JP6379389B2 - Dicing die bonding sheet - Google Patents

Description

  The present invention relates to a dicing die bonding sheet provided with an adhesive layer on a substrate.

  A dicing die bonding sheet comprising an adhesive layer on a substrate is a process from dicing a semiconductor wafer through picking up a semiconductor chip to bonding the picked up semiconductor chip to a substrate, a lead frame, another semiconductor chip, etc. Used in the process.

  In such a sheet, since the adhesive layer is usually colorless and transparent, the adhesive layer is bonded to an object to be bonded such as a semiconductor wafer or a semiconductor chip when the sheet is precut or when die bonding of a semiconductor chip is performed. It is difficult to detect whether or not If the adhesive layer is not adhered to a desired location, trouble occurs in the manufacturing process of the semiconductor device. In addition, when the adhesive layer is cleaved by stealth dicing or cool expand, the adhesive layer is colorless and transparent. It will decline.

  In the manufacturing process of the semiconductor device, the detection of the adhesive layer is performed using, for example, an optical sensor capable of detecting light in a wavelength range of 290 to 450 nm. Its detection is becoming difficult.

  Under such circumstances, an adhesive layer that is easy to detect has been disclosed that contains a pigment that absorbs or reflects light having a wavelength range of 290 to 450 nm (see Patent Document 1). Such an adhesive layer is colored by containing a pigment, and the presence or absence thereof can be easily confirmed visually.

JP 2009-059917 A

  However, since the adhesive layer described in Patent Document 1 contains a pigment, when the thickness is small, aggregates and uneven color are generated, and cracks occur in the finally obtained semiconductor package. There is a problem that reliability may be lowered.

  The present invention has been made in view of the above circumstances, and provides a dicing die bonding sheet in which presence / absence and state of an adhesive layer can be easily confirmed and a highly reliable semiconductor package can be obtained. Let it be an issue.

In order to solve the above problems, the present invention comprises an adhesive layer containing a binder resin (a), an epoxy thermosetting resin (b), and a dye (s) on a base material, Content of the said dye (s) is 0.05-8.3 mass% , and content of the epoxy-type thermosetting resin (b) of the said adhesive bond layer is 100 mass parts of binder resin (a). A dicing die bonding sheet characterized in that the color difference in the L ^* a ^* b ^* color system between 1 and 100 parts by mass between the base material and the adhesive layer is 30 to 53 provide.
In the dicing die bonding sheet of the present invention, the dye (s) is preferably a disazo dye.
In the dicing die bonding sheet of the present invention, the dye (s) preferably contains no metal atom or metal ion in its structure.

  ADVANTAGE OF THE INVENTION According to this invention, the dicing die bonding sheet | seat which can confirm the presence or absence and state of an adhesive layer easily and can obtain a highly reliable semiconductor package is provided.

<< Dicing die bonding sheet >>
The dicing die bonding sheet according to the present invention includes an adhesive layer containing a dye on a substrate, and the content of the dye in the adhesive layer is 8.3 mass% or less, and the substrate and the substrate The color difference in the L ^* a ^* b ^* color system (hereinafter sometimes abbreviated as “ΔE”) between the adhesive layer and the adhesive layer is 30 to 53.
In the present specification, L ^* , a ^* and b ^* are calculated according to JIS Z8781-4: 2013.

  In the dicing die bonding sheet, the color difference (ΔE) falls within a predetermined range because the adhesive layer contains a specific amount of dye. As a result, it can be easily recognized whether or not the dicing die bonding sheet has an adhesive layer.

  In addition, by using the dicing die bonding sheet, the adhesive layer is bonded to a bonding target such as a semiconductor wafer or a semiconductor chip when pre-cut processing is performed, or when a semiconductor chip is picked up and die bonded. It is possible to easily visually check whether or not the problem occurs in the semiconductor device manufacturing process.

Further, by using the dicing die bonding sheet, in the process of manufacturing a semiconductor chip, the dicing die bonding sheet on which a wafer having a brittle part formed by laser irradiation is expanded to expand the wafer and Even when performing so-called stealth dicing for cleaving the sheet, whether or not the adhesive layer has been cleaved can be easily visually confirmed, and a decrease in the manufacturing efficiency of the semiconductor device can be suppressed.
Also, whether or not the adhesive layer could be cleaved reliably in the same way as when performing stealth dicing when expanding and cleaving the adhesive layer in which the brittle part is formed at a low temperature. The state can be easily visually confirmed, and the decrease in the manufacturing efficiency of the semiconductor device can be suppressed.
Usually, when performing these expansions, it is confirmed whether the adhesive layer has been cleaved by visual observation or observation with a microscope. However, according to the present invention, the adhesive layer is easily visible, so it can be confirmed in a short time. it can. If the adhesive layer is not cleaved, peripheral chips are also lifted at the same time when the target chip is picked up, causing trouble.

  Furthermore, since the adhesive layer contains a dye and the content thereof is 8.3% by mass or less, the semiconductor package obtained using the dicing die bonding sheet suppresses cracks and peeling at the joint. As a result, the reliability becomes high. When the adhesive layer contains a pigment instead of a dye, if the thickness of the adhesive layer is thin, especially when the thickness is about 10 μm or less, aggregates and color unevenness occur in the adhesive layer. As a result, cracks may occur in the finally obtained semiconductor package, resulting in a decrease in reliability.

<Base material>
The substrate has a color difference (ΔE) that satisfies the above relationship with the adhesive layer.
The color of the substrate is not particularly limited as long as it is not the same as the color of the adhesive layer, but it is usually preferable to be white.

The base material has a pressure-sensitive adhesive layer on its surface (hereinafter sometimes referred to as “adhesive base material”. In this case, the base material in contact with the pressure-sensitive adhesive layer is abbreviated as “support base material”. May be), or may not be provided with an adhesive layer (hereinafter may be abbreviated as “non-adhesive substrate”).
When the base material is the pressure-sensitive adhesive base material, the laminated structure of the support base material and the pressure-sensitive adhesive layer may be integrated and satisfy the above color difference (ΔE) relationship with the adhesive layer.

  The material of the non-adhesive substrate and the support substrate is preferably various resins. Specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.) )), Polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate copolymer, ionomer resin, ethylene ( Examples include (meth) acrylic acid copolymers, ethylene / (meth) acrylic acid ester copolymers, polystyrene, polycarbonate, fluororesins, water additives, modified products, cross-linked products or copolymers of any of these resins. it can.

  The non-adhesive substrate and the supporting substrate may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, the material of each layer may be the same. , All may be different or only some may be the same.

  Although the thickness of the said non-adhesive base material and a support base material can be suitably selected according to the objective, it is preferable that it is 50-300 micrometers, and it is more preferable that it is 60-100 micrometers.

The non-adhesive substrate and the support substrate are provided with a layer provided thereon, i.e., an adhesive layer or a pressure-sensitive adhesive layer, in order to improve the adhesion with the sandblasting, solvent treatment, etc., corona discharge The surface may be subjected to oxidation treatment such as treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment. Further, the non-adhesive base material and the support base material may have a surface subjected to primer treatment.
Among these, the non-adhesive base material and the support base material are particularly preferably those whose surfaces are subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the base material due to blade friction during dicing is suppressed.

[Adhesive layer]
A well-known thing can be used suitably for the said adhesive layer. When the pressure-sensitive adhesive layer is colorless, the pressure-sensitive adhesive base material reflects the color of the support base material. When the pressure-sensitive adhesive layer is colored (colored), the pressure-sensitive adhesive base material is sticky. It reflects the color of the agent layer or the colors of both the support substrate and the pressure-sensitive adhesive layer.

An adhesive layer can be formed using the adhesive composition containing the various components for comprising this. The ratio of the content of non-volatile components in the pressure-sensitive adhesive composition is the same in the pressure-sensitive adhesive layer.
When the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with energy rays, the semiconductor chip can be picked up by irradiating the energy rays to reduce the adhesiveness. Such a pressure-sensitive adhesive layer can be formed using, for example, various pressure-sensitive adhesive compositions containing an energy ray-polymerizable acrylic polymer that is polymerized by irradiation with energy rays.

  Preferred examples of the pressure-sensitive adhesive composition include the acrylic polymer and an energy ray polymerizable compound (pressure-sensitive adhesive composition (i)), a hydroxyl group, and a polymerizable group in the side chain. Examples include acrylic polymers (for example, those having a hydroxyl group and a polymerizable group in the side chain via a urethane bond) and an isocyanate-based crosslinking agent (adhesive composition (ii)). Further, those containing a solvent are preferable.

  In addition to the above-mentioned components, the pressure-sensitive adhesive composition further includes any one of various additives such as a photopolymerization initiator, a dye, a pigment, a deterioration preventing agent, an antistatic agent, a flame retardant, a silicone compound, and a chain transfer agent. It may be contained.

  Although the thickness of an adhesive layer can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 1-60 micrometers, and it is especially preferable that it is 1-30 micrometers.

An adhesive composition is obtained by mix | blending the various components for comprising an adhesive layer, such as an acrylic polymer, for example.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
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 at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
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 pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the support substrate and drying it. At this time, you may bridge | crosslink by heating the apply | coated adhesive composition as needed. The heating conditions can be, for example, 100 to 130 ° C. for 1 to 5 minutes, but are not limited thereto. Alternatively, the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the release layer of the release material and drying it, and bonding the surface to the surface of the support substrate and removing the release material. .

  Application to the surface of the support substrate of the pressure-sensitive adhesive composition or the surface of the release layer of the release material may be performed by a known method, such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, Examples include a method using various coaters such as a curtain coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.

<Adhesive layer>
The adhesive layer contains a dye. Unlike the pigment, the dye hardly generates aggregates in the adhesive layer, so that the dicing die bonding sheet maintains high quality.

Although the thickness of an adhesive bond layer can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 5-75 micrometers, and it is especially preferable that it is 5-50 micrometers.
In the present invention, even when the thickness of the adhesive layer is as thin as about 10 μm or less, unlike the case where a pigment is used as a coloring component, the generation of aggregates in the adhesive layer is suppressed. Therefore, the occurrence of cracks in the finally obtained semiconductor package is suppressed.

The color of the adhesive layer is not particularly limited as long as it is not the same as the color of the base material (adhesive base material and non-adhesive base material). Usually, the ring frame tape is black, so that it can be easily distinguished from this. Therefore, a color other than black is preferable. Among them, when the substrate is white, ΔE is a preferable range, and the presence or absence of the adhesive layer and the state of the state as described above are more easily visible. Those having a blue to red color toward the long wavelength side are preferred, and as such, L ^* (lightness) in the L ^* a ^* b ^* color system is 15 to 97, and Examples include a ^* (chromaticity) of -11 to +15 and b ^* (chromaticity) of -30 to +5. Especially, it is preferable that an adhesive bond layer is blue.

  The content of the dye in the adhesive layer is 8.3% by mass or less, and preferably 8.1% by mass or less. By being in such a range, the harmful effect by containing a dye is suppressed. More specifically, when a semiconductor package is manufactured using a dicing die bonding sheet provided with such an adhesive layer, the resulting semiconductor package may cause peeling or cracks at the junction between the substrate and the semiconductor chip. Occurrence of (package crack) is suppressed, and a decrease in reliability is suppressed. Moreover, when the said adhesive base material is used in a dicing die bonding sheet, transfer of the dye from an adhesive bond layer to an adhesive layer is also suppressed.

  The lower limit of the content of the dye in the adhesive layer is not particularly limited as long as ΔE described later becomes a target value. However, the content of the dye in the adhesive layer is preferably 0.05% by mass or more, more preferably 0.07% by mass or more from the viewpoint that ΔE can be easily adjusted to a preferable range. It is particularly preferably 10% by mass or more.

The dye is not particularly limited as long as the effect of the present invention is not impaired as long as the adhesive layer can be colored as described above, and a known one can be used as appropriate.
Specific dyes include azo dyes, nitroso dyes, quinoline dyes, sulfur dyes, nitro dyes, methine dyes, polymethine dyes, aminoketone dyes, thiazole dyes, oxyketone dyes, stilbene dyes, indamine dyes, indophenol dyes, diphenylmethane dyes, Examples include anthraquinone dyes, triarylmethane dyes, azine dyes, indigoid dyes, xanthene dyes, oxazine dyes, thiazine dyes, phthalocyanine dyes, and acridine dyes.

  The dye may be either a water-soluble dye or a water-insoluble dye, but is preferably a water-insoluble dye, and more preferably an oil-soluble dye.

The dye is preferably an azo dye having an azo group (—N═N—) because it is easily available and the adhesive layer can be easily adjusted to the intended properties.
The azo dye is a monoazo dye, disazo dye, trisazo dye, tetrakisazo dye or polyazo dye (having 5 or more azo groups in one molecule) depending on the number of azo groups in one molecule. Any of them may be used, but a disazo dye is preferable from the viewpoint that the structure is relatively rigid, heat resistance is higher, and an adhesive layer having good characteristics can be easily formed.

  The dye preferably does not contain a metal atom or metal ion in its structure from the viewpoint of further improving the reliability of the semiconductor package as described above and maintaining the conductivity of the adhesive layer low.

The color difference (ΔE) in the L ^* a ^* b ^* color system between the substrate and the adhesive layer is 30 to 53, preferably 31 to 52, and preferably 32 to 52. More preferred. When ΔE is in such a range, the presence / absence and state of the adhesive layer as described above can be easily recognized.

More specifically, ΔE can be calculated according to the following formula (I) by calculating L ^* , a ^* , and b ^* for each of the base material and the adhesive layer.
^{ΔE = [(L1 * -L2 *} ) 2 + (a1 * -a2 *) 2 + (b1 * -b2 *) 2] 1/2 ···· (I)
(Where L1 ^* is the value of L ^* of the substrate, L2 ^* is the value of L ^* of the adhesive layer, a1 ^* is the value of a ^* of the substrate, and a2 ^* is the adhesive layer) a of ^{a *} value, b1 ^* is the value of ^{b *} of the substrate, b2 ^* is the value of ^{b *} of the adhesive layer.)

  The adhesive layer preferably has pressure-sensitive adhesive properties, preferably has heat-curing properties, and more preferably has both pressure-sensitive adhesive properties and heat-curing properties. An adhesive layer having both pressure-sensitive adhesiveness and heat-curing property can be applied by lightly pressing various adherends in an uncured state. The adhesive layer may be one that can be applied to various adherends by heating and softening. The adhesive layer finally becomes a cured product having high impact resistance after being thermally cured, and the cured product is excellent in shear strength and can retain sufficient adhesive properties even under severe high temperature and high humidity conditions.

[Adhesive composition]
The adhesive layer can be formed using an adhesive composition containing components for constituting the adhesive layer such as the dye, and the ratio of the content of non-volatile components in the adhesive composition The same applies to the agent layer.
The adhesive layer is formed using an adhesive composition containing a binder resin (a), an epoxy thermosetting resin (b), and the dye (hereinafter sometimes referred to as “dye (s)”). The ones made are preferred.

(Binder resin (a))
The binder resin (a) is a polymer compound for imparting film forming properties and flexibility to the adhesive layer.
Binder resin (a) may be used individually by 1 type, and may use 2 or more types together.

  As the binder resin (a), an acrylic resin, a polyester resin, a urethane resin, an acrylic urethane resin, a silicone resin, a rubber polymer, a phenoxy resin, or the like can be used, and an acrylic resin is preferable.

A publicly known acrylic polymer can be used as the acrylic resin.
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. If the weight average molecular weight of the acrylic resin is too small, the adhesive force between the adhesive layer and the pressure-sensitive adhesive layer becomes high, and a pickup failure of the semiconductor chip may occur. Further, if the weight average molecular weight of the acrylic resin is too large, the adhesive layer may not follow the uneven surface of the adherend, which may cause generation of voids and the like.
In the present specification, the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

  The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. If the Tg of the acrylic resin is too low, the peeling force between the adhesive layer and the pressure-sensitive adhesive layer increases, which may cause a pickup failure of the semiconductor chip. Further, if the Tg of the acrylic resin is too high, the adhesive force for fixing the semiconductor wafer may be insufficient.

As a monomer constituting the acrylic resin, the alkyl group such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate has 1 carbon atom. An alkyl (meth) acrylate that is -18;
Cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) (Meth) acrylate having a cyclic skeleton such as acrylate;
Hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
Examples include (meth) acrylic acid esters such as glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate.
The acrylic resin may be one obtained by copolymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
The monomer constituting the acrylic resin may be only one type or two or more types.
In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”, and “(meth) acrylate” means “acrylate” and “methacrylate”. It is a concept that includes both.

  The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. Bonding with another compound may be performed via a crosslinking agent (f) described later, or the functional group may be directly bonded to another compound without passing through the crosslinking agent (f). . When the acrylic resin is bonded by these functional groups, the reliability of the semiconductor package using the dicing die bonding sheet tends to be improved.

The content of the acrylic resin in the solid content of the adhesive composition is preferably 50% by mass or more. By doing in this way, when using for the process of lump-hardening an adhesive bond layer at the time of resin sealing of a semiconductor chip, an adhesive bond layer becomes a preferable property. This is because, in such a process, wire bonding to the chip is performed before the resin sealing of the semiconductor chip, but even when the adhesive layer before curing is exposed to a high temperature, a certain degree of hardness is obtained. This is because wire bonding can be performed in a maintained state. That is, if the content of the acrylic resin in the adhesive composition is relatively large, the storage elastic modulus of the adhesive layer can be increased even before thermosetting. For this reason, even when the adhesive layer is uncured or semi-cured, the vibration and displacement of the chip during wire bonding are suppressed, and wire bonding can be performed stably.
Furthermore, the content of the acrylic resin in the solid content of the adhesive composition is more preferably 50 to 85% by mass. When the content of the acrylic resin is in such a range, the easy pick-up property of the semiconductor chip is improved.

In the present invention, in order to improve the peelability of the adhesive layer and improve the easy pick-up property, or to suppress the generation of voids and the like by following the adhesive layer to the uneven surface of the adherend, ) As the binder resin, a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) may be used alone or in combination with an acrylic resin.
The thermoplastic resin preferably has a weight average molecular weight of 1000 to 100,000, more preferably 3000 to 80000.
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 resin, urethane resin, phenoxy resin, polybutene, polybutadiene, and polystyrene.
The said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  By using the thermoplastic resin, the above-described effects can be obtained. On the other hand, the hardness when the adhesive layer before curing is exposed to a high temperature is reduced, and the adhesive layer in an uncured or semi-cured state There is a concern that the wire bonding suitability is lowered. Therefore, the content of the acrylic resin in the adhesive composition is preferably set in consideration of such influence.

(Epoxy thermosetting resin (b))
Epoxy thermosetting resin (b) consists of an epoxy resin and a thermosetting agent.
Epoxy thermosetting resin (b) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the epoxy resin include known ones, specifically, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and the like can be exemplified by bifunctional or higher functional epoxy compounds.

Moreover, as the epoxy resin, an epoxy resin having an unsaturated hydrocarbon group may be used. Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of an epoxy resin of a polyfunctional epoxy resin into a group containing an unsaturated hydrocarbon group. Such a compound can be produced, for example, by addition reaction of acrylic acid to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group containing an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin can be illustrated. An unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically includes an ethenyl group (vinyl group), a 2-propenyl group (allyl group), an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group. Etc., and an acryloyl group is preferable.
An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, the package reliability of a semiconductor device improves by using the adhesive composition containing the epoxy resin which has an unsaturated hydrocarbon group.

  The epoxy resin preferably has a high softening point or glass transition temperature from the viewpoint of improving easy pick-up property.

The number average molecular weight of the epoxy resin is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000 from the viewpoints of curability of the adhesive layer, strength after curing, and heat resistance. 500 to 3000 is particularly preferable.
The epoxy equivalent of the epoxy resin is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.

  The said epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The thermosetting agent functions as a curing agent for the epoxy resin.
As a thermosetting agent, the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule can be illustrated. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, and an acid group are groups in which an anhydride is converted. Are preferred, more preferably a phenolic hydroxyl group or an amino group, and particularly preferably a phenolic hydroxyl group.

Among the thermosetting agents, examples of the phenol-based curing agent (curing agent having a phenolic hydroxyl group) include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
Among the thermosetting agents, examples of the amine-based curing agent (curing agent having an amino group) include DICY (dicyandiamide).

The thermosetting agent may have an unsaturated hydrocarbon group.
As the thermosetting agent having an unsaturated hydrocarbon group, a compound obtained by substituting a part of the hydroxyl group of the phenol resin with a group containing an unsaturated hydrocarbon group, an unsaturated hydrocarbon group on the aromatic ring of the phenol resin. Examples thereof include a compound in which the containing group is directly bonded. The unsaturated hydrocarbon group in the thermosetting agent is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

  The thermosetting agent preferably has a high softening point or glass transition temperature from the viewpoint of improving easy pick-up property.

  The number average molecular weight of the thermosetting agent is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.

  The said thermosetting agent may be used individually by 1 type, and may use 2 or more types together.

  The content of the thermosetting agent in the adhesive composition is preferably 0.1 to 500 parts by mass and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin. . If the content of the thermosetting agent is too small, the adhesiveness may not be obtained due to insufficient curing, and if the content of the thermosetting agent is excessive, the moisture absorption rate of the adhesive layer increases and the package reliability is lowered. Sometimes.

  The content of the epoxy thermosetting resin (b) in the adhesive composition (total content of the epoxy resin and the thermosetting agent) is 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin (a). It is preferable that it is 1.5-75 mass parts, and it is especially preferable that it is 2-60 mass parts. When the content of the epoxy thermosetting resin (b) is within such a range, the hardness of the adhesive layer before curing tends to be maintained, and the adhesive layer in an uncured or semi-cured state The wire bonding aptitude is improved. In addition, the easy pick-up property of the semiconductor chip is improved.

(Dye (s))
The dye (s) is as described above.
The content of the dye (s) in the solid content of the adhesive composition is preferably the same as the content of the dye in the adhesive layer described above.

In order to improve various physical properties of the adhesive layer, in addition to the binder resin (a), the epoxy thermosetting resin (b) and the dye (s), if necessary, other components not corresponding to these It may be formed using an adhesive composition containing
Among the other components preferable for the adhesive composition, inorganic filler (c), curing accelerator (d), coupling agent (e), cross-linking agent (f), epoxy thermosetting resin ( Other thermosetting resins (g) and general-purpose additives (h) that do not fall under b) can be exemplified.

(Inorganic filler (c))
Since the adhesive composition further contains an inorganic filler (c), the thermal expansion coefficient thereof can be easily adjusted, and the thermal expansion coefficient of the adhesive layer after curing with respect to a semiconductor chip, metal, or organic substrate. By optimizing the package reliability of the package can be improved.
Moreover, the adhesive composition can also reduce the moisture absorption rate of the cured adhesive layer by further containing an inorganic filler (c).

Preferred inorganic fillers (c) include silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride and the like; beads formed by spheroidizing these silicas; surface modified products such as silica Examples thereof include single crystal fibers such as silica; glass fibers and the like.
Among these, the inorganic filler (c) is preferably a silica filler, an alumina filler, or a surface modified product thereof.
An inorganic filler (c) may be used individually by 1 type, and may use 2 or more types together.

  When using an inorganic filler (c), it is preferable that content of the inorganic filler (c) in solid content of an adhesive composition is 1-80 mass%.

(Curing accelerator (d))
The curing accelerator (d) is used for adjusting the curing rate of the adhesive composition.
Preferred curing accelerators (d) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (groups in which one or more hydrogen atoms are other than hydrogen atoms) Substituted imidazole); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, trif Tetraphenyl boron salts such as sulfonyl phosphine tetraphenyl borate can be mentioned.
A hardening accelerator (d) may be used individually by 1 type, and may use 2 or more types together.

  When using a hardening accelerator (d), content of the hardening accelerator (d) in an adhesive composition is 0.01-10 with respect to 100 mass parts of content of an epoxy-type thermosetting resin (b). It is preferable that it is a mass part, and it is more preferable that it is 0.1-1 mass part. When the content of the curing accelerator (d) is within such a range, the adhesive layer has excellent adhesive properties even under high temperature and high humidity conditions, and is exposed to severe reflow conditions. Can achieve high package reliability. When there is too little content of a hardening accelerator (d), the effect by using a hardening accelerator (d) will not fully be acquired, but when the content of a hardening accelerator (d) is excessive, it will be highly polar. The curing accelerator (d) moves to the side of the adhesion interface with the adherend in the adhesive layer under high temperature and high humidity conditions and segregates, thereby reducing the reliability of the package.

(Coupling agent (e))
By using a coupling agent (e) having a functional group that reacts with an inorganic compound and a functional group that reacts with an organic functional group, the adhesion and adhesion of the adhesive layer to the adherend can be improved. it can. Further, by using the coupling agent (e), the water resistance of the cured product obtained by curing the adhesive layer can be improved without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group that reacts with the functional group of the binder resin (a), the epoxy thermosetting resin (b), etc., and is preferably a silane coupling agent. desirable.
Preferred examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacryloxy). Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Methoxysi Examples thereof include orchid, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.
A coupling agent (e) may be used individually by 1 type, and may use 2 or more types together.

  When using the coupling agent (e), the content of the coupling agent (e) in the adhesive composition is 100 parts by mass with respect to the total content of the binder resin (a) and the epoxy thermosetting resin (b). It 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. If the content of the coupling agent (e) is too small, the above-mentioned effect due to the use of the coupling agent (e) may not be obtained. If the content of the coupling agent (e) is too large, Outgas may occur.

(Crosslinking agent (f))
When the above-mentioned acrylic resin having a functional group capable of binding to another compound such as an isocyanate group is used as the binder resin (a), a cross-linking agent ( f) can be used. By crosslinking using the crosslinking agent (f), the initial adhesive force and cohesive force of the adhesive layer can be adjusted.
Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of the organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, and adducts (ethylene glycol, propylene glycol). A reaction product with a low molecular active hydrogen-containing compound such as neopentyl glycol, trimethylolpropane or castor oil, such as trimethylolpropane adduct xylylene diisocyanate), or an organic polyvalent isocyanate compound and a polyol compound. The terminal isocyanate urethane prepolymer obtained can be exemplified.

  More specifically, as the organic polyvalent isocyanate compound, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4 '-Diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethylolpropane, etc. Examples include compounds in which tolylene diisocyanate or hexamethylene diisocyanate is added to all or some of the hydroxyl groups of polyol, lysine diisocyanate, and the like.

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

  When an isocyanate crosslinking agent is used as the crosslinking agent (f), a hydroxyl group-containing polymer is preferably used as the acrylic resin that is the binder resin (a). When the crosslinking agent (f) has an isocyanate group and the acrylic resin has a hydroxyl group, a crosslinked structure can be easily introduced into the adhesive layer by a reaction between the crosslinking agent (f) and the acrylic resin.

  When using a crosslinking agent (f), it is preferable that content of the crosslinking agent (f) in adhesive composition is 0.01-20 mass parts with respect to 100 mass parts of binder resin (a) content. Preferably, it is 0.1-10 mass parts, It is especially preferable that it is 0.5-5 mass parts.

(Other thermosetting resin (g))
Other thermosetting resins (g) may be those that do not correspond to the epoxy resin in the epoxy thermosetting resin (b), such as thermosetting polyimide resin, polyurethane resin, unsaturated polyester resin, silicone resin, and the like. Can be illustrated.

(General-purpose additive (h))
Examples of the general-purpose additive (h) include known plasticizers, antistatic agents, antioxidants, pigments, dyes, gettering agents and the like.

(solvent)
When the adhesive composition further contains a solvent, the handleability is improved by dilution.
The solvent contained in the adhesive composition is not particularly limited, but preferred are hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1 Examples include alcohols such as butanol; 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.
The solvent contained in the adhesive composition may be only one type or two or more types.
The solvent contained in the adhesive composition is preferably methyl ethyl ketone from the viewpoint of uniformly mixing the components used in the adhesive composition.

An adhesive composition is obtained by mix | blending dye (s) and the component for comprising an adhesive bond layer other than 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.
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 at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
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.

  An adhesive bond layer can be formed by the same method as the case where an adhesive layer is formed on the above support bases using an adhesive composition. However, when using the said adhesive base material, it is difficult to apply | coat an adhesive composition directly on an adhesive layer normally. Therefore, for example, the adhesive layer formed by applying and drying the adhesive composition on the surface of the release layer of the release material is bonded to the surface of the pressure-sensitive adhesive layer, and the release material is removed. A method of forming it separately and bonding it to the surface of the pressure-sensitive adhesive layer is preferable.

  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.

<Manufacture of dicing die bonding sheet>
[Examples 1-6, Comparative Examples 1-2]
(Manufacture of adhesive composition)
Each component was mix | blended with the quantity shown in Table 1, and also it diluted with methyl ethyl ketone, and obtained the adhesive composition.
The symbol of each component in Table 1 has the following meaning, respectively.

・ Binder resin (a)
(A) -1: Acrylic resin (made by Toyochem, weight average molecular weight 500000, glass transition temperature 9 ° C., copolymerized methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass) )
-Epoxy thermosetting resin (b)
(B) -11: Cresol novolac type epoxy resin having acryloyl group (“CNA-147” manufactured by Nippon Kayaku Co., Ltd.)
(B) -21: Aralkylphenol resin ("Mirex XLC-4L" manufactured by Mitsui Chemicals, Inc.)
・ Filler (c)
(C) -1: Methacrylic group-modified filler (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, silica treated with 3-methacryloxypropyltrimethoxysilane)
・ Coupling agent (e)
(E) -1: Silane coupling agent (“MKC silicate MSEP2” manufactured by Mitsubishi Chemical Corporation))
・ Crosslinking agent (f)
(F) -1: Aromatic polyvalent isocyanate ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd., Tolylene diisocyanate trimer adduct of trimethylolpropane)
・ Dye (s)
(S) -1: Solvent Black 3 ("OIL Black 860" manufactured by Orient Chemical Industry Co., Ltd., oil-soluble disazo dye)
(S) -2: Solvent Red 18 (“Red TR-71”, Chuo Kasei Chemical Co., Ltd., oil-soluble disazo dye)

(Manufacture of dicing die bonding sheet)
The adhesive composition obtained above is applied to the release-treated surface of the release sheet from which one side of the polyethylene terephthalate film has been peel-treated, and dried at 120 ° C. for 3 minutes, so that the thickness is 5 μm or 20 μm. An adhesive layer was formed. Further, the same release sheet as described above was bonded to the adhesive layer to produce two types of non-carrier films having an adhesive layer thickness of 5 μm and 20 μm.
Next, among these non-carrier films, those having an adhesive layer thickness of 20 μm were used, one of the release sheets was peeled off, and the adhesive layer was adhered to a dicing tape (“G-562” manufactured by Lintec Corporation). It transferred on the agent layer and obtained the dicing die bonding sheet. The dicing tape has a white base material and a colorless pressure-sensitive adhesive layer.

<Evaluation of dicing die bonding sheet>
About the dicing die-bonding sheet obtained above, the visibility of the adhesive layer and the reliability of the semiconductor package were evaluated by the following methods.

(Color difference between substrate and adhesive layer (ΔE))
Using a spectrophotometer (“UV-VIS-NIR SPECTROTOPOMETER UV-3600” manufactured by SHIMADZU) and the above-mentioned dicing tape (“G-562” manufactured by Lintec Corporation) and the thickness obtained above are 5 μm. The light transmittance of the agent layer was measured. In addition, about the dicing tape, the light transmittance was measured from the adhesive layer side. At this time, measurement was performed using a large sample chamber MPC-3100 attached to the spectrophotometer without using a built-in integrating sphere.
And according to JIS Z8781-4: 2013 from the measurement result of the obtained light transmittance, L ^* , a ^* , b ^* are calculated for each of the dicing tape as the base material and the adhesive layer, and the above formula ( According to I), the color difference (ΔE) was calculated. The results are shown in Table 1. Table 1 also shows L ^* , a ^* , and b ^* of the adhesive layer. The L ^* of the dicing tape was 46, a ^* was 1.6, and b ^* was -2.9.

(Visibility of adhesive layer)
Using a tape mounter (“Adwill RAD2500” manufactured by Lintec Corporation) on the polished surface of a dry-polished silicon wafer (150 mm diameter, 75 μm thick), the adhesive layer of the dicing die bonding sheets of Examples and Comparative Examples A film having a thickness of 20 μm was pasted through the adhesive layer, and this silicon wafer was fixed to a ring frame for wafer dicing. Next, the silicon wafer was diced into a size of 8 mm × 8 mm using a dicing apparatus (“DFD651” manufactured by Disco Corporation) to obtain a chip. At the time of this dicing, the substrate was cut by 20 μm from the surface.

  The above chip with the dicing die bonding sheet attached thereto was picked up from the substrate together with the adhesive layer of the dicing die bonding sheet. A circuit pattern is formed on the copper foil (thickness 18 μm) of the copper foil-clad laminate (“CCL-HL830” manufactured by Mitsubishi Gas Chemical Company), and a solder resist (“PSR-4000” manufactured by Taiyo Ink Co., Ltd.) is formed on this circuit pattern. AUS303 ”) is used, and the chip with the adhesive layer is placed on the substrate at 120 ° C. via the adhesive layer on the substrate (“ LN001E-001 PCB (Au) AUS303 ”manufactured by Chiken Giken Co., Ltd.). Crimping was performed under the conditions of 2.45 N (250 gf) and 0.5 seconds. Further, among the dicing die bonding sheets obtained above, a chip having an adhesive layer thickness of 5 μm was used to obtain a chip in the same procedure as described above, and the chip was then dicing die bonding sheet. The substrate was picked up from the base material together with the adhesive layer, and further pressed onto the chip press-bonded to the substrate via the adhesive layer. In this process, the color of the adhesive layer visible between the ring frame and the wafer and the color of the pick-up location of the chip with the adhesive layer are visually observed, and these colors are different from each other, that is, the adhesive layer is the chip. It was confirmed whether or not it was clearly visible by visual observation. The results are shown in Table 1.

(Reliability of semiconductor packages)
The laminate of the substrate and the chip with the adhesive layer, which was produced during the evaluation of the visibility of the adhesive layer, was heated at 175 ° C. for 1 hour using an oven. Next, the laminate, which is taken out from the oven and cooled to room temperature, is sealed using a mold resin (“KE-1100AS3” manufactured by Kyocera Chemical Co., Ltd.) and a sealing device (“MPC-06M TriAl Press” manufactured by Apic Yamada). The mold resin was cured by sealing at a thickness of 400 μm and heating at 175 ° C. for 5 hours. Then, the sealed laminate is affixed to a dicing tape (“Adwill D-510T” manufactured by Lintec Corporation) and diced into a size of 8 mm × 8 mm using a dicing apparatus (“DFD651” manufactured by Disco Corporation). Thus, a semiconductor package for reliability evaluation was obtained.

  The semiconductor package obtained above was allowed to absorb moisture by leaving it for 168 hours at 85 ° C. and a relative humidity of 60%, and then using a reflow furnace (“WL-15-20DNX type” manufactured by Sagami Riko Co., Ltd.). IR reflow was performed 3 times under the conditions of a maximum heating temperature of 260 ° C. and a heating time of 1 minute. And about the semiconductor package which performed this IR reflow, the cross-section observation of the presence or absence of the floating and peeling of the junction part of a board | substrate and a semiconductor chip is carried out, and the case where peeling of 0.5 mm or more is observed in the said junction part is peeling Therefore, the number of the 25 semiconductor packages that were not peeled was counted. Moreover, about the semiconductor package which performed this IR reflow, the presence or absence of generation | occurrence | production of a package crack was confirmed using the scanning ultrasonic flaw detector (Hitachi Construction Machinery Finetech Co., Ltd. "Hye-Focus"). The results are shown in Table 1.

As is clear from the above results, the dicing die bonding sheets of Examples 1 to 6 have a predetermined ΔE when the adhesive layer contains a dye with a content of 0.1 to 8.3 mass%. The adhesive layer was excellent in visibility and the reliability of the obtained semiconductor package was high.
On the other hand, in the dicing die bonding sheet of Comparative Example 1, since the adhesive layer did not contain the dye, ΔE was outside the predetermined range, and the adhesive layer was inferior in visibility.
Further, in the dicing die bonding sheet of Comparative Example 2, even when the adhesive layer contained a dye, ΔE was outside the predetermined range, and the adhesive layer was inferior in visibility. Furthermore, due to the excessive amount of dye in the adhesive layer, the obtained semiconductor package has many peelings observed at the junction between the substrate and the semiconductor chip, and package cracks have occurred, resulting in low reliability. It was.

  The present invention can be used for manufacturing semiconductor chips and the like.

Claims (3)

Provided with an adhesive layer containing a binder resin (a), an epoxy-based thermosetting resin (b) and a dye (s) on the base material,
Wherein a 8.3 wt% 0.05 content of the dye in the adhesive layer (s),
The content of the epoxy thermosetting resin (b) in the adhesive layer is 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin (a),
A dicing die bonding sheet, wherein a color difference in an L ^* a ^* b ^* color system between the base material and the adhesive layer is 30 to 53.   The dicing die bonding sheet according to claim 1, wherein the dye (s) is a disazo dye.   The dicing die bonding sheet according to claim 1 or 2, wherein the dye (s) does not contain a metal atom or metal ion in its structure.