JP6038919B2 - Protective film forming layer, protective film forming sheet, and method of manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a protective film forming layer capable of forming a protective film on a semiconductor wafer or a semiconductor chip and capable of improving the manufacturing efficiency of the semiconductor chip, and a protective film forming sheet having the protective film forming layer. In particular, the present invention relates to a protective film forming sheet used for manufacturing a semiconductor chip to be mounted by a so-called face down method. The present invention also relates to a method for manufacturing a semiconductor device using the protective film forming layer or the protective film forming sheet.

  2. Description of the Related Art In recent years, semiconductor devices have been manufactured using a so-called “face down” mounting method. In the face-down method, a semiconductor chip (hereinafter simply referred to as “chip”) having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.

  The exposed back surface of the chip may be protected by an organic film. Conventionally, a chip having a protective film made of an organic film is obtained by applying a liquid resin to the back surface of a wafer by spin coating, drying and curing, and cutting the protective film together with the wafer. However, since the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.

  In order to solve the above problems, a protective film-forming sheet for a chip having a support sheet and a protective film-forming layer comprising a heat or energy ray-curable component and a binder polymer component formed on the support sheet is disclosed. (Patent Document 1).

  By the way, the required physical properties of recent semiconductor devices have become very strict. For example, a semiconductor device is required to have high reliability in a severe hot and humid environment. In connecting electronic components, a surface mounting method (reflow) is performed in which the entire semiconductor device is exposed to a high temperature equal to or higher than the solder melting point. In recent years, the mounting temperature has increased to about 260 ° C. due to the shift to lead-free solder. For this reason, the stress generated inside the semiconductor device is larger than before, and there is an increased possibility of causing problems such as peeling at the interface between the protective film and the chip.

  Therefore, usually, a silane coupling agent is used to improve the adhesion between the chip and the protective film, and the peeling at the interface between the protective film and the chip is suppressed.

JP 2002-280329 A

  However, even when a silane coupling agent is used, when the protective film forming sheet is used after being stored for a certain period of time, especially when the protective film is formed on the chip and then subjected to hot and humid conditions, the protective film and the chip In some cases, the adhesive strength between the films decreases, or a void occurs between the protective film and the chip.

  An object of the present invention is to provide a protective film-forming layer having excellent adhesive strength with a chip even after being subjected to severe heat and humidity conditions and a reflow process after being stored for a certain period of time, a protective film-forming sheet having the protective film-forming layer, and the A method of manufacturing a semiconductor device using a sheet is provided.

  The present inventors have intensively studied to solve the above problems. As a result, it was found that the above problems can be solved by using a highly reactive oligomer type silane coupling agent together with a low reactivity monomer type silane coupling agent as a silane coupling agent, and the present invention was completed. It came to do.

That is, the gist of the present invention is as follows.
[1] Binder polymer component (A), thermosetting component (B), inorganic filler (C), alkoxy group and reactive functional group other than alkoxy group, molecular weight of 300 or more, alkoxy equivalent of 13 mmol / g Protection comprising a larger silane coupling agent (D) and a silane coupling agent (E) having an alkoxy group and a reactive functional group other than an alkoxy group, having a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less Film forming layer.

[2] The protective film forming layer according to [1], wherein the reactive functional group other than the alkoxy group in either one or both of the silane coupling agent (D) and the silane coupling agent (E) is an epoxy group. .

[3] The binder polymer component (A) is an acrylic polymer, and the monomer constituting the acrylic polymer does not include a monomer having an epoxy group, or the total mass of the monomers constituting the acrylic polymer is epoxy. The protective film-forming layer according to [1] or [2], wherein the mass ratio of the monomer having a group exceeds 0% by mass and is 10% by mass or less, and the thermosetting component (B) contains an epoxy resin. .

[4] The protective film forming layer according to any one of [1] to [3], further including a colorant (G).

[5] The content of the inorganic filler (C) is 1 to 80 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer. Protective film forming layer.

[6] A protective film-forming sheet formed by forming the protective film-forming layer according to any one of [1] to [5] on a support sheet.

[7] A method for manufacturing a semiconductor device, comprising a step of attaching a protective film forming layer of the protective film forming sheet according to [6] to a semiconductor wafer to obtain a semiconductor chip having the protective film.

[8] A method for manufacturing a semiconductor device, further including the following steps (1) to (3), wherein the steps (1) to (3) are performed in an arbitrary order;
Step (1): peeling off the protective film-forming layer or protective film according to any one of [1] to [5] and the support sheet,
Step (2): The protective film forming layer according to any one of [1] to [5] is cured to obtain a protective film.
Step (3): Dicing the semiconductor wafer and the protective film forming layer or protective film according to any one of [1] to [5].

  According to the present invention, the protective film forming layer having excellent adhesion to the chip when subjected to severe heat and humidity conditions and a reflow process even after being stored for a certain period of time, and the protective film forming sheet having the protective film forming layer And the manufacturing method of a semiconductor device using the same can be provided. Moreover, according to the protective film formation layer, a highly reliable semiconductor device can be obtained.

  Hereinafter, details of the protective film forming layer, the protective film forming sheet, and the semiconductor device manufacturing method of the present invention will be described.

[Protective film forming layer]
The protective film forming layer has a reactive functional group other than the binder polymer component (A), thermosetting component (B), inorganic filler (C), alkoxy group and alkoxy group, has a molecular weight of 300 or more and an alkoxy equivalent. Silane coupling agent (E) having a silane coupling agent (D) greater than 13 mmol / g and an alkoxy group and a reactive functional group other than an alkoxy group, having a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less including.

(A) Binder polymer component The binder polymer component (A) is used for imparting sufficient adhesion and film forming property (sheet forming property) to the protective film forming layer. As the binder polymer component (A), conventionally known acrylic polymers, polyester resins, urethane resins, acrylic urethane resins, phenoxy resins, silicone resins, rubber polymers, and the like can be used.

  The weight average molecular weight (Mw) of the binder polymer component (A) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,200,000. If the weight average molecular weight of the binder polymer component (A) is too low, the peeling force between the protective film-forming layer and the support sheet described later increases, and transfer failure of the protective film-forming layer may occur. The adhesiveness of the layer may be reduced and transfer to a chip or the like may not be possible, or the protective film may be peeled off from the chip or the like after transfer.

  An acrylic polymer is preferably used as the binder polymer component (A). The glass transition temperature (Tg) of the acrylic polymer is preferably -60 to 50 ° C, more preferably -50 to 40 ° C, and particularly preferably -40 to 30 ° C. If the glass transition temperature of the acrylic polymer is too low, the peeling force between the protective film-forming layer and the support sheet may increase, resulting in transfer failure of the protective film-forming layer, and if it is too high, the adhesion of the protective film-forming layer will be reduced. In some cases, the film cannot be transferred to the chip or the like, or the protective film may be peeled off from the chip after the transfer.

The monomer constituting the acrylic polymer in the present invention includes at least a (meth) acrylic acid ester or a derivative thereof.
(Meth) acrylic acid ester or derivative thereof includes (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms, (meth) acrylic acid ester having a cyclic skeleton, and (meth) acrylic acid having a hydroxyl group. Examples include esters, (meth) acrylic acid esters having a glycidyl group, (meth) acrylic acid esters having an amino group, and (meth) acrylic acid esters having a carboxyl group.

Examples of the (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Examples include decyl, lauryl (meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.
Examples of (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl ester, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( Examples thereof include (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate.
Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and the like.
Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl (meth) acrylate.
Examples of the (meth) acrylic acid ester having an amino group include monoethylamino (meth) acrylate and diethylamino (meth) acrylate.
Examples of the (meth) acrylic acid ester having a carboxyl group include 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxypropyl phthalate.
In addition, the acrylic polymer includes monomers having a carboxyl group other than (meth) acrylic acid esters such as (meth) acrylic acid and itaconic acid, (meth) acrylic acid such as vinyl alcohol and N-methylol (meth) acrylamide. Monomers having a hydroxyl group other than esters, (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, styrene and the like may be copolymerized.
When an acrylic polymer containing a monomer having a hydroxyl group is used, the acrylic polymer can be easily cross-linked by using an organic polyvalent isocyanate compound or the like as a cross-linking agent (K) to be described later. The cohesiveness of the previous protective film forming layer can be controlled.

Moreover, when an epoxy resin is employed as the thermosetting resin in the thermosetting component (B) described later, the mass ratio of the monomer having an epoxy group in the total mass of the monomers constituting the acrylic polymer is It is preferable to limit it low. This tends to increase the adhesive strength between the protective film and the chip. The reason is presumed as follows. When the mass ratio of the monomer having an epoxy group is low in the total mass of monomers constituting the acrylic polymer, the compatibility between the epoxy resin and the acrylic polymer is lowered, and A phase separation structure having a main component is formed. As a result, the structure mainly composed of acrylic polymer plays a role in buffering distortion in the protective film, and local peeling of the adhesive interface due to deformation of the protective film even after the protective film has undergone a thermal history. It is thought that this is difficult to occur. As the blending amount of the monomer having an epoxy group in the total mass of the monomer constituting the acrylic polymer, the monomer constituting the acrylic polymer does not include the monomer having an epoxy group, or the acrylic polymer It is preferable that the mass ratio of the monomer having an epoxy group is more than 0% by mass and 10% by mass or less in the total mass of the monomers constituting the epoxy group. It is more preferable that the mass ratio of the monomer having an epoxy group exceeds 0% by mass and is 7% by mass or less in the total mass of the monomers constituting the acrylic polymer.
As a monomer which has an epoxy group, the norbornene monomer etc. which have an epoxy group other than the glycidyl (meth) acrylate etc. which were mentioned above, for example are mentioned.

  Furthermore, you may mix | blend thermoplastic resins other than an acrylic polymer as a binder polymer component (A). As a thermoplastic resin other than the acrylic polymer, those having a weight average molecular weight of 1,000 to 100,000 are preferable, and those of 3000 to 80,000 are more preferable. The glass transition temperature of the thermoplastic resin other than the acrylic polymer is preferably -30 to 120 ° C, more preferably -20 to 120 ° C. Examples of thermoplastic resins other than acrylic polymers include polyester resins; urethane resins; acrylic urethane resins; phenoxy resins; silicone resins; rubber-based polymers such as polybutene and polybutadiene; Thermoplastic resins other than these acrylic polymers can be used alone or in combination of two or more. When a thermoplastic resin other than these acrylic polymers is used, it may be used in combination with the acrylic polymer, or the acrylic polymer may not be blended. When an acrylic polymer and a thermoplastic resin other than the acrylic polymer are used in combination, the protective film forming layer may follow the transfer surface of the protective film forming layer, and an effect that generation of voids or the like can be suppressed may be obtained.

  An acrylic polymer or a phenoxy resin containing a monomer having an epoxy group as a monomer constituting the polymer is included in the concept of the epoxy resin described later in terms of words. In the present invention, such an acrylic polymer or a phenoxy resin is used. Is not contained in the epoxy resin, but is contained in the binder polymer component (A).

(B) Thermosetting component As the thermosetting component (B), a thermosetting resin and a thermosetting agent are used. As the thermosetting resin, for example, an epoxy resin is preferable.

  A conventionally well-known epoxy resin can be used as an epoxy resin. Specific examples of epoxy resins include 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, and bisphenols. Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as A-type epoxy resin, bisphenol F-type epoxy resin, and phenylene skeleton-type epoxy resin. These can be used individually by 1 type or in combination of 2 or more types.

  In the protective film forming layer, the thermosetting resin is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and particularly preferably 20 to 200 parts by weight with respect to 100 parts by weight of the binder polymer component (A). included. When the content of the thermosetting resin is less than 1 part by mass, sufficient adhesiveness may not be obtained. When the content exceeds 1000 parts by mass, the peeling force between the protective film forming layer and the support sheet increases, and the protective film is formed. Layer transfer failure may occur.

  The thermosetting agent functions as a curing agent for thermosetting resins, particularly epoxy resins. A preferable thermosetting agent for the thermosetting resin made of an epoxy resin includes a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.

Specific examples of thermosetting agents having phenolic hydroxyl groups (phenolic curing agents) include polyfunctional phenolic resins, biphenols, novolac phenolic resins, dicyclopentadiene phenolic resins, zylocic phenolic resins, and aralkylphenolic resins. Is mentioned.
A specific example of the thermosetting agent having an amino group (amine-based curing agent) is DICY (dicyandiamide).
These can be used individually by 1 type or in mixture of 2 or more types.

  It is preferable that content of a thermosetting agent is 0.1-500 mass parts with respect to 100 mass parts of thermosetting resins, and it is more preferable that it is 1-200 mass parts. If the content of the thermosetting agent is small, the adhesiveness may not be obtained due to insufficient curing, and if it is excessive, the moisture absorption rate of the protective film forming layer may increase and the reliability of the semiconductor device may be reduced.

(C) Inorganic filler By blending the inorganic filler (C) in the protective film forming layer, it is possible to adjust the thermal expansion coefficient in the cured protective film, and the heat of the protective film after curing with respect to the semiconductor chip. The reliability of the semiconductor device can be improved by optimizing the expansion coefficient. Moreover, it becomes possible to reduce the moisture absorption rate of the protective film after hardening. Furthermore, by applying laser marking to the protective film, the inorganic filler (C) is exposed in the portion scraped off by the laser light, and the reflected light diffuses to exhibit a color close to white. Thereby, when a protective film formation layer contains the coloring agent (G) mentioned later, there exists an effect that a contrast difference is obtained by a laser marking part and another part, and printing becomes clear.

  Preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like, beads formed by spheroidizing these, single crystal fibers, glass fibers, and the like. Among these, silica filler and alumina filler are preferable. The said inorganic filler (C) can be used individually or in mixture of 2 or more types. The range of the content of the inorganic filler (C) for obtaining the above-described effects more reliably is preferably 1 to 80 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer. Preferably it is 20-75 mass parts, Most preferably, it is 40-70 mass parts.

(D) Silane coupling agent having an alkoxy group and a reactive functional group other than an alkoxy group, having a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol / g. The protective film forming layer of the present invention includes an alkoxy group and an alkoxy group. Silane coupling agent (D) having a reactive functional group other than that and having a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol / g (hereinafter simply referred to as “silane coupling agent (D)”) Is included).
The reactive functional group other than the alkoxy group in the silane coupling agent (D) is preferably one that reacts with the functional group of the binder polymer component (A), the thermosetting component (B), or the like. Specific examples of reactive functional groups other than alkoxy groups include epoxy groups, amino groups, (meth) acryloyl groups, vinyl groups other than vinyl groups in (meth) acryloyl groups, and mercapto groups. Among these, an epoxy group is preferable. The alkoxy equivalent represents the absolute number of alkoxy groups contained per unit weight of the compound and is the same in the present invention.

  The silane coupling agent (D) which is a high molecular weight body is susceptible to hydrolysis reaction. Therefore, when the protective film forming layer is heated and cured, the silane coupling agent (D) efficiently and easily causes a chemical reaction with the surface of the adherend (semiconductor wafer, chip, etc.) and binds to the adherend surface. In addition, it is easy to have a dipolar interaction with the adherend surface. Therefore, even when the protective film forming layer is formed and used immediately without leaving a storage period, adhesion at the interface between the protective film forming layer and the adherend surface can be strengthened. As a result, even if the protective film forming layer is exposed to high temperature and high humidity, moisture can be prevented from entering the adhesive interface between the protective film forming layer and the adherend, and the adhesive state can be maintained even after thermal stimulation. The effect that can be performed (hereinafter, sometimes referred to as “adhesion state maintaining effect after heat and humidity”) is high.

  Specific examples of the silane coupling agent (D) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ- (methacrylopropyl). And a low molecular silane coupling agent having two or three alkoxy groups such as trimethoxysilane; and the like, which are products obtained by condensation of alkoxy groups by hydrolysis and dehydration condensation. In particular, among the above low molecular silane coupling agents, a low molecular silane coupling agent having two or three alkoxy groups and a low molecular silane coupling agent having four alkoxy groups are condensed by dehydration condensation. Preferably, the oligomer is a compound having a high reactivity of alkoxy groups and a sufficient number of organic functional groups. For example, 3- (2,3-epoxypropoxy) propylmethoxysiloxane and dimethoxysiloxane The oligomer which is a polymer is mentioned.

  In the protective film forming layer of the present invention, the content of the silane coupling agent (D) is usually 0.01 to 7.0 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer. Preferably it is 0.1-2.0 mass parts. In addition, the content of the silane coupling agent (D) is preferably 0.01 to 10 parts by mass, more preferably 0 with respect to 100 parts by mass (in terms of solid content) of the components (A) to (E). .1 to 4 parts by mass. By setting the content of the silane coupling agent (D) within the above range, the silane coupling agent (D) causes a chemical reaction with the adherend surface during the heat curing of the protective film forming layer, The coupling agent (D) can have a dipolar interaction with the adherend surface. As a result, the protective film forming layer can exhibit excellent adhesion to the adherend. When the content of the silane coupling agent (D) exceeds the above range, the surface tension of the protective film forming layer is increased, and when the protective film forming layer is formed into a sheet, it causes repelling and is difficult to manufacture. Sometimes. In addition, the protective film forming layer remains adhered to the back surface of the chip and cannot be peeled off from the support sheet, which may make processing difficult. That is, manufacturing and processing problems may occur.

  The protective film-forming layer of the present invention has a silane compound (D ′) having a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol / g and having no reactive functional group other than an alkoxy group. D ′) ”) may be included. Since the silane compound (D ′) does not have a reactive functional group, it does not react with the functional group of the binder polymer component (A), the thermosetting component (B), etc., but has an alkoxy group. It reacts with the alkoxy group, the surface of the adherend, and the surface of the inorganic filler (C) and participates in the curing of the protective film forming layer. Examples of the silane compound (D ′) include polymethoxysiloxane, polyethoxysiloxane, a copolymer of methoxysiloxane and dimethylsiloxane, and the like.

(E) Silane coupling agent having an alkoxy group and a reactive functional group other than an alkoxy group, a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less. The protective film forming layer of the present invention includes an alkoxy group and an alkoxy group. Silane coupling agent (E) having a reactive functional group other than a group, having a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less (hereinafter, simply referred to as “silane coupling agent (E)”) Is included).
As the reactive functional group other than the alkoxy group in the silane coupling agent (E), those reactive with the functional group of the binder polymer component (A), the thermosetting component (B) and the like are preferable. Specific examples of reactive functional groups other than alkoxy groups include epoxy groups, amino groups, (meth) acryloyl groups, vinyl groups other than vinyl groups in (meth) acryloyl groups, and mercapto groups. Among these, an epoxy group is preferable.

  Since the silane coupling agent (E) has a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less, the silane coupling agent (E) is less reactive than the silane coupling agent (D) and hardly undergoes a hydrolysis reaction. Therefore, the alkoxy group derived from the silane coupling agent (E) tends to remain in the protective film forming layer even after storage for a certain period. In addition, when a certain storage period is set after the formation of the protective film forming layer, some alkoxy groups derived from the silane coupling agent (E) are poorly reactive, but some undergo a condensation reaction between molecules, resulting in multimerization. To do. For this reason, the silane coupling agent (E) is easily bonded to the adherend surface, like the silane coupling agent (D), during the heat curing of the protective film forming layer after storage for a certain period of time. It becomes easier to have a dipolar interaction. Thereby, since the adhesion at the interface between the protective film forming layer and the adherend surface can be strengthened, the effect of maintaining the adhesive state after heat and humidity after storage for a certain period is high.

  Specific examples of the silane coupling agent (E) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacrylopropyl) trimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-6- (aminoethyl) -γ -Aminopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, vinyltriacetoxysilane and the like.

  In the protective film forming layer of the present invention, the content of the silane coupling agent (E) is usually 0.01 to 7.0 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer. Preferably it is 0.1-2.0 mass parts. Moreover, content of a silane coupling agent (E) becomes like this. Preferably it is 0.01-10 mass parts with respect to a total of 100 mass parts (solid content conversion) of component (A)-(E), More preferably, it is 0. .1 to 4 parts by mass. By setting the content of the silane coupling agent (E) in the above range, it is possible to express excellent adhesion to the adherend when the protective film forming layer is heated and cured after being stored at room temperature or higher for a certain period of time. it can. When the content of the silane coupling agent (E) exceeds the above range, the surface tension of the protective film forming layer is increased, and when the protective film forming layer is formed into a sheet shape, it causes repelling and is difficult to manufacture. Sometimes. In addition, the protective film forming layer remains adhered to the back surface of the chip and cannot be peeled off from the support sheet, which may make processing difficult. That is, manufacturing and processing problems may occur.

  The protective film-forming layer of the present invention has a silane compound (E ′) having a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less and having no reactive functional group other than an alkoxy group (hereinafter simply referred to as “silane compound”). (E ′) ”may be included.). Since the silane compound (E ′) does not have a reactive functional group, it does not react with the functional group of the binder polymer component (A), the thermosetting component (B), etc., but has an alkoxy group. It reacts with the alkoxy group, the surface of the adherend, and the surface of the inorganic filler (C) and participates in the curing of the protective film forming layer. As the silane compound (E ′), for example, phenyltriethoxysilane, decyltriethoxysilane, or the like can be used.

Effect obtained by the combined use of silane coupling agent (D) and silane coupling agent (E) The silane coupling agent (D) is used without a certain storage period immediately after the production of the protective film forming layer. In addition, while the effect of maintaining the adhesion state after heat and humidity is high, after the production of the protective film-forming layer, when a certain storage period is set, the alkoxy group of the silane coupling agent (D) is replaced with other alkoxy groups or inorganic fillers (C ) And disappear due to the reaction with the surface of the adherend, and it becomes difficult to have a dipolar interaction with the surface of the adherend. The adhesion at the interface cannot be strengthened, and the effect of maintaining the adhesion state after heat and humidity may be reduced.

  On the other hand, when the silane coupling agent (E) is used after a protective film forming layer is produced after a certain period of storage, the silane coupling agent (E) has a high effect of maintaining the adhesive state after heat and humidity, while the protective film forming layer is produced. When used immediately without a storage period, it is inherently inferior in reactivity and is not subject to hydrolysis reaction, so it is difficult to bind to the adherend surface, and it also has a dipolar interaction with the adherend surface. It is hard to have. As a result, the adhesion at the interface between the adhesive layer and the adherend surface cannot be strengthened, and the effect of maintaining the adhesive state after heat and humidity may be reduced.

  Since the protective film-forming layer of the present invention contains both the silane coupling agent (D) and the silane coupling agent (E), these compensate for each other's disadvantages of maintaining the adhesive state after heat and humidity before and after the storage period. In both the storage period and the storage period, a high effect of maintaining the adhesive state after hot moisture is obtained. As a result, the protective film forming layer of the present invention is excellent in storage stability.

  The ratio (d) / (e) between the content (d) of the silane coupling agent (D) and the content (e) of the silane coupling agent (E) is as follows. What is necessary is just the range of quantity, ie, 0.0014-700 normally, Preferably it is 0.05-20.

Other component protective film formation layers contain the said component (A)-(E) as an essential component, and may contain the following component other than the said component (D ') and (E').

(F) Other silane coupling agent In the present invention, in order to further improve the adhesion of the protective film forming layer to the adherend, other silanes besides the silane coupling agent (D) and the silane coupling agent (E) are used. A coupling agent (F) may be used.

  As the silane coupling agent (F), a compound having a group that reacts with a functional group of the binder polymer component (A), the thermosetting component (B), or the like is preferably used.

  Specifically, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxy Silane, imidazole silane, etc. are mentioned. These other silane compounds may be used alone or in combination of two or more.

(G) It is preferable that a coloring agent protective film formation layer contains a coloring agent (G). By blending a colorant into the protective film forming layer, when a semiconductor device is incorporated in equipment, infrared rays generated from surrounding devices can be shielded, and malfunction of the semiconductor device due to them can be prevented. Visibility of characters when a product number or the like is printed on a protective film obtained by curing the protective film forming layer is improved. That is, in a semiconductor device or semiconductor chip on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off by laser light and printed). By containing the colorant (G), a sufficient difference in contrast between the portion of the protective film scraped by the laser beam and the portion not removed is obtained, and the visibility is improved. As the colorant (G), organic or inorganic pigments and dyes are used.
As the dye, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used. The pigment is not particularly limited, and can be appropriately selected from known pigments.
Among these, black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties. Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor device.

  The blending amount of the colorant (G) is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 25 parts by weight, particularly preferably 100 parts by weight of the total solid content constituting the protective film forming layer. Is 1-15 parts by mass.

(H) Curing accelerator The curing accelerator (H) is used to adjust the curing rate of the protective film forming layer. The curing accelerator (H) is preferably used particularly when the epoxy resin and the thermosetting agent are used in combination in the thermosetting component (B).

  Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. These can be used individually by 1 type or in mixture of 2 or more types.

  The curing accelerator (H) is preferably contained in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermosetting component (B). By containing the curing accelerator (H) in an amount within the above range, the protective film-forming layer has excellent adhesive properties even when exposed to high temperatures and high humidity, and is exposed to severe reflow conditions. Even high reliability can be achieved. Further, if the content of the curing accelerator (H) is excessive, the curing accelerator having a high polarity moves to the adhesion interface side in the protective film forming layer under high temperature and high humidity, and segregates, so that the semiconductor device May reduce reliability.

(I) The energy ray polymerizable compound protective film forming layer may contain an energy ray polymerizable compound. The energy ray polymerizable compound (I) contains an energy ray polymerizable group and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams. Specific examples of the energy ray polymerizable compound (I) include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, and 1,4. Examples include acrylate compounds such as butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer. Such a compound has at least one polymerizable double bond in the molecule, and usually has a weight average molecular weight of about 100 to 30,000, preferably about 300 to 10,000. The amount of the energy beam polymerizable compound (I) is not particularly limited, but it is preferably used at a ratio of about 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer.

(J) When the photopolymerization initiator protective film-forming layer contains the energy beam polymerizable compound (I) described above, in use, the energy beam polymerizable compound is irradiated by irradiating energy rays such as ultraviolet rays. Harden. At this time, by including the photopolymerization initiator (J) in the composition, the polymerization curing time and the amount of light irradiation can be reduced.

  Specific examples of such a photopolymerization initiator (J) include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. 2,4-diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy- 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and β-alkyl Examples thereof include roll anthraquinone. A photoinitiator (J) can be used individually by 1 type or in combination of 2 or more types.

  It is preferable that 0.1-10 mass parts is contained with respect to 100 mass parts of energy-beam polymeric compounds (I), and, as for the mixture ratio of a photoinitiator (J), it is more preferable that 1-5 mass parts is contained. . If the amount is less than 0.1 parts by mass, satisfactory transferability may not be obtained due to insufficient photopolymerization. If the amount exceeds 10 parts by mass, a residue that does not contribute to photopolymerization is generated, and the curability of the protective film forming layer is increased. May be insufficient.

(K) In order to adjust the initial adhesive force and cohesive force of the crosslinker protective film forming layer, a crosslinker may be added. Examples of the crosslinking agent (K) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.

  Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds. And a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound with a polyol compound.

  Examples of organic polyvalent isocyanate compounds include 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 adduct tolylene diisocyanate and lysine Isocyanates.

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

  A crosslinking agent (K) is 0.01-20 mass parts normally with respect to 100 mass parts of binder polymer components (A), Preferably it is 0.1-10 mass parts, More preferably, it is a ratio of 0.5-5 mass parts. Used.

(L) In addition to the above, various additives may be blended in the general-purpose additive protective film forming layer as necessary. Examples of various additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, and the like.

The protective film forming layer comprising the above components is excellent in storage stability, and has adhesiveness (for example, pressure-sensitive adhesiveness and thermal adhesiveness) and heat curable properties. When the protective film-forming layer has pressure-sensitive adhesiveness, the uncured protective film-forming layer can be pressed and attached to the adherend. Moreover, when a protective film formation layer has heat adhesiveness, when pressing to a to-be-adhered body, a protective film formation layer can be heated and affixed. The thermal adhesiveness in the present invention means that there is no pressure-sensitive adhesiveness at room temperature, but it is softened by heat and can adhere to an adherend. Further, the protective film forming layer has a function of temporarily holding various adherends (semiconductor wafers, chips, etc.) in an uncured state. The protective film-forming layer of the present invention can provide a protective film with high impact resistance through heat curing, even after storage for a certain period of time, and in addition, balance between shear strength and peel strength. Excellent adhesiveness even under severe heat and humidity conditions.
The protective film forming layer may have a single layer structure, or may have a multilayer structure as long as one or more layers including the above components are arranged on the outermost layer in contact with the chip.

The protective film-forming layer of the present invention is obtained using a protective film-forming composition obtained by mixing each of the above components at an appropriate ratio. When mixing the above components, each component may be diluted with a solvent in advance, or a solvent may be added during mixing. Moreover, you may dilute with a solvent at the time of use of the composition for protective film formation.
Examples of such a solvent include ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, cyclohexane, toluene, heptane and the like.

  The thickness of the protective film forming layer is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and particularly preferably 7 to 200 μm.

  The maximum transmittance at a wavelength of 300 to 1200 nm, which is a scale showing the transmittance of visible light and / or infrared rays and ultraviolet rays in the protective film forming layer, is preferably 20% or less, more preferably 0 to 15%. More preferably, it is more than 0% and 10% or less, particularly preferably 0.001 to 8%. By setting the maximum transmittance of the protective film forming layer at a wavelength of 300 to 1200 nm within the above range, the transmittance in the visible light wavelength region and / or the infrared wavelength region is reduced, and the malfunction of the semiconductor device due to the infrared rays is prevented. In addition, the effect of improving the visibility of printing can be obtained. The maximum transmittance of the protective film forming layer at a wavelength of 300 to 1200 nm can be adjusted by the colorant (G). In addition, the maximum transmittance of the protective film forming layer is the total light transmission at 300 to 1200 nm of the cured protective film forming layer (thickness 25 μm) using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation). The transmittance was measured, and the highest transmittance (maximum transmittance) was obtained.

  As the protective film forming layer of the present invention, a semiconductor chip made of silicon, gallium arsenide, or the like can be used as an adherend. The protective film forming layer of the present invention can also be used as a protective film for a semiconductor assembly including a resin seal in which a semiconductor wafer or a semiconductor chip is embedded.

[Protective film forming sheet]
The protective film-forming sheet according to the present invention is formed by detachably forming the protective film-forming layer on a support sheet. The shape of the protective film-forming sheet according to the present invention may take any shape such as a tape shape or a label shape.
The method for producing the protective film-forming sheet is not particularly limited, and the protective film-forming composition obtained by mixing each of the above components in an appropriate solvent in an appropriate solvent is applied and dried on the supporting sheet, and then the supporting sheet is formed. A method for forming a protective film forming layer thereon, or a process for forming a protective film on a film different from the support sheet, and drying to form a protective film forming layer. This protective film forming layer There is a method of transferring the material onto a support sheet.

  As the support sheet, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A film such as a resin film is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient. Moreover, the film which colored these can also be used.

  The protective film-forming sheet of the present invention is affixed to various adherends, and in some cases, the adherend is subjected to required processing such as dicing on the protective film-forming sheet. Thereafter, the support film is peeled off while the protective film forming layer remains fixed to the adherend. That is, it is used in a process including a step of transferring the protective film forming layer from the support sheet to the adherend. For this reason, the surface tension of the surface in contact with the protective film forming layer of the support sheet is preferably 40 mN / m or less, more preferably 37 mN / m or less, and particularly preferably 35 mN / m or less. The lower limit is usually about 25 mN / m. Such a support sheet having a relatively low surface tension can be obtained by appropriately selecting the material, and can also be obtained by applying a release agent to the surface of the support sheet and performing a release treatment. .

  As the release agent used for the release treatment, alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like are used. In particular, alkyd, silicone, and fluorine release agents are heat resistant. This is preferable.

  In order to release the surface of a film or the like as a substrate of a support sheet using the above release agent, the release agent is used without any solvent, or diluted or emulsified with a solvent, and then a gravure coater, Mayer bar coater, air knife coater. The support sheet coated with a release agent may be applied at room temperature or under heating, or may be cured with an electron beam to form a release agent layer.

  Further, the surface tension of the support sheet may be adjusted by laminating films by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, or the like. That is, a film in which the surface tension of at least one surface is within a preferable range as the surface in contact with the protective film forming layer of the support sheet is changed so that the surface is in contact with the protective film forming layer. It is good also as a support sheet by manufacturing the laminated body laminated | stacked with this film.

  Moreover, you may use the adhesive sheet which formed the releasable adhesive layer on the said film as a support sheet. In this case, a protective film formation layer is laminated | stacked on the releasable adhesive layer provided in the support sheet. The re-peelable pressure-sensitive adhesive layer may be a weak-adhesive layer having an adhesive strength that can peel off the protective film-forming layer, or an energy-ray curable layer whose adhesive strength is reduced by energy beam irradiation. May be used. In addition, when an energy ray-curable removable pressure-sensitive adhesive layer is used, the region where the protective film forming layer is laminated is preliminarily irradiated with energy rays to reduce adhesiveness, while other regions are irradiated with energy rays. For example, for the purpose of bonding to a jig, the adhesive strength may be kept high. In order not to irradiate the energy beam only to other regions, for example, an energy beam shielding layer may be provided by printing or the like in a region corresponding to the other region of the support sheet, and the energy beam irradiation may be performed from the support sheet side. . The re-peelable pressure-sensitive adhesive layer is a variety of conventionally known pressure-sensitive adhesives (for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives, energy ray curable type) Adhesive, thermal expansion component-containing adhesive, etc.). When the protective film forming sheet has such a configuration, the protective film forming sheet functions as a dicing sheet for supporting the workpiece and the chip in the dicing process, as will be described later. Adhesiveness between the forming layers is maintained, and an effect of suppressing the chip with the protective film forming layer from being peeled off from the support sheet in the dicing step is obtained.

  The thickness of the support sheet is usually 10 to 500 μm, preferably 15 to 300 μm, and particularly preferably 20 to 250 μm. When providing a re-peeling adhesive layer, 3-50 micrometers in a support sheet is the thickness of a re-peeling adhesive layer.

  In addition, in order to protect the protective film forming layer before use of the protective film forming sheet, a light peelable release film may be laminated on the upper surface of the protective film forming layer separately from the support sheet. Good.

  In addition, an adhesive layer or an adhesive tape may be separately provided on the outer peripheral portion of the surface of the protective film forming layer (the surface in contact with the adherend) in order to fix other jigs such as a ring frame. .

  The protective film forming layer of such a protective film forming sheet can be used as a protective film of an adherend. The protective film forming layer is attached to the back surface of the semiconductor wafer for chip or the semiconductor chip of the face-down type, and has a function of protecting the semiconductor chip as an alternative to the sealing resin by being cured by an appropriate means. When pasted on a semiconductor wafer, the protective film has a function of reinforcing the wafer, so that damage to the wafer can be prevented. In addition, by using the protective film forming layer of the present invention, since the adhesiveness with the adherend is excellent even after a certain time has elapsed since the production of the protective film forming layer, the reliability of the semiconductor device is excellent.

[Method for Manufacturing Semiconductor Device]
Next, a method of using the protective film forming sheet according to the present invention will be described by taking as an example the case where the sheet is applied to the manufacture of a semiconductor device.

The method for manufacturing a semiconductor device according to the present invention preferably includes a step of attaching a protective film forming layer of the protective film forming sheet to a semiconductor wafer to obtain a semiconductor chip having the protective film. Specifically, a protective film forming layer of a protective film forming sheet is attached to the back surface of a semiconductor wafer having a circuit formed on the front surface, and then a semiconductor chip having a protective film on the back surface is obtained. The protective film is preferably a protective film for a semiconductor wafer or a semiconductor chip. In addition, the semiconductor device manufacturing method according to the present invention preferably further includes the following steps (1) to (3), and the steps (1) to (3) are performed in an arbitrary order.
Step (1): peeling off the protective film forming layer or protective film and the support sheet,
Step (2): The protective film forming layer is cured to obtain a protective film.
Step (3): dicing the semiconductor wafer and the protective film forming layer or the protective film.

  The semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Formation of a circuit on the wafer surface can be performed by various methods including conventionally used methods such as an etching method and a lift-off method. Next, the opposite surface (back surface) of the circuit surface of the semiconductor wafer is ground. The grinding method is not particularly limited, and grinding may be performed by a known means using a grinder or the like. At the time of back surface grinding, an adhesive sheet called a surface protection sheet is attached to the circuit surface in order to protect the circuit on the surface. In the back surface grinding, the circuit surface side (that is, the surface protection sheet side) of the wafer is fixed by a chuck table or the like, and the back surface side on which no circuit is formed is ground by a grinder. The thickness of the wafer after grinding is not particularly limited, but is usually about 50 to 500 μm.

  Thereafter, if necessary, the crushed layer generated during back grinding is removed. The crushed layer is removed by chemical etching, plasma etching, or the like.

  Subsequently, the protective film formation layer of the said protective film formation sheet is affixed on the back surface of a semiconductor wafer. Thereafter, steps (1) to (3) are performed in an arbitrary order. As an example, the case where it performs in order of process (1), (2), (3) is demonstrated.

  First, the protective film formation layer of the said protective film formation sheet is affixed on the back surface of the semiconductor wafer in which the circuit was formed on the surface. Next, the support sheet is peeled from the protective film forming layer to obtain a laminate of the semiconductor wafer and the protective film forming layer. Next, the protective film forming layer is thermally cured to form a protective film on the entire surface of the wafer. When the energy ray polymerizable compound (I) is blended in the protective film forming layer, the protective film forming layer can be cured by irradiation with energy rays. Or may be performed sequentially. Examples of the energy rays to be irradiated include ultraviolet rays (UV) and electron beams (EB), and preferably ultraviolet rays are used. As a result, a protective film made of a cured resin is formed on the back surface of the wafer, and the strength is improved as compared with the case of the wafer alone, so that damage during handling of the thinned wafer can be reduced. In addition, the thickness of the protective film is excellent compared to a coating method in which a coating solution for a resin film is directly applied to the back surface of a wafer or chip.

  Next, the laminated body of the semiconductor wafer and the protective film is diced for each circuit formed on the wafer surface. Dicing is performed so as to cut both the wafer and the protective film. The wafer is diced by a conventional method using a dicing sheet. As a result, a semiconductor chip having a protective film on the back surface is obtained.

  Thereafter, the diced chip is picked up by a general-purpose means such as a collet to obtain a semiconductor chip having a protective film on the back surface. According to the present invention as described above, a protective film having high thickness uniformity can be easily formed on the back surface of the chip, and cracks after the dicing process and packaging are less likely to occur.

  Finally, a semiconductor device can be manufactured by mounting a semiconductor chip on a predetermined base by a face-down method. Further, a semiconductor device can be manufactured by adhering a semiconductor chip having a protective film on the back surface to another member (on the chip mounting portion) such as a die pad portion or another semiconductor chip.

  When the protective film forming layer of the protective film forming sheet is attached to the back surface of the semiconductor wafer and then the step (3) is performed before the step (1), the protective film forming sheet serves as a dicing sheet. be able to. That is, it can be used as a sheet for supporting the workpiece and the chip during the dicing process. In this case, the work piece is attached to the inner peripheral portion of the protective film forming sheet via the protective film forming layer, and the outer peripheral portion of the protective film forming sheet is joined to another jig such as a ring frame. The protective film forming sheet affixed to the workpiece is fixed to the apparatus, and dicing is performed.

  The protective film-forming layer and protective film-forming sheet of the present invention can be used for protecting semiconductor compounds, glass, ceramics, metals and the like in addition to the above-described methods of use.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, about the sheet | seat for protective film formation obtained in the Example or the comparative example, the sheet | seat for protective film formation which performed the acceleration | stimulation process (40 degreeC, 7 day standing), 23 degreeC, without performing an acceleration | stimulation process Each of the following evaluations was performed using a protective film-forming sheet stored for 7 days in a 50% humidity environment. Moreover, the semiconductor chip with a protective film used for each evaluation was manufactured as follows.

Production of semiconductor chip with protective film # 2000 Polished silicon wafer (200 mm diameter, 350 μm thick) on the polished surface of the release film was removed from the protective film forming sheet of Example or Comparative Example by tape mounter (Adwill RAD, manufactured by Lintec) -3600 F / 12) was applied while heating to 70 ° C., and then the support sheet was peeled off. Thereafter, the protective film forming layer was cured by heating at 130 ° C. for 2 hours to obtain a laminate of the silicon wafer and the protective film.

  The protective film side of the laminate obtained above is affixed to a dicing tape (Adwill D-686H, manufactured by Lintec), and is evaluated by dicing to a size of 3 mm × 3 mm using a dicing device (DFD651, manufactured by Disco). A semiconductor chip with a protective film was obtained.

<Measurement of shear strength>
The measurement stage of the bond tester (bond tester Series 4000 manufactured by Dage) was set to 25 ° C., and the chip side of the semiconductor chip with protective film was placed on the measurement stage. At a position 10 μm higher than the interface between the protective film and the semiconductor chip (adhesion interface), the protective film is stressed by applying stress to the side of the protective film in a horizontal direction (shear direction) with respect to the interface at a speed of 200 μm / second. The force (shear strength) (N) when the protective film of the semiconductor chip with film was broken was measured. At this time, when the measurement jig of the bond tester was in contact with the semiconductor chip due to an error of the measuring apparatus (bond tester), the measurement was performed again using another semiconductor chip with a protective film.
Ten measurement values were obtained, and the average value was taken as the shear strength (N).

<Reliability evaluation>
The obtained semiconductor chip with a protective film was allowed to stand for 168 hours under conditions of 85 ° C. and 85% relative humidity to absorb moisture, and then IR reflow (reflow oven: manufactured by Sagami Riko Co., Ltd.) with a maximum temperature of 260 ° C. and a heating time of 1 minute. WL-15-20DNX type) was performed three times. Further, this protective semiconductor-coated semiconductor chip was placed in a thermal shock apparatus (TSE-11A manufactured by ESPEC), held at −40 ° C. for 10 minutes, and then held at 125 ° C. for 10 minutes for 1000 cycles.

After that, for the semiconductor chip with a protective film taken out from the thermal shock apparatus, peeling at the junction between the semiconductor chip and the protective film by scanning ultrasonic flaw detector (Hy-Focus manufactured by Hitachi Construction Machinery Finetech) and cross-sectional observation The case where a crack in the protective film was observed was judged as “bad”.
The above evaluation was performed on 25 semiconductor chips with a protective film, and the number of defects (number of defects) in which peeling of the joints or cracks in the protective film occurred was counted.

[Composition for forming protective film]
Each component which comprises the composition for protective film formation is shown below.
(A) Binder polymer component:
(A1) Acrylic polymer obtained by copolymerizing 55 parts by mass of butyl acrylate, 10 parts by mass of methyl methacrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 900,000, (Glass transition temperature: -28 ° C)
(A2) Acrylic polymer obtained by copolymerizing 85 parts by mass of methyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 400,000, glass transition temperature: 6 ° C.)
(B) Thermosetting component:
(B1) Bisphenol A type epoxy resin (epoxy equivalent 180-200 g / eq)
(B2) Dicyclopentadiene type epoxy resin (Dainippon Ink Chemical Co., Ltd. Epiklon HP-7200HH)
(B3) Dicyandiamide (Adekaha Donor 3636AS manufactured by Asahi Denka)
(C) Inorganic filler: Silica filler (fused quartz filler (average particle size 3 μm))
(D) Silane coupling agent having an alkoxy group and a reactive functional group other than an alkoxy group, a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol:
(D1) Copolymer of 3- (2,3-epoxypropoxy) propylmethoxysiloxane and dimethoxysiloxane (methoxy equivalent 13.7 to 13.8 mmol / g, molecular weight 2000 to 3000) (MKC silicate manufactured by Mitsubishi Chemical Corporation) MSEP2 (mixture with D ′, D1: D ′ (mass ratio) = 82: 18))
(D2) Oligomer type silane coupling agent (X-41-1056 methoxy equivalent 17.1 mmol / g, molecular weight 500-1500, manufactured by Shin-Etsu Chemical Co., Ltd.)
(D ′) Silane compound having a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol / g and having no reactive functional group other than an alkoxy group: polymethoxysiloxane (methoxy equivalent 20.8 mmol / g, molecular weight 600) (Mitsubishi Chemical) MKC silicate MSEP2 (mixture with D1, D1: D ′ (mass ratio) = 82: 18))
(E) Silane coupling agent having an alkoxy group and a reactive functional group other than an alkoxy group, a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less:
(E1) γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403 methoxy equivalent 12.7 mmol / g, molecular weight 236.3)
(E2) γ-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBE-403 methoxy equivalent 8.1 mmol / g, molecular weight 278.4)
(E3) γ-glycidoxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. KBE-402 methoxy equivalent 10.8 mmol / g, molecular weight 248.4)
(G) Colorant: Black pigment (carbon black, manufactured by Mitsubishi Chemical Corporation # MA650, average particle size 28 nm)
(H) Curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ manufactured by Shikoku Chemicals Co., Ltd.)

(Examples and Comparative Examples)
The above components were blended in the blending amounts shown in Table 1 to obtain a protective film forming composition. The compounding quantity of each component in Table 1 shows the mass part of solid content conversion, and solid content means all components other than a solvent in this invention. In Example 1 and Comparative Example 1, components D1 and D ′ were added to the protective film-forming composition by adding these mixtures, MKC silicate MSEP2 manufactured by Mitsubishi Chemical Corporation. A protective film-forming composition having the composition shown in Table 1 was diluted with methyl ethyl ketone so that the solid content was 50% by weight, and a release-treated polyethylene terephthalate film (SP manufactured by Lintec Corporation) was used as a support sheet. The coating film was dried and dried (drying condition: 100 ° C. in an oven for 3 minutes) to obtain a protective film-forming layer formed on the support sheet. Then, the protective film formation layer and the polyethylene terephthalate film (SP-PET381031 by Lintec Co., Ltd.) by which the peeling process was carried out as a peeling film were bonded together, and the protective film formation sheet | seat with which the peeling film was bonded together was obtained. Each evaluation result is shown in Table 2.

From Table 2, in the examples, high shear strength is maintained even after the acceleration treatment is performed, and the reliability of the semiconductor chip is excellent even when exposed to severe reflow conditions. That is, it shows that the protection performance of the semiconductor chip is excellent. Therefore, according to the semiconductor chip with a protective film manufactured using the protective film forming layer of the present invention, a semiconductor device with excellent reliability can be obtained.
On the other hand, in the comparative examples, the protective film forming layers (Comparative Examples 2 to 5) that do not contain the silane coupling agent (D) are inferior in shear strength and reliability evaluation before and after the acceleration treatment as compared with the examples. It is inferior to each evaluation before performing an acceleration process. That is, the protective film forming layers of Comparative Examples 2 to 5 cannot obtain excellent chip protection performance when used immediately after production.
Moreover, the protective film formation layer (comparative example 1) which does not contain a silane coupling agent (E) is inferior in the shear strength after performing an acceleration | stimulation process compared with an Example, and reliability evaluation is also falling. . That is, the protective film forming layer of Comparative Example 1 cannot obtain excellent chip protection performance when used after storage for a certain period of time from its manufacture.

Claims (8)

  A silane having a binder polymer component (A), a thermosetting component (B), an inorganic filler (C), an alkoxy group and a reactive functional group other than an alkoxy group, a molecular weight of 300 or more and an alkoxy equivalent of greater than 13 mmol / g Protective film forming layer containing coupling agent (D) and silane coupling agent (E) having an alkoxy group and a reactive functional group other than alkoxy group, having a molecular weight of 300 or less and an alkoxy equivalent of 13 mmol / g or less .   The protective film forming layer according to claim 1, wherein the reactive functional group other than the alkoxy group in one or both of the silane coupling agent (D) and the silane coupling agent (E) is an epoxy group.   The binder polymer component (A) is an acrylic polymer, and the monomer constituting the acrylic polymer does not include a monomer having an epoxy group, or has an epoxy group in the total mass of the monomer constituting the acrylic polymer. The protective film forming layer according to claim 1 or 2, wherein the mass ratio of the monomer exceeds 0 mass% and is 10 mass% or less, and the thermosetting component (B) contains an epoxy resin.   Furthermore, the protective film formation layer in any one of Claims 1-3 containing a coloring agent (G).   The protective film forming layer according to any one of claims 1 to 4, wherein the content of the inorganic filler (C) is 1 to 80 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer.   The protective film formation sheet formed by forming the protective film formation layer in any one of Claims 1-5 on a support sheet.   A method for manufacturing a semiconductor device, comprising a step of attaching a protective film forming layer of the protective film forming sheet according to claim 6 to a semiconductor wafer to obtain a semiconductor chip having the protective film. A method of manufacturing a semiconductor device, further comprising the following steps (1) to (3), wherein the steps (1) to (3) are performed in an arbitrary order;
Step (1): peeling off the protective film forming layer or protective film according to any one of claims 1 to 5 and the support sheet,
Step (2): The protective film forming layer according to any one of claims 1 to 5 is cured to obtain a protective film.
Step (3): dicing the semiconductor wafer and the protective film forming layer or the protective film according to any one of claims 1 to 5.