KR20120010971A - Adhesive composition and adhesive film - Google Patents

Abstract

PURPOSE: An adhesive composition is provided to improve softening point by including an adhesive resin, and a filler. CONSTITUTION: An adhesive composition comprises an adhesive resin, and a filler. The content of the filler is 20-70 weight% on the basis of the resin. The average particle diameter of the filler is 0.5-5 micron. The filler is an inorganic filler. The heat resistance of the filler is 300°C or more. The resin is hydrocarbon resin. The hydrocarbon resin is selected from a group consisting of a cycloolefin-based polymer, a terphene resin, a rosin-based resin, and a petroleum based resin. The adhesive film comprises an adhesive layer containing the adhesive composition.

Description

Adhesive Composition and Adhesive Film {ADHESIVE COMPOSITION AND ADHESIVE FILM}

The present invention relates to an adhesive composition and an adhesive film for bonding a wafer.

As an adhesive composition, patent document 1 describes the adhesive agent containing a hydrocarbon resin. Further, Patent Document 2 describes an adhesive resin composition containing silica fine powder having an organic group chemically reacted with an adhesive resin component on its surface, and Patent Document 3 describes an adhesive in which filler is added to a main material. have.

Japanese Patent Application Laid-Open No. 2010-109324 Japanese Patent Application Laid-Open No. 10-287854 Japanese Patent Laid-Open No. 8-319466

However, after adhering the wafer and the glass substrate or the like using the adhesive of the prior art as described above, if a high temperature process is performed at around 250 ° C., for example, the so-called delamination in which the adhesive melts from the end face of the wafer ( The adhesive melts from the end face of the wafer). For this reason, it is desired to further improve (higher) the softening temperature of the adhesive composition.

SUMMARY OF THE INVENTION The present invention has been devised in view of the above problems of the prior art, and an object thereof is to provide an adhesive composition and an adhesive film with a further improved softening temperature (higher) in order to bond wafers.

In order to solve the said subject, the adhesive composition which concerns on this invention is characterized by including resin and filler which have adhesiveness as an adhesive composition for bonding a wafer.

Moreover, it is preferable that the adhesive composition which concerns on this invention is 20 weight% or more and 70 weight% or less of the said filler with respect to the said resin.

Moreover, it is preferable that the average particle diameter of the said filler is 0.5 micrometer or more and 5 micrometers or less in the adhesive composition which concerns on this invention.

In the adhesive composition according to the invention, the filler is preferably an inorganic filler.

Further, in the adhesive composition according to the present invention, it is preferable that the heat resistance of the filler is 300 ° C or higher.

In addition, in the adhesive composition according to the present invention, the resin is preferably a hydrocarbon resin.

In the adhesive composition according to the present invention, the hydrocarbon resin is preferably selected from the group consisting of cycloolefin-based polymers, terpene resins, rosin-based resins and petroleum resins.

In order to solve the said subject, the adhesive film which concerns on this invention is provided with the adhesive bond layer containing any one of the above-mentioned adhesive compositions on a film.

The adhesive composition according to the present invention, as described above, is an adhesive composition for bonding a wafer, and includes a resin and a filler having adhesiveness. Thus, it is possible to provide an adhesive composition and an adhesive film with an improved softening temperature (higher).

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the measurement result using TMA (thermomechanical analyzer) with respect to the adhesive composition by Example 3 of this invention.
2 is a graph showing a measurement result using TMA with respect to the adhesive composition according to Example 4 of the present invention.
3 is a graph showing a measurement result using TMA with respect to the adhesive composition according to Example 7 of the present invention.
4 is a graph showing a measurement result using TMA with respect to the adhesive composition according to Example 8 of the present invention.
5 is a graph showing a measurement result using TMA with respect to the adhesive composition according to Example 9 of the present invention.
6 is a graph showing a measurement result using TMA with respect to the adhesive composition according to Example 10 of the present invention.
It is a graph which shows the measurement result using TMA with respect to the adhesive composition by the comparative example of this invention.
It is a graph which shows the relationship between the stress and filler content at the time of using the adhesive composition by each Example of this invention.

One embodiment which concerns on this invention is described in detail below.

Adhesive Composition

The adhesive composition which concerns on this embodiment contains resin and filler which have adhesiveness as an adhesive composition for bonding a wafer.

Since the adhesive composition of this embodiment contains a filler, since melt | dissolution at high temperature is physically suppressed, a softening temperature further improves (becomes high). Therefore, by adhering the wafer to a glass substrate or the like using such an adhesive composition, it is possible to suppress that the adhesive melts from the end face of the wafer (delamination) during subsequent high temperature processes (such as deposition processes such as PVD and CVD). have. Therefore, the adhesive composition concerning this embodiment can be used suitably for wafer bonding.

Hereinafter, each component which an adhesive composition contains is demonstrated.

<Filler>

Although a filler is not specifically limited, For example, it is preferable that it is an inorganic filler. As the inorganic filler, silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrite type, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, alkaline magnesium carbonate, calcium carbonate, zinc carbonate, Valium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mud, mica, montmorillonite, bentonite, sepiolite, imogolite, cerisart, glass fiber, glass beads, silica-based balloons, nitriding Aluminum, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, zinc borate, various magnetic components, and the like.

In addition, the inorganic filler may be surface-treated by various coupling agents, such as a silane system and a titanate system. As a method of surface treatment, the method of processing various coupling agents directly with an inorganic filler by a dry method, a slurry method, a spray method, etc., methods, such as the integral blend method, such as a direct method and a master batch method, or a dry concentrate method, are mentioned. .

As a commercial item which can be used as a filler, the silicone resin powder, silicone composite powder, silicone rubber powder, etc. made from Shin-Etsu Chemical Co., Ltd. are mentioned, for example.

It is preferable that the content rate of the filler with respect to resin is 20 weight% or more and 70 weight% or less. Delamination can be suppressed because the softening temperature of an adhesive agent becomes high enough that the content rate of a filler is 20 weight% or more. Moreover, sufficient adhesive force can be maintained as it is 70 weight% or less. Here, "the content rate of the filler with respect to resin" means the content rate at the time of making resin 100 weight%.

In addition, the content rate of a filler should just be an amount which can avoid peeling of the wafer adhere | attached with the adhesive composition, and it is preferable from a viewpoint of the raise of the softening temperature of an adhesive agent, and the relaxation of a stress. Therefore, as for content of a filler, 50 weight% or more and 70 weight% or less are more preferable.

As for the average particle diameter of a filler, 0.5 micrometer or more and 5 micrometers or less are preferable. Thereby, since it is disperse | distributed without sedimentation in an adhesive composition, the function can fully be exhibited. Moreover, as for the average particle diameter of a filler, 0.5 micrometer or more and 1 micrometer or less are preferable from a viewpoint of relieving the stress of a wafer. When using the adhesive composition containing the filler which has such an average particle diameter, when the high temperature process is performed after adhering a wafer to a glass substrate etc., the curvature state amount of a wafer can be reduced. Thus, subsequent process flows are possible.

Moreover, it is preferable that the heat resistance of a filler is 300 degreeC or more. Thereby, delamination can be suppressed effectively. In addition, in this specification, "having heat resistance of 300 degreeC or more" means that the weight change rate at the time of heating from room temperature to 300 degreeC is 1% or less.

<Resin>

What is necessary is just to provide adhesiveness as resin, For example, hydrocarbon resin, acrylic-styrene resin, maleimide resin, etc. are mentioned.

(Hydrocarbon resin)

As the hydrocarbon resin, at least one resin selected from the group consisting of a cycloolefin-based polymer (hereinafter sometimes referred to as "resin (A)"), a terpene resin, a rosin-based resin, and a petroleum resin (hereinafter referred to as "resin ( B) "may be referred to.), But is not limited to these.

As resin (A), it may be resin formed by superposing | polymerizing the monomer component containing a cycloolefin type monomer. Specifically, the ring-opening (co) polymer of the monomer component containing a cycloolefin monomer, resin which added (co) polymerized the monomer component containing a cycloolefin monomer, etc. are mentioned.

As said cycloolefin type monomer contained in the monomer component which comprises resin (A), For example, tricyclics, such as a dicyclic, such as norbornene and norbornadiene, dicyclopentadiene, and dihydroxy pentadiene, tetra Tetracyclics such as cyclododecene, Tetracyclics such as cyclopentadiene trimers, Tetracyclics such as tetracyclopentadiene, Alkyl (methyl, ethyl, propyl, butyl, etc.) substituents of these polycyclic compounds, Alkenyl (vinyl, etc.) ) Substituent, alkylidene (ethylidene and the like) substituent, aryl (phenyl, tolyl, naphthyl and the like) and the like. Especially, the norbornene-type monomer chosen from the group which consists of norbornene, tetracyclo dodecene, or these alkyl substituents is preferable.

The monomer component which comprises resin (A) may contain the other monomer copolymerizable with the cycloolefin monomer mentioned above. For example, it is preferable to contain an alkene monomer. As an alkene monomer, ethylene, propylene, 1-butene, isobutene, 1-hexene, (alpha)-olefin, etc. are mentioned, for example. The alkene monomer may be linear or branched.

It is preferable that 50 mass% or more of the monomer component which comprises resin (A) is the said cycloolefin type monomer, More preferably, it is preferable that 60 mass% or more is the said cycloolefin type monomer. When the cycloolefin monomer is 50% by mass or more of the entire monomer component, the adhesive strength in a high temperature environment is good.

In addition, resin (A), for example, resin which does not have a polar group like resin formed by superposing | polymerizing the monomer component which consists of a cycloolefin type monomer and an alkene monomer is preferable in gas generation suppression at high temperature.

There are no particular restrictions on the polymerization method, polymerization conditions, and the like when the monomer components are polymerized, and the polymerization may be carried out according to a conventional method.

As a commercial item which can be used as resin (A), for example, "TOPAS" made from polyplastics company, "APEL" made by Mitsui Chemicals company, "ZEONOR" made by Japan Xeon company, "ZEONOR" made by Japan Zeon company, "ARTON" made by JSR company, etc. Can be mentioned.

It is preferable that the glass transition point (Tg) of resin (A) is 60 degreeC or more. It is preferable that especially the glass transition point of resin (A) is 70 degreeC or more. When the glass transition point of resin (A) is 60 degreeC or more, softening of an adhesive layer can be further suppressed when an adhesive composition is exposed to high temperature environment.

Resin (B) is at least 1 sort (s) of resin chosen from the group which consists of terpene resin, rosin-type resin, and petroleum resin. Specifically as terpene-type resin, a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, etc. are mentioned, for example. As rosin resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymeric rosin, polymeric rosin ester, modified rosin etc. are mentioned, for example. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, cycloaliphatic petroleum resins, coumarone and indene petroleum resins. Among these, hydrogenated terpene resin and hydrogenated petroleum resin are preferable.

Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of resin (B) is 80 degreeC or more, it can suppress softening when an adhesive composition is exposed to high temperature environment, and a bad adhesion does not arise. On the other hand, when the softening point of resin (B) is 160 degrees C or less, the peeling speed at the time of peeling an adhesive composition becomes favorable.

Although the molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3000. When the molecular weight of resin (B) is 300 or more, it will have sufficient heat resistance and will have a small amount of degassing in high temperature environment. On the other hand, when the molecular weight of resin (B) is 3000 or less, the peeling speed at the time of peeling an adhesive composition becomes favorable. In addition, the molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

Moreover, what mixed resin (A) and resin (B) can be used as resin. By mixing, heat resistance and peeling rate become favorable. For example, when the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio), the peeling rate, heat resistance and flexibility in a high temperature environment are It is preferable because it is excellent.

(Acrylic-styrene resin)

As acryl-styrene resin, resin which superposed | polymerized using styrene or the derivative of styrene, (meth) acrylic acid ester, etc. as a monomer is mentioned, for example.

As (meth) acrylic acid ester, the (meth) acrylic-acid alkylester which has a chain structure, the (meth) acrylic acid ester which has an aliphatic ring, and the (meth) acrylic acid ester which has an aromatic ring are mentioned, for example. Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acryl-based long chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms, and the like. As an acryl-type long-chain alkyl ester, the alkyl group of acrylic acid or methacrylic acid whose n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-ecosyl group etc. is mentioned. Alkyl esters. In addition, the alkyl group may be branched.

As an acryl-type alkyl ester which has a C1-C14 alkyl group, the well-known acryl-type alkyl ester used for the existing acryl-type adhesive agent is mentioned. For example, acrylic acid or methacrylic which an alkyl group consists of a methyl group, an ethyl group, a propyl group, a butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. And alkyl esters of acids.

As (meth) acrylic acid ester which has an aliphatic ring, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobonyl ( Meta) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like, but isobornyl methacrylate, dicyclopentanyl ( Meth) acrylate is more preferable.

Although it does not specifically limit as (meth) acrylic acid ester which has an aromatic ring, As an aromatic ring, a phenyl group, benzyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthracenyl group, phenoxy A methyl group, a phenoxy ethyl group, etc. are mentioned. In addition, the aromatic ring may have a C1-C5 linear or branched alkyl group. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)

As maleimide resin, For example, as a monomer, N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N- Isobutyl maleimide, N-sec-butyl maleimide, N-tert-butyl maleimide, N-n-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl Maleimide having an alkyl group such as maleimide, N-lauryl maleimide, N-stearyl maleimide, N-cyclopropyl maleimide, N-cyclobutyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide Maleimide which has aliphatic hydrocarbon groups, such as a mead, N-cycloheptyl maleimide, and N-cyclooctyl maleimide, N-phenyl maleimide, N-m-methylphenyl maleimide, N-o-methylphenyl maleimide, N-p- Such as methylphenyl maleimide The resin obtained by superposing | polymerizing the aromatic maleimide etc. which have an aryl group is mentioned.

<Method for Producing Adhesive Composition>

The adhesive composition which concerns on this embodiment can be manufactured by mixing the resin and filler mentioned above using a well-known method. As resin, the solution (resin solution) diluted with the organic solvent can be used as needed.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, ethylene glycol mono acetate, diethylene glycol, diethylene glycol mono acetate Polyhydric alcohols and derivatives thereof such as mono methyl ether, mono ethyl ether, mono propyl ether, mono butyl ether or mono phenyl ether of propylene glycol, propylene glycol mono acetate, dipropylene glycol or dipropylene glycol mono acetate; dioxane and the like; Cyclic ethers thereof; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyrrate, ethyl pyrrate, methyl methoxy propionate and ethyl ethoxy propionate; and terpene solvents; have. These can be used independently and can mix and use 2 or more types.

As a terpene-type solvent, For example, (alpha)-pinene, a camphor, refuge, myrcene, dihydro myrcene, p-mentan, 3-carene, p-mentadiene, (alpha)-terpinene, (beta) -terpinene, (alpha)- Ferrandene, ocymen, limonene, p-simen, γ-terpinene, terpinolene, 1,4-cineol, 1,8-cineol, rose oxide, linarol oxide, phencone, α-cyclocyene Traral, Oshimenol, Tetrahydrorinalol, Linarol, Tetrahydromuguol, Isopregol, Dihydrorinalol, Isodihydrolabandulol, β-cyclocitral, Citroneral, L-Menton, Linaryl Formate , Dihydroterpineol, β-terpineol, menthol, myrsenol, L-menthol, pinokalbeol, α-terpineol, γ-terpineol, nopol, myrtenol, dihydrocalbeol, citronone Nol, mytenal, dihydrocarbon, d-pregon, geranylethyl ether, geranyl formate, neryl formate, terfinyl formate, isohydrohydrovanduril acetate Terpinyl acetate, linaryl acetate, myrsenyl acetate, carbonyl acetate, menthyl propionate, linaryl propionate, neol, carveol, perilla alcohol, geraniol, safranal, citral, perillaaldehyde, citroneryloxy Acetaldehyde, hydroxycitroneral, berbenone, d-carbon, L-carbon, piperitone, piperitenone, citronyl formate, isobornyl acetate, menthyl acetate, citroneryl acetate, carbyl acetate , Dimethyloctanyl acetate, neryl acetate, isopre acetate, dihydrocarbyl acetate, nofil acetate, geranyl acetate, bonyl propionate, neryl propionate, carbionate propionate, terpinyl, propionate citroneryl, propionate isobornyl, Isobutyric acid linaryl, isobutyric acid neryl, butyric acid linaryl, butyric acid neryl, isobutyric acid terfinyl, buty Terpinyl sorbate, geranyl isobutyrate, citroneryl butyrate, citroneryl hexanoate, menthyl isotyl acetate, β-cariopinene, cedrene, bisaborene, hydroxycitronerole, farnesol and rosinyl isobutyrate Etc. can be mentioned. Among these, from a viewpoint of solubility, limonene and p-mentan are more preferable, and p-mentan is especially preferable.

[Adhesive Film]

The adhesive composition which concerns on this embodiment mentioned above can employ | adopt various usage methods according to a use. For example, the method of apply | coating on a to-be-processed object, such as a semiconductor wafer, in a liquid state, and forming an adhesive bond layer can be used, and it is mentioned above on the adhesive film which concerns on this embodiment, ie, a film, such as a flexible film beforehand. After forming the adhesive bond layer containing any one adhesive composition, it can dry, and the method (adhesive film method) of sticking the said film (adhesive film) to a to-be-processed object and using it can be used.

Thus, the adhesive film which concerns on this embodiment is equipped with the adhesive bond layer containing any one of the above adhesive compositions on a film. Therefore, since the softening temperature of an adhesive composition is high, delamination in a high temperature process can be suppressed.

An adhesive film can coat | cover and use a protective film further on this adhesive bond layer. In this case, an adhesive layer can be easily provided on a to-be-processed object by peeling the protective film on an adhesive bond layer, making the adhesive layer exposed on a to-be-processed object overlap, and peeling a film from an adhesive layer.

Therefore, when using the adhesive film in this embodiment, compared with the case where an adhesive composition is apply | coated directly on a to-be-processed object, a layer with favorable film thickness uniformity and surface smoothness can be formed.

Moreover, as a film used for manufacture of an adhesive film, the adhesive layer formed by the film | membrane on a film can be peeled from a film, and the reshaped type which can transfer an adhesive bond layer to to-be-processed surfaces, such as a protective substrate and a wafer, is made. The film is not particularly limited. For example, the flexible film which consists of synthetic resin films, such as polyethylene terephthalate of 15-125 micrometers of thickness, polyethylene, a polypropylene, a polycarbonate, polyvinyl chloride, is mentioned. It is preferable that a film is reshaped as needed for easy transfer.

As a method of forming an adhesive bond layer on a film, you may use the well-known method suitable according to the film thickness and uniformity of a desired adhesive bond layer. Although it is not specifically limited, For example, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, etc. are used, and the dry film thickness of an adhesive bond layer on a film becomes 10-1000 micrometers in this invention, The method of apply | coating the adhesive composition which follows is mentioned. Among them, the roll coater is preferable because it is excellent in uniformity of the film thickness and can form a thick film efficiently.

In addition, when using a protective film, it is although it does not specifically limit as long as it can peel from an adhesive bond layer, For example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable. In addition, it is preferable that each protective film is coated or engraved with silicone from the viewpoint of the ease of peeling from the adhesive layer. Although the thickness of a protective film is not specifically limited, 15-125 micrometers is preferable from a viewpoint of ensuring the flexibility of the adhesive film provided with a protective film.

The method of using the adhesive film is not particularly limited, but, for example, in the case of using a protective film, the adhesive film is peeled off, and then the exposed adhesive layer is superimposed on the workpiece, and the film is formed (the back side of the formed surface of the adhesive layer). The method of thermopressing an adhesive bond layer to the to-be-processed object surface is mentioned by moving a heating roller from the inside. At this time, if the protective film peeled from an adhesive film is wound up in roll form with a winding roller etc. one by one, it can be recycled after storage.

[Use of adhesive composition and adhesive film]

The use of the adhesive composition and the adhesive film of the present invention is not particularly limited as long as the adhesive composition and the adhesive film are used for the bonding of the wafer. The adhesive composition and the adhesive film of the present invention can be suitably used for bonding a protective substrate for precision processing of a semiconductor wafer to a substrate such as a semiconductor wafer. .

This invention is not limited to embodiment mentioned above, A various change is possible in the range as described in a claim. That is, the embodiment which can be obtained by combining the technical means suitably changed in the range as described in a claim is also included in the technical scope of this invention.

[Example]

[Production of Adhesive Composition]

Resin provided with adhesiveness was melt | dissolved in p-mentane, and the resin solid content concentration was set as the resin solution of 30 mass%. Thereafter, a filler was added to the resin solution (based on the resin solid content), mixed using a planetary mixer, and the adhesive compositions of Examples 1 to 10 were prepared.

As a filler, any one of the filler 1 and the filler 2 which are silicon particle was used. Filler 1 roneun, poly Organic nosil process siloxane (RSi _{3/2) n} is water three-dimensionally crosslinked silicone resin powder ( "KMP-701" (product name) of;? 3.5㎛ particle size, particle size distribution 6㎛ one, or more 400 ℃ heat resistance, Shin-Etsu Chemical company) was used. As the filler 2, silicon composite powder ("X-52-3030" (product name); particle size 0.8 micrometer, particle size distribution 0.2-2 micrometers, heat resistance of 300 degreeC or more, the product made by Shin-Etsu Chemical Co., Ltd.) in which silicone was coat | covered with the silicone resin was used. .

As resin with adhesiveness, either one of resin 1 and resin 2 was used. As the resin 1, a cycloolefin copolymer (“TOPAS” (trade name) 8007, manufactured by Polyplastics) was used. As the resin 2, a cycloolefin copolymer (“APEL” (trade name) 8008, manufactured by Mitsui Chemicals, Inc.) was used.

As an adhesive composition in a comparative example, resin 1 was used and the adhesive composition which does not contain a filler was manufactured.

The composition of the adhesive composition in Examples 1-10 and a comparative example is shown in Table 1 below.

filler Filler content (wt%) Suzy Example 1
Filler 1 10%


Resin 1
Example 2 20% Example 3 50% Example 4 70% Example 5

Filler 2
10% Example 6 20% Example 7 50% Example 8 70% Example 9 50% Resin 2
Example 10 70% Comparative example none 0% Resin 1

[Measurement of Glass Transition Point and Softening Point]

Next, the glass transition point and softening point of each adhesive composition were measured.

After apply | coating each adhesive composition on the 125 mm wafer, it dried at 110 degreeC, 150 degreeC, and 200 degreeC for 3 minutes, respectively, and formed the coating film. About the formed coating film, the glass transition point (Tg) and softening point (SP) of the adhesive composition were measured using TMA (thermomechanical analyzer), respectively. As measurement conditions, weighting was 800 mN / cm <^2> and the temperature rise recipe was made into normal temperature-200 degreeC (5 degreeC / min). In this condition, the point at which the lowering starts is taken as the glass transition point, and the point at which the lowering starts further is made the softening point.

1-6 are graphs showing the measurement results using TMA for the adhesive composition in Examples 3, 4, 7, 8, 9 or 10 of the present invention, respectively. 7 is a graph which shows the measurement result using TMA with respect to the adhesive composition in the comparative example of this invention. In addition, the glass transition point and softening point which can be obtained from this measurement result are shown in Table 2 below.

Glass transition point (℃) Softening point (℃) Example 3 73.2 166 Example 4 66.0 164 Example 7 68.0 154 Example 8 68.6 177 Example 9 60.9 163 Example 10 60.9 194 Comparative example 68.0 153

As shown in Table 2, it turns out that the adhesive composition of Example 3, 4, 7, 8, 9, and 10 has a high softening point and the softening temperature is improved compared with a comparative example. In addition, it was shown that such an effect can be obtained regardless of the type of resin used.

In addition, the measurement result (FIGS. 1-6) using TMA in the adhesive composition of Examples 3, 4, 7, 8, 9, and 10 showed the behavior different from the comparative example (FIG. 7). In the adhesive composition of Examples 3 and 4 containing the filler 1 of 3.5 micrometers in particle size, the fall in 120 degreeC-150 degreeC was gentle.

In addition, in the adhesive composition of Examples 7 and 8 containing the filler 2 with a particle diameter of 0.8 micrometer, the fall was small from room temperature to about 170 degreeC compared with the comparative example, Examples 3 and 4. Therefore, it turns out that softening temperature improves, so that the particle size of the filler contained in an adhesive composition is small.

[Measurement of stress]

Next, the stress (film stress) in the case of using each adhesive composition was measured.

The adhesive composition was applied onto a 125 mm wafer, dried at 110 ° C., 150 ° C., and 200 ° C. for 3 minutes, respectively, and after forming an adhesive layer, a glass substrate was adhered on this adhesive layer. Then, the stress in 23 degreeC was measured using the bending state film | membrane stress measuring apparatus (FLX-2908, KLA-Tencor make).

The results are shown in FIG. 8 and Table 3 below. 8 is a graph showing the relationship between filler content and stress in the case of using the adhesive composition of each embodiment of the present invention. As shown in FIG. 8 and Table 3, especially when the adhesive composition (Examples 5-8) containing the filler 2 was used, the more content of a filler, the stress reduced.

Film thickness (㎛) Curved state (㎛) Stress (MPa) Example 1 12.4 13.56 8.3 Example 2 12.6 18.80 9.0 Example 3 34.2 46.26 9.3 Example 4 36.5 46.49 8.4 Example 5 12.7 16.23 8.0 Example 6 14.1 18.34 7.9 Example 7 55.9 55.10 6.3 Example 8 54.3 48.89 3.2 Comparative example 11.4 19.25 9.3

Therefore, it shows that by using the adhesive composition containing a filler, stress can be relaxed and the amount of curvature of a wafer can be reduced. In particular, it was found that by containing 50% by weight or more of the filler, a more favorable effect can be obtained in relaxation of stress. In addition, it is understood that the smaller the particle size of the filler, the higher the effect of relieving stress.

The adhesive composition and adhesive film which concern on this invention can be used suitably for the process of processes, such as a semiconductor wafer.

Claims (8)

In the adhesive composition for bonding a wafer,
Adhesive composition containing resin and filler which have adhesiveness. The method according to claim 1,
Adhesive content of the said filler with respect to the said resin is 20 weight% or more and 70 weight% or less. The method according to claim 1 or 2,
The average particle diameter of the said filler is 0.5 micrometer or more and 5 micrometers or less, The adhesive composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The filler is an adhesive composition, characterized in that the inorganic filler. The method according to any one of claims 1 to 4,
Adhesive composition characterized in that the heat resistance of the filler is 300 ℃ or more. The method according to any one of claims 1 to 5,
The resin composition, characterized in that the hydrocarbon resin. The method of claim 6,
The hydrocarbon resin is an adhesive composition, characterized in that selected from the group consisting of cycloolefin-based polymers, terpene resins, rosin-based resins and petroleum resins. An adhesive film for adhering a wafer comprising an adhesive layer containing the adhesive composition of any one of claims 1 to 7 on a film.

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