the curing accelerator (c) during storage of the film adhesive.

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

The carboxylic acid that is a host compound is preferably an aromatic carboxylic acid.
The aromatic carboxylic acid may be either a monocyclic aromatic carboxylic acid or a polycyclic aromatic carboxylic acid.
The aromatic carboxylic acid includes 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 an aromatic hydrocarbon ring and an aromatic heterocycle as a ring skeleton. Any of the carboxylic acids possessed together may be used.

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

Preferable examples of the inclusion compound include, for example, that the imidazole is 2-phenyl-4-methyl-5-hydroxymethylimidazole (in this specification, sometimes abbreviated as “2P4MHZ”), An inclusion compound in which the carboxylic acid is 5-hydroxyisophthalic acid (sometimes abbreviated as “HIPA” in this specification), and 2 molecules of 2P4MHZ and 1 molecule of HIPA More preferably, the clathrate compound is constituted.

In the adhesive composition and the 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, 85 The content is more preferably from 100 to 100% by mass, still more preferably from 90 to 100% by mass, for example, from 95 to 100% by mass. The storage stability of a film adhesive becomes higher because the ratio of the said content is more than the said lower limit.
And from the point which the storage stability of a film adhesive becomes still higher, in an adhesive composition and a film adhesive, it is comprised with the above-mentioned 2P4MHZ and HIPA with respect to the total content of a hardening accelerator (c). The content ratio of the clathrate compound is preferably 80 to 100% by mass, more preferably 85 to 100% by mass, further preferably 90 to 100% by mass, for example, 95 to 100%. It may be mass%.

(Filler (d))
By including the filler (d), the film-like adhesive can easily adjust its thermal expansion coefficient, and the film-like adhesive is optimized by optimizing the thermal expansion coefficient for the object to be adhered to the film-like adhesive. The reliability of the package obtained using the adhesive is improved. Moreover, when a film adhesive contains a filler (d), the moisture absorption rate of the film adhesive after hardening can be reduced or heat dissipation can also be improved.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or 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, and further preferably 0.5 to 100 μm. 1 to 75 μm is particularly preferable. As another aspect, the average particle diameter of the filler (d) may be 0.001 to 0.05 μm. When the average particle diameter of the filler (d) is in such a range, the effect of using the filler (d) can be sufficiently obtained, and the storage stability of the film adhesive can be further increased.
In the present specification, “average particle size” means the value of the particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. .

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

When the filler (d) is used, the ratio of the content of the filler (d) to the total content (total mass) of all components other than the solvent in the adhesive composition (that is, the filler of the film adhesive) The content of (d) 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 80 Is preferably 100 to 100% by mass, more preferably 85 to 100% by mass, further preferably 90 to 100% by mass, and may be 95 to 100% by mass, for example. The storage stability of a film adhesive becomes higher because the ratio of the said content is more than the said lower limit.

(Coupling agent (e))
When the film adhesive contains the coupling agent (e), the adhesion and adhesion to the adherend are improved. Moreover, when a film adhesive contains a coupling agent (e), the hardened | cured material improves water resistance, without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. It is more preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomer type Or a polymer type organosiloxane etc. are mentioned.

As for the coupling agent (e) which an adhesive composition and a film adhesive contain, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily. .
In one aspect, the coupling agent (e) includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and an oligomer type silane coupling agent having an epoxy group, a methyl group and a methoxy group. It is preferably at least one selected from the group consisting of

In the case where the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film adhesive is the total of the polymer component (a) and the epoxy thermosetting resin (b). The content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to the content of 100 parts by mass.
When the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved, the adhesion of the film adhesive to the adherend is improved, and the like. The effect obtained by using the coupling agent (e) is more remarkably obtained. Generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

The coupling agent (e) is preferably an oligomer type or polymer type organosiloxane among the above. The oligomer type or polymer type organosiloxane is an organosiloxane having an oligomer structure or a polymer structure, which can be regarded as formed by polymerization reaction of a polymerizable compound. By using such an oligomer-type or polymer-type organosiloxane, the effect obtained by using the coupling agent (e) can be sufficiently obtained, and the storage stability of the film adhesive can be further increased.

In the adhesive composition and the film adhesive, the ratio of the content of the oligomer type or polymer type organosiloxane to the total content of the coupling agent (e) is preferably 80 to 100% by mass, 85 It is more preferably from ˜100% by mass, even more preferably from 90 to 100% by mass, for example, from 95 to 100% by mass. The storage stability of a film adhesive becomes higher because the ratio of the said content is more than the said lower limit.

(Crosslinking agent (f))
As the polymer component (a), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the adhesive composition and the film adhesive may contain a crosslinking agent (f) for bonding the functional group with another compound to crosslink. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (that is, a crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (that is, having an aziridinyl group). A crosslinking agent).

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.

Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine 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 cross-linking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, the cross-linking structure can be simplified in the film adhesive by the reaction between the cross-linking agent (f) and the polymer component (a). Can be introduced.

The cross-linking agent (f) contained in the adhesive composition and the film adhesive may be only one kind, two or more kinds, and in the case of two or more kinds, the combination and ratio 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 with respect to 100 parts by mass of the polymer component (a). The content is more preferably ˜1 part by mass, and particularly preferably 0 part by mass, that is, it is particularly preferred that the adhesive composition and the film adhesive do not contain the crosslinking agent (f). When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. The storage stability of a film adhesive becomes higher because the content of the crosslinking agent (f) is not more than the upper limit.

(Energy ray curable resin (g))
Since the film adhesive contains the energy beam curable resin (g), the properties can be changed by irradiation with the energy beam.

The energy beam curable resin (g) is obtained by polymerizing (curing) an energy beam curable compound.
Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.

Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30000, and more preferably 300 to 10000.

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

When the energy ray curable resin (g) is used, the content of the energy ray curable resin (g) is preferably 1 to 95% by mass with respect to the total mass of the adhesive composition. More preferably, the content is 10% by mass, and particularly preferably 10 to 85% by mass.

(Photopolymerization initiator (h))
When the adhesive composition contains the energy beam curable resin (g), the adhesive composition may contain the photopolymerization initiator (h) in order to efficiently advance the polymerization reaction of the energy beam curable resin (g). Good.

Examples of the photopolymerization initiator (h) in the adhesive composition include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6 Acylphosphine oxide compounds such as -trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethylthiuram monosulfate Sulfide compounds such as amides; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 1-chloroanthraquinone; And quinone compounds such as 2-chloroanthraquinone.
Moreover, as a photoinitiator (h), photosensitizers, such as an amine, etc. are mentioned, for example.

1 type may be sufficient as the photoinitiator (h) which an adhesive composition contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

When using a photoinitiator (h), in an adhesive composition, content of a photoinitiator (h) is 0.1 with respect to 100 mass parts of energy beam curable resin (g) content. It is preferably ˜20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

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

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

(solvent)
It is preferable that the adhesive composition further contains a solvent. The adhesive composition containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol and the like. And alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
As for the solvent which an adhesive composition contains, only 1 type may be sufficient, and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

<< Method for Producing Adhesive Composition >>
An adhesive composition is obtained by mix | blending each component for comprising this.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.

The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◇ Semiconductor Processing Sheet The semiconductor processing sheet of the present invention includes a support sheet, and the film adhesive is provided on the support sheet. That is, the semiconductor processing sheet of the present invention includes a support sheet and the film adhesive provided on the support sheet.
The semiconductor processing sheet is suitable as a dicing die bonding sheet, for example.

As described above, the film adhesive has high storage stability, suppresses changes in properties during storage, and can sufficiently exhibit the intended action during use. Therefore, the semiconductor package formed by taking in the film adhesive using the semiconductor processing sheet has high reliability. Moreover, the semiconductor package formed by incorporating such a film-like adhesive having high storage stability can suppress the change in characteristics caused by the change in the characteristics of the film-like adhesive even during the 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 support sheet is composed 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 as long as the effects of the present invention are not impaired.

Preferable support sheets include, for example, those composed only of a base material; those provided with a base material, and provided with 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; it may be a support sheet including a base material and an intermediate layer provided on the base material.

The support sheet made of only the base material is suitable as a carrier sheet or a dicing sheet. The sheet for semiconductor processing provided with such a support sheet composed only of the base material is a surface opposite to the side provided with the support sheet (that is, the base material) of the film adhesive (in this specification, “ The first surface is sometimes referred to as “the first surface”, and is attached to the surface opposite to the side on which the circuit of the semiconductor wafer is formed (in this specification, sometimes referred to as the “back surface”). Is done.

On the other hand, the support sheet provided with a base material and provided with an intermediate layer on the base material is suitable as a dicing sheet. The semiconductor processing sheet provided with such a support sheet also has a surface (first surface) opposite to the side provided with the support sheet of the film adhesive and the side on which the circuit of the semiconductor wafer is formed. Is affixed to the opposite side (back side) and used.

The method for using the semiconductor processing sheet will be described in detail later.
Hereinafter, each layer which comprises a support sheet is demonstrated.

<Base material>
The base material 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 (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), and high density polyethylene (sometimes abbreviated as HDPE). Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer Ethylene copolymers such as ethylene-norbornene copolymer (that is, copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (that is, monomers) Resin obtained using vinyl chloride as Styrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, wholly aromatic polyesters in which all structural units have aromatic cyclic groups, etc. Polyester; Copolymer of two or more of the above polyesters; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Is mentioned.
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

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

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

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 150 μm. When the thickness of the base material is in such a range, the flexibility of the semiconductor processing sheet and the adhesiveness to the semiconductor wafer or the semiconductor chip are further improved.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.

The base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.

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

The substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.

In order to improve the adhesion with other layers such as an intermediate layer provided on the substrate, the substrate is subjected to uneven blasting treatment such as sandblasting treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, The surface may be subjected to an oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, or the like.
The base material may have a surface subjected to primer treatment.
In addition, the base material is an antistatic coating layer; a layer that prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the semiconductor processing sheets are stacked and stored. It may have.

The base material 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.

<Intermediate layer>
The intermediate layer is not particularly limited as long as it is disposed between the base material and the film adhesive and exhibits its function.
More specifically, examples of the intermediate layer include a peelability improving layer in which one surface is peeled.

○ Peelability improvement layer The said peelability improvement layer is a sheet form or a film form.
As a peelability improvement layer, what consists of a resin layer and the peeling process layer formed on the said resin layer is comprised, for example, and it consists of a plurality of layers. In the sheet for semiconductor processing, the peelability improving layer is arranged with the release treatment layer facing the film adhesive.

Among the peelability improving layers, the resin layer can be produced by molding a resin composition containing a resin.
And a peelability improvement layer can be manufactured by carrying out the peeling process of one surface of the said resin layer.

The release treatment of the resin layer can be performed by various known release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin or wax.
In terms of heat resistance, the release agent is preferably an alkyd, silicone or fluorine release agent.

The resin that is a constituent material of the resin layer may be appropriately selected according to the purpose, and is not particularly limited.
Preferred examples of the resin include polyethylene terephthalate (sometimes abbreviated as PET), polyethylene naphthalate (sometimes abbreviated as PEN), polybutylene terephthalate (sometimes abbreviated as PBT), polyethylene ( PE (sometimes abbreviated as PE), polypropylene (sometimes abbreviated as PP), and the like.

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

The thickness of the peelability improving layer (total thickness of the resin layer and the release 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 improving layer is equal to or more than the lower limit, the action of the peelability improving layer becomes more remarkable, and further, the effect of suppressing breakage such as cutting of the peelability improving layer becomes higher. When the thickness of the peelable improvement layer is less than or equal to the above upper limit value, the pick-up force is easily transmitted to the semiconductor chip with the film adhesive when picking up the semiconductor chip with the film adhesive to be described later, making the pickup easier Can be done.

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

FIG. 2 is a cross-sectional view schematically showing an embodiment of the semiconductor processing sheet of the present invention.
In FIG. 2 and subsequent figures, the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.

The semiconductor processing sheet 1 A shown here includes a support sheet 10, and a film adhesive 13 on the support sheet 10. The support sheet 10 is composed only of the base material 11, and in other words, the semiconductor processing sheet 1 A is on one surface (which may be referred to as “first surface” in this specification) 11 a of the base material 11. The film adhesive 13 is laminated. The semiconductor processing sheet 1 A further includes a release film 15 on the film adhesive 13.

In the semiconductor processing sheet 1A, a film adhesive 13 is laminated on the first surface 11a of the substrate 11, and the surface of the film adhesive 13 opposite to the side on which the substrate 11 is provided (this specification) The jig adhesive layer 16 is laminated on a part of the portion 13a, that is, in the vicinity of the peripheral portion, and the first surface 13a of the film adhesive 13 is formed. Among them, the release film 15 is formed on the surface on which the jig adhesive layer 16 is not laminated and on the surface 16 a (upper surface and side surface) of the jig adhesive layer 16 that is not in contact with the film adhesive 13. Are stacked.
Here, the first surface 11 a of the substrate 11 is also referred to as the first surface 10 a 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.

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.

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

FIG. 3 is a cross-sectional view schematically showing another embodiment of the semiconductor processing sheet of the present invention.
The semiconductor processing sheet 1B shown here is the same as the semiconductor processing sheet 1A shown in FIG. 2 except that the jig processing adhesive layer 16 is not provided. That is, in the semiconductor processing sheet 1B, 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 entire surface of the first surface 13a of the film adhesive 13 is obtained. Further, a release film 15 is laminated.
In other words, the semiconductor processing sheet 1B is configured by laminating the base material 11, the film adhesive 13, and the release film 15 in this order in the thickness direction.

The semiconductor processing sheet 1B shown in FIG. 3 is the center of the first surface 13a of the film adhesive 13 in a state where the release film 15 is removed, as in the case of the semiconductor processing sheet 1A shown in FIG. The rear surface of the semiconductor wafer (not shown) is attached to a partial region on the side, and the region near the peripheral edge of the film adhesive 13 is attached to a jig such as a ring frame for use.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the semiconductor processing sheet of the present invention.
The semiconductor processing sheet 1 C shown here is the same as the semiconductor processing sheet 1 A shown in FIG. 2 except that an intermediate layer 12 is further provided between the base material 11 and the film adhesive 13. It is. The support sheet 10 is a laminated body of the base material 11 and the intermediate layer 12, and the semiconductor processing sheet 1 C has a configuration in which the film adhesive 13 is laminated on the first surface 10 a of the support sheet 10.

In the semiconductor processing sheet 1C, the intermediate layer 12 is laminated on the first surface 11a of the base material 11, and the surface of the intermediate layer 12 opposite to the base material 11 side (in this specification, “first surface The film adhesive 13 is laminated on the entire surface of 12a, and a jig adhesive layer is formed on a part of the first surface 13a of the film adhesive 13, that is, in the vicinity of the peripheral edge. 16 is laminated, and the surface of the first surface 13a of the film adhesive 13 on which the jig adhesive layer 16 is not laminated and the jig adhesive layer 16 out of contact with the film adhesive 13 The release film 15 is laminated on the surface 16a (upper surface and side surface) that is not formed.

In the sheet for semiconductor processing 1C, when the intermediate layer 12 is the peelability improving layer, for example, the layer on the base material 11 side of the intermediate layer 12 becomes the resin layer (not shown), and the film of the intermediate layer 12 The layer on the side of the adhesive 13 becomes the release treatment layer (not shown). Therefore, in this case, the first surface 12a of the intermediate layer 12 is a peeling treatment surface. Such an intermediate layer 12 is easy to peel off the film-like adhesive (those obtained by cutting the film-like adhesive 13 in FIG. 4) when picking up a semiconductor chip with a film-like adhesive described later.

The semiconductor processing sheet 1C shown in FIG. 4 has a semiconductor wafer (not shown) attached to the first surface 13a of the film adhesive 13 with the release film 15 removed, and further bonded to a jig. The upper surface of the surface 16a of the agent layer 16 is used by being attached to a jig such as a ring frame.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the semiconductor processing sheet of the present invention.
The semiconductor processing sheet 1D shown here is the same as the semiconductor processing sheet 1C shown in FIG. 4 except that the jig processing adhesive layer 16 is not provided and the shape of the film adhesive is different. That is, the semiconductor processing sheet 1 D includes the base material 11, the intermediate layer 12 on the base material 11, and the film adhesive 23 on the intermediate layer 12. The support sheet 10 is a laminate of the base material 11 and the intermediate layer 12, and the semiconductor processing sheet 1 D also has a configuration in which the film adhesive 23 is laminated on the first surface 10 a of the support sheet 10.

In the semiconductor processing sheet 1D, the intermediate layer 12 is laminated on the first surface 11a of the base material 11, and the film-like adhesive 23 is formed in a part of the first surface 12a of the intermediate layer 12, that is, in the central region. Are stacked. And the area | region where the film adhesive 23 is not laminated | stacked among the 1st surfaces 12a of the intermediate | middle layer 12, and the surface 23a (upper surface and side surface) which are not contacting the intermediate | middle layer 12 among the film adhesives 23. A release film 15 is laminated on the top.

When the semiconductor processing sheet 1D is viewed from above and viewed in plan, the film adhesive 23 has a surface area smaller than that of the intermediate layer 12, and has, for example, a circular shape.

In the semiconductor processing sheet 1D shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is pasted on the upper surface of the surface 23a of the film adhesive 23 in a state where the release film 15 is removed. Of the 12 first surfaces 12a, a region where the film adhesive 23 is not laminated is attached to a jig such as a ring frame and used.

In the semiconductor processing sheet 1D shown in FIG. 5, in the first surface 12a of the intermediate layer 12, the region where the film adhesive 23 is not laminated is cured in the same manner as shown in FIGS. A tool adhesive layer may be laminated (not shown). As in the case of the semiconductor processing sheet shown in FIGS. 2 and 4, the semiconductor processing sheet 1 D provided with such a jig adhesive layer has an upper surface of the surface of the jig adhesive layer. Used by sticking to a jig such as a frame.

Thus, the sheet for semiconductor processing may be provided with an adhesive layer for jigs regardless of the form of the support sheet and the film-like adhesive. However, normally, as shown in FIGS. 2 and 4, the semiconductor processing sheet provided with the jig adhesive layer preferably has a jig adhesive layer on the film adhesive.

The semiconductor processing sheet of the present invention is not limited to that shown in FIGS. 2 to 5, and a part of the configuration shown in FIGS. 2 to 5 is changed or deleted within a range not impairing the effects of the present invention. In addition, another configuration may be added to what has been described so far.

For example, in the semiconductor processing sheets shown in FIGS. 2 to 5, layers other than the base material, the intermediate layer, the film adhesive, and the release film may be provided at any location.
Moreover, in the sheet | seat for semiconductor processing, some clearance gaps may arise between the peeling film and the layer which is directly contacting with this peeling film.
In the semiconductor processing sheet, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

◇ Method of using film-like adhesive and semiconductor processing sheet The film-like adhesive and semiconductor processing sheet of the present invention are used to manufacture a semiconductor package and a semiconductor device after manufacturing a semiconductor chip with a film-like adhesive. Can be used.

After the film-like adhesive not provided with the support sheet is affixed to the back surface of the semiconductor wafer, for example, the peeling film is removed as necessary, and the exposed surface (in other words, the side affixed to the semiconductor wafer) A dicing sheet is affixed to the opposite surface (sometimes referred to as a “second surface” in this specification). The laminated structure obtained by laminating the dicing sheet, the film adhesive, and the semiconductor wafer in this order in the thickness direction is then subjected to a known dicing process. The laminated structure of the dicing sheet and the 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 film adhesive after the cutting is provided on the back surface. A semiconductor chip (sometimes referred to as a semiconductor chip with a film adhesive) is obtained.

Meanwhile, the semiconductor processing sheet already has a structure as a dicing die bonding sheet. Therefore, when the semiconductor processing sheet is affixed to the back surface of the semiconductor wafer, the semiconductor processing sheet (dicing sheet, film adhesive) and the semiconductor wafer are stacked in this order in the thickness direction. After obtaining the body, as described above, using a film-like adhesive not provided with a support sheet, in the same manner as when a dicing sheet was attached to the second surface, and thereafter with a film-like adhesive A semiconductor chip is obtained.

The method for dicing the semiconductor wafer may be a known method and is not particularly limited.
As a preferable dicing method of the semiconductor wafer, for example, a method using a blade (namely, blade dicing), a method performed by laser irradiation (namely, laser dicing), and a method performed by spraying water containing an abrasive (namely, water dicing). And a method of cutting a semiconductor wafer.

Regardless of whether the film adhesive or the semiconductor processing sheet is used, the obtained semiconductor chip with the film adhesive is then separated (picked up) from the dicing sheet and adhered in the film form. It is die-bonded to the circuit forming surface of the substrate by the agent. Thereafter, the semiconductor package and the semiconductor device are manufactured by the same method as the conventional method.
For example, if necessary, at least one semiconductor chip is further laminated on this die-bonded semiconductor chip, wire bonding is performed, and then the entire product is sealed with a resin, whereby a semiconductor package is obtained. Is produced. Then, a target semiconductor device is manufactured using this semiconductor package.
By using the film adhesive of the present invention, the obtained semiconductor package has high reliability.

As one aspect, the film adhesive of the present invention is a film adhesive having the following properties:
(I-1) 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 of the film adhesive before storage is T ₀ . When
The T ₁₆₈ is 50 to 78 ° C .;
The T ₀ is 59 to 71 ° C .;
The difference ΔT ₁₆₈ between the T ₁₆₈ and the T ₀ is 0-7 ° C .;
(II-1) When the gel fraction of the film adhesive after storage for 168 hours at 40 ° C. is W _168, and the gel fraction of the film adhesive before storage is W ₀ ,
W ₁₆₈ is _9-12 %,
W ₀ is 3-8% or 5-8%,
The change rate RW ₁₆₈ of the gel fraction obtained from the W ₁₆₈ and the W ₀ is 113 to 150%; and (III-1) JIS K7161: after the film adhesive is stored at 40 ° C. for 168 hours When the breaking elongation measured according to 1994 is F _168, and the breaking elongation measured according to JIS K7161: 1994 before the storage of the film adhesive is F ₀ ,
The F ₁₆₈ is 0 to 23%, or 5 to 23%,
The F ₀ is 700 to 800%;
The decrease rate RF _{168 of the} elongation at break obtained from the F ₁₆₈ and the F ₀ is 560 to 700%.

Furthermore, the film adhesive is formed from a film adhesive composition,
The film adhesive composition includes a polymer component (a), an epoxy 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 with respect to 100 parts by mass of the polymer component (a)), methyl acrylate (preferably 70 to 100 parts by mass of the polymer component (a)) To 80 parts by mass), glycidyl methacrylate (preferably 2 to 5 parts by mass with respect to 100 parts by mass of the polymer component (a)), and 2-hydroxyethyl acrylate (100 parts by mass of the polymer component (a)). An acrylic resin obtained by copolymerizing 15 to 20 parts by mass with respect to parts, or n-butyl acrylate (preferably 40 to 50 parts by mass with respect to 100 parts by mass of the polymer component (a)). Parts), ethyl acrylate (preferably 20 to 30 parts by weight with respect to 100 parts by weight of the polymer component (a)), and acrylonitrile (with respect to 100 parts by weight of the polymer component (a)). Ku 20 to 40 parts by weight) and for glycidyl methacrylate (the polymer component (a) 100 parts by weight, preferably acrylic resin obtained by copolymerizing 2 to 5 parts by weight);
The epoxy thermosetting resin (b) comprises an epoxy resin (b1) and a thermosetting agent (b2);
The epoxy resin (b1) is
A bisphenol A type epoxy resin and a polyfunctional aromatic type (triphenylene type) epoxy resin, or a bisphenol F type epoxy resin and a dicyclopentadiene type epoxy resin;
The thermosetting agent (b2) is an o-cresol type novolac resin;
The curing accelerator (c) is
An inclusion compound of one molecule of 5-hydroxyisophthalic acid (HIPA) and two molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ), or 2-phenyl-4,5-dihydroxymethylimidazole;
The filler (d) is spherical silica (preferably having an average particle size of 0.01 to 0.05 μm); and the coupling agent (e) is an oligomeric silane having an epoxy group, a methyl group and a methoxy group A coupling agent, or an oligomeric silane coupling agent having an epoxy group, a methyl group and a methoxy group, and 3-glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane.
A film adhesive may be used.

Furthermore, the film adhesive is
The content of the polymer component (a) is 7 to 12 with respect to the total content of all the components constituting the film adhesive composition (that is, the total mass of the film adhesive composition). % By weight;
The proportion of the content of the structural unit derived from the 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 thermosetting resin (b) is 600 to 1000 parts by mass with respect to 100 parts by mass of the polymer component (a);
The content of the curing accelerator (c) is 0.1 to 2 parts by mass with respect to 100 parts by mass of the epoxy thermosetting resin (b);
The content of the filler (d) is 15 to 30 masses with respect to the total content of all components constituting the film adhesive composition (that is, the total mass of the film adhesive composition). And the content of the coupling agent (e) is from 0.1 to 100 parts by mass with respect to 100 parts by mass of the total content of the polymer component (a) and the epoxy thermosetting resin (b). 5 parts by mass,
A film adhesive may be used.

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

<Monomer>
In the examples and comparative examples, the formal names of the monomers abbreviated are shown below.
BA: n-butyl acrylate MA: methyl acrylate HEA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate EA: ethyl acrylate AN: acrylonitrile

<Production raw material of adhesive composition>
In the examples and comparative examples, the raw materials used for the production of the adhesive composition are shown below.

[Polymer component (a)]
(A) -1: Acrylic resin (weight average molecular weight 350,000, glass transition) obtained by copolymerizing BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass) and HEA (15 parts by mass) Temperature-1 ° C).
(A) -2: Acrylic resin (weight average molecular weight 700,000, glass transition) obtained by copolymerizing BA (40 parts by mass), EA (25 parts by mass), AN (30 parts by mass) and GMA (5 parts by mass) Temperature -14 ° C).
(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 ° C).
(A) -4: Thermoplastic resin, polyester (Toyobo “Byron 220”, weight average molecular weight 35000, glass transition temperature 53 ° C.)
[Epoxy resin (b1)]
(B1) -1: Bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq)
(B1) -2: Polyfunctional aromatic type (triphenylene type) epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku 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 Kayaku Co., Ltd., epoxy equivalent 248 g / eq)
(B1) -5: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (“BPA328” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 235 g / eq)
(B1) -6: Dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent of 255 to 260 g / eq)
[Thermosetting agent (b2)]
(B2) -1: o-cresol type novolak resin (“Phenolite KA-1160” manufactured by DIC)
(B2) -2: Novolac type phenolic resin (novolak resin other than o-cresol type, “BRG-556” manufactured by Showa Denko KK)
(B2) -3: Dicyandiamide (“ADEKA HARDNER EH-3636AS” manufactured by ADEKA, solid dispersion type latent curing agent, active hydrogen amount 21 g / eq)
[Curing accelerator (c)]
(C) -1: an inclusion compound of one molecule of 5-hydroxyisophthalic acid (HIPA) and two molecules of 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) (“HIPA-2P4MHZ” manufactured by Nippon Soda Co., Ltd.) )
(C) -2: 2-phenyl-4,5-dihydroxymethylimidazole (“Cureazole 2PHZ-PW” manufactured by Shikoku Chemicals)
[Filler (d)]
(D) -1: Spherical silica modified with an epoxy group (“Admanano YA050C-MKK” manufactured by Admatechs, average particle size 50 nm)
(D) -2: Silica filler (“SC2050MA” manufactured by Admatechs, silica filler surface-modified with an epoxy compound, 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: Oligomer type 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 Co., silane coupling agent)
(E) -5: A silicate compound to which 3-glycidoxypropyltrimethoxysilane is added (“MKC silicate MSEP2” manufactured by Mitsubishi Chemical Corporation)
[Crosslinking agent (f)]
(F) -1: Tolylene diisocyanate trimer adduct of trimethylolpropane (“BHS8515” manufactured by Toyochem)
[Energy ray curable resin (g)]
(G) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., UV curable resin, molecular weight 304)
[Photoinitiator (h)]
(H) -1: 1-hydroxycyclohexyl phenyl ketone (“IRGACURE (registered trademark) 184” manufactured by BASF)
(H) -2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE® 369” manufactured by BASF)

[Example 1]
<< Manufacture of film adhesive >>
<Manufacture 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 weight), curing accelerator (c) -1 (0.3 parts by weight), filler (d) -1 (20 parts by weight), coupling agent (e) -1 (0.3 parts by weight), cup The solid component concentration is obtained by dissolving or dispersing the ring agent (e) -2 (0.4 parts by mass) and the coupling agent (e) -3 (0.5 parts by mass) in methyl ethyl ketone and stirring at 23 ° C. An adhesive composition having a content of 55% by mass was obtained. In addition, all the compounding quantities of components other than the methyl ethyl ketone shown here are solid content conversion values.

<Manufacture of film adhesive>
The adhesive composition obtained above on the release-treated surface of a release film (“SP-PET381031H” manufactured by Lintec Co., Ltd., thickness 38 μm) in which one side of a polyethylene terephthalate (PET) film is subjected to release treatment by silicone treatment Was applied and dried at 100 ° C. for 2 minutes to form a film adhesive having a thickness of 20 μm.

<< Manufacture of semiconductor processing sheets >>
By bonding a polyethylene film (thickness: 100 μm) as a base material to the surface (exposed surface) opposite to the side provided with the release film of the film-like adhesive obtained above, a base material, A sheet for semiconductor processing was obtained, in which a film adhesive and a release film were laminated in this order in the thickness direction.

<< Evaluation of film adhesive >>
<Calculation of initial detected temperature difference ΔT ₁₆₈ of melt viscosity>
From the film adhesive obtained above, a cylindrical test piece having a diameter of 10 mm and a height of 20 mm was immediately prepared.
Place the test piece immediately after the preparation at the measurement point of the capillary rheometer (“CFT-100D” manufactured by Shimadzu Corporation), and apply the force of 5.10 N (50 kgf) to the test piece. The temperature was raised from 50 ° C. to 120 ° C. at 10 ° C./min. Then, when the extrusion of the test piece from the hole of 0.5 mm in diameter and 1.0 mm in height provided in the die is started, that is, the temperature at which the detection of the melt viscosity of the test piece is started (initial detection temperature). T ₀ ) (° C.) was determined. The results are shown in Table 1.

Separately, the film-like adhesive obtained above was stored at 168 hours (one week) at 40 ° C. in a dark place in an air atmosphere immediately after its production.
The same cylindrical test piece as described above was immediately produced from the film-like adhesive after storage.
Then, in the same manner as in the case of the test piece prepared from the film-like adhesive immediately after the preparation, the temperature at which the detection of the melt viscosity was started (initial detection) for the test piece prepared from the film-like adhesive after storage. Temperature T ₁₆₈ ) (° C.) was determined. Further, a difference ΔT ₁₆₈ (° C.) between T ₁₆₈ and T ₀ was calculated. These results are shown in Table 1.

<Calculation of change rate RW ₁₆₈ of gel fraction>
A sheet-like test piece (0.5 g) having a size of 2.5 cm × 4.0 cm × 600 μm was immediately prepared from the film-like adhesive obtained above.
The test piece immediately after the production was wrapped with a # 200 mesh made of polyester, 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 of the methyl ethyl ketone together with the mesh, and the test piece from which the mesh was removed was dried at 120 ° C. for 1 hour.
The dried test piece was stored for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then the mass of the test piece was measured. Then, the measured value, the mass before immersion of the test piece and (0.5 g), from the calculated gel fraction _W 0 (percent). The results are shown in Table 1.

Separately, the film-like adhesive obtained above was stored at 168 hours (one week) at 40 ° C. in a dark place in an air atmosphere immediately after its production.
The same sheet-like test piece as described above was immediately produced from the film-like adhesive after storage. And gel fraction _W168 (%) was computed about the test piece produced from the film-like adhesive after this preservation | save by the same method as the case of the test piece produced from said film-like adhesive immediately after preparation. Furthermore, according to the formula (i), the rate of change RW ₁₆₈ (%) of the gel fraction of the test piece was calculated. These results are shown in Table 1.

<Calculation of reduction ratio _{RF 168} elongation at break>
In accordance with JIS K7161: 1994, a test piece was immediately produced from the film-like adhesive obtained above, and the breaking elongation F ₀ (%) of the test piece immediately after the production was measured. The results are shown in Table 1.

Separately, the film-like adhesive obtained above was stored at 168 hours (one week) at 40 ° C. in a dark place in an air atmosphere immediately after its production.
Then, immediately, in accordance with 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. It was measured. Furthermore, the reduction rate RF ₁₆₈ (%) of the breaking elongation of the test piece was calculated according to the above formula (ii). These results are shown in Table 1.

<Evaluation of semiconductor package reliability>
(Manufacture of semiconductor chip with film adhesive)
Surface protection tape (“Adwill E-3125KN” manufactured by Lintec) is applied to the mirror surface of an 8-inch silicon mirror wafer (thickness: 720 μm) at room temperature using a tape bonding device (“RAD3510” manufactured by Lintec). Then, using a grinder (“DFG8760” manufactured by DISCO), the surface of the silicon wafer opposite to the surface to which the surface protective tape was applied (ie, the back surface) was ground. The grinding at this time was performed until the thickness of the silicon wafer reached 50 μm, and the ground surface was dry-polished.

Next, the release film was removed from the semiconductor processing sheet obtained above. Then, using a laminating apparatus (“VA-400” manufactured by Taisei Laminator Co., Ltd.), a semiconductor processing sheet was attached to the ground surface (back surface) of the silicon mirror wafer with the film adhesive. At this time, the semiconductor processing sheet was heated to 60 ° C. and pasted under conditions of a pasting speed of 0.6 m / min and a pasting pressure of 0.5 MPa.

Next, the base material was removed from the film-like adhesive of the semiconductor processing sheet after being attached to the silicon mirror wafer. Then, an expanded tape (“ADWILL DG889SO5” manufactured by Lintec) was attached to the exposed surface of the newly formed film adhesive using a laminating apparatus (“VA-400” manufactured by Taisei Laminator). At this time, the expanded tape was applied at normal temperature under the conditions of an application speed of 0.6 m / min and an application pressure of 0.5 MPa.

Next, a double-sided tape for fixing a ring frame (“ADWILL G-01DF ^* ” manufactured by Lintec) was attached to an exposed surface in the vicinity of the peripheral edge of the expanded tape that was not attached to the film adhesive. Then, the first laminated structure in which the expanded tape, the film adhesive, and the silicon mirror wafer were laminated in this order in the thickness direction was fixed to the ring frame with the double-sided tape.

Next, the surface protection tape is removed from the mirror surface of the silicon mirror wafer, and the silicon mirror wafer is divided by dicing using a dicing apparatus (“DFD6361” manufactured by Disco), and the film adhesive is also cut. A silicon chip having a size of 8 mm × 8 mm was obtained. In this dicing, the moving speed of the dicing blade is 50 mm / sec, the rotational speed of the dicing blade is 40,000 rpm, and the expanded tape is cut with a dicing blade to a depth of 20 μm from the adhesive surface of the film adhesive. went.
As described above, a plurality of silicon chips (in other words, a plurality of silicon chips with a film-like adhesive) provided with a cut film-like adhesive on the back surface are aligned on the expanded tape by the film-like adhesive. The 2nd laminated structure fixed by is obtained.

(Manufacture of semiconductor packages)
A circuit pattern is formed on a copper foil (thickness 18 μm) of a copper foil-clad laminate (“HL832NX-A” manufactured by Mitsubishi Gas Chemical Company) as a substrate, and a solder resist (“PSR-” manufactured by Taiyo Ink Co., Ltd.) is formed on this circuit pattern. A substrate (“LN001E-001 PCB (Au) AUS308” manufactured by CIMA ELECTRONICS) was prepared.

On the other hand, the second laminated structure obtained above was installed in an expanding unit of a pickup / die bonding apparatus (“BESTEM D02” manufactured by Canon Machinery Co., Ltd.).
Next, with the five pins, the second laminated structure was pushed up from the expanded tape side under the conditions of a push-up speed of 300 mm / min and a push-up amount of 200 μm, and further, using a collet with a size of 8 mm × 8 mm, The silicon chip with film adhesive was picked up by pulling it away from the expanded tape.

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

Next, a layer made of a sealing resin (“KE-G1250” manufactured by Kyocera Chemical Co., Ltd.) was formed on the silicon chip after bonding using a sealing device (“MPC-06M TriAl Press” manufactured by Apic Yamada). And this sealing resin was hardened and the sealing substrate was obtained by forming the 400-micrometer-thick sealing layer. The curing of the sealing resin at this time was performed by applying a pressure of 7 MPa to the sealing resin heated to 175 ° C. for 2 minutes.

Next, a dicing tape (“adwill D-510T” manufactured by Lintec Co., Ltd.) is attached to this sealing substrate, and this dicing blade is rotated at 4000 rpm using a dicing apparatus (“DFD6361” manufactured by Disco). By dicing the substrate, a semiconductor package having a size of 15 mm × 15 mm was obtained.

(Evaluation of semiconductor package reliability)
The semiconductor package obtained above was immediately subjected to IR reflow three times with a maximum temperature of 260 ° C. and heating for 1 minute. The IR reflow at this time was performed using a desktop reflow furnace (“STR-2010N2M” manufactured by Senju Metal Industry Co., Ltd.).

Next, using an ultrasonic microscope (“D-9600” manufactured by Sonoscan), the semiconductor package after the IR reflow was observed to check whether the joint was lifted, the joint was peeled off, and the package was cracked. confirmed. Then, when all of the joint floating, the peeling of the joint, and the package crack were not confirmed, it was determined as “A”, and when any one or more was confirmed, it was determined as “B”. The results are shown in Table 1.

Separately, according to JEDEC Level2, the semiconductor package obtained above was allowed to absorb moisture by standing still for 168 hours (1 week) under a moist heat condition of 85 ° C. and a relative humidity of 60%.
Then, immediately after the moisture absorption, the semiconductor package after IR reflow was evaluated by performing IR reflow three times in the same manner as in the case of the semiconductor package immediately after manufacture. The results are shown in Table 1.

<< Production of film adhesive and semiconductor processing sheet, and evaluation of film adhesive >>
[Example 2, Comparative Examples 1 and 2]
The point which changed either one or both of the kind of compounding component and the compounding quantity at the time of manufacture of an adhesive composition so that the kind and content of the component of adhesive composition may become as showing in Table 1. Except for the above, a film adhesive and a semiconductor processing sheet were produced in the same manner as in Example 1, and the film adhesive was evaluated. The results are shown in Table 1.

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

As described above, the film adhesives of Examples 1 and 2 had stable melt viscosity, gel fraction and elongation at break during storage, and the storage stability of the film adhesive was high.
Reflecting these results, in Examples 1 and 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 the storage of the film adhesive, the melt viscosity was not stable and increased remarkably. Moreover, although W ₀ was 8% and RW ₁₆₈ was 300% and the gel fraction before storage of the film adhesive was low, the gel fraction was not stable during storage of the film adhesive. , Was significantly increased. Further, RF ₁₆₈ was 85.4%, and during the storage of the film adhesive, the elongation at break was not stable and significantly decreased.

Thus, the film-like adhesive of Comparative Example 1 was not stable in terms of storage viscosity, gel fraction and elongation at break, and the storage stability of the film-like adhesive was low.
Reflecting 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 completely low.

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

Thus, the film-like adhesive of Comparative Example 2 had a gel fraction that was consistently high from the beginning (immediately after production) and could not be judged to have high storage stability.
And reflecting these results, in Comparative Example 2, the reliability of the semiconductor package was low both immediately after manufacture and after moisture absorption.

The present invention can provide a film adhesive capable of producing a highly reliable semiconductor package based on the storage stability, and a semiconductor processing sheet provided with the film adhesive. Since it can be used for manufacturing, it is extremely useful industrially.

1A, 1B, 1C, 1D ... Semiconductor processing sheet,
10 ... support sheet,
12 ... intermediate layer,
13, 23 ... Film adhesive

Claims

Film adhesive with the following properties:
(I) The initial detection temperature of the melt viscosity after storage for 168 hours at 40 ° C. of the film adhesive is T 168 ,
When the initial detected temperature of the melt viscosity before the saving of the film adhesive was a T 0,
The difference ΔT 168 between the T 168 and the T 0 is less than 10 ° C., and (II) W 0 is 15 when the gel fraction before storing the film adhesive at 40 ° C. is W 0. % Or less,
Film adhesive.
Film adhesive with the following properties:
(I ′) The gel fraction of the film adhesive after storage at 40 ° C. for 168 hours is defined as W 168 .
When the gel fraction before storage of the film adhesive is W 0 ,
The change rate RW 168 of the gel fraction obtained from the W 168 and the W 0 is 200% or less, and
(II ′) The gel fraction W 0 is 15% or less,
Film adhesive.
Film adhesive with the following properties:
(I ″) The elongation at break measured according to JIS K7161: 1994 after storing the film adhesive at 40 ° C. for 168 hours is F 168 ,
When the elongation at break measured according to JIS K7161: 1994 before the storage of the film adhesive is F 0 ,
The reduction rate of elongation at break RF 168 calculated from the F 168 and the F 0 is less than 30%, and (II ″) the film adhesive before the film adhesive is stored at 40 ° C. When the gel fraction is W 0 , the W 0 is 15% or less.
Film adhesive.
A semiconductor processing sheet comprising a support sheet and the film adhesive according to any one of claims 1 to 3 provided on the support sheet.