KR102108776B1 - Protective-membrane-forming film - Google Patents

Abstract

The film for forming a protective film according to the present invention is a film for forming a protective film for forming a protective film for protecting a semiconductor chip, wherein the film for forming a protective film includes (A) an acrylic polymer, (B) an epoxy curable component, and (C) a filler. And (D1) a silane coupling agent, and (A) the monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer, or contains an epoxy group-containing monomer in a proportion of 8% by mass or less of the total monomers, ( A) The glass transition temperature of the acrylic polymer is -3 ° C or higher, and the molecular weight of the (D1) silane coupling agent is 300 or higher.

Description

Protective film forming film {PROTECTIVE-MEMBRANE-FORMING FILM}

The present invention relates to, for example, a film for forming a protective film used to protect the back surface of a semiconductor chip.

Conventionally, semiconductor devices using a mounting method called a face-down method have been manufactured. In the face-down method, the semiconductor chip is protected by a protective film because the surface of the chip on which an electrode such as a bump is formed is bonded to a substrate or the like and the back surface of the chip is exposed. In addition, marks, characters, and the like are printed on the protective film by laser printing or the like on the back surface of the semiconductor chip (hereinafter referred to as a "chip with a protective film") protected by the protective film.

Although the protective film was formed by, for example, resin coating or the like, recently, for example, as disclosed in Patent Document 1, in order to secure uniformity of the film thickness, the sheet for forming a protective film is continuously put into practical use. Is becoming. The sheet for forming a protective film is formed by forming a film for forming a protective film containing a thermosetting component containing an epoxy resin or the like and a binder polymer component containing an acrylic polymer or the like on the support sheet.

On the other hand, it is known variously as an adhesive film used for a semiconductor, for example, Patent Document 2, an adhesive film used for a semiconductor package, etc., separated from each other in the B-stage state, the resin A having an elastic modulus of 3500 to 10000 GPa, and an elastic modulus of 1 It is disclosed that a mixture of resin B to 3000 MPa is an essential component. In the adhesive film of Patent Document 2, for example, an epoxy resin is used as the resin A, and an acrylic rubber that is a copolymer of a methacrylic acid ester and acrylonitrile is used as the resin B.

Japanese Patent Publication No. 2002-280329 Japanese Patent Publication No. 2001-220556

When the protective film of the semiconductor chip is formed from the sheet for forming a protective film disclosed in Patent Literature 1, the chip provided with the protective film may be lifted or peeled off at the junction between the chip and the protective film or cracks in the protective film due to long-term use. Problems such as occurrence are likely to occur, and reliability may be poor. In addition, if a composition in which two kinds of components as disclosed in Patent Document 2 are phase-separated is converted to a sheet for forming a protective film, reliability may be improved, but sufficient reliability may not be obtained.

The present invention has been made in view of the above problems, and an object thereof is to obtain a chip having a protective film with sufficiently improved reliability.

The inventors of the present invention have repeatedly studied in order to solve the above problems. As a result, the silane coupling agent having an acrylic copolymer as a predetermined blend, a glass transition temperature of the acrylic polymer in a predetermined range, and a molecular weight of a predetermined value or more By using, it was found that the reliability of the film for forming a protective film was improved, and the following invention was completed.

That is, the present invention provides the following (1) to (7).

(1) a film for forming a protective film for forming a protective film for protecting a semiconductor chip,

The film for forming a protective film contains (A) an acrylic polymer, (B) an epoxy curable component, (C) a filler, and (D1) a silane coupling agent,

(A) The monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer or contains an epoxy group-containing monomer in a proportion of 8% by mass or less of the total monomers, and (A) the glass transition temperature of the acrylic polymer is -3. ℃ or higher,

(D1) A film for forming a protective film having a molecular weight of 300 or more of a silane coupling agent.

(2) The film for forming a protective film according to the above (1), wherein the monomer constituting the acrylic polymer (A) includes an alkyl (meth) acrylate.

(3) The film for forming a protective film according to (2) above, wherein the monomer constituting the acrylic polymer (A) contains a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group at a ratio of 12% by mass or less of the total monomers.

(4) The film for forming a protective film according to the above (3), wherein the alkyl group having 4 or more carbon (meth) acrylate alkyl ester is (meth) acrylate butyl.

(5) The film for forming a protective film according to any one of (1) to (4) above, which further contains a colorant (E).

(6) The film for forming a protective film according to any one of (1) to (5), wherein the (D1) silane coupling agent is a compound having an alkoxy equivalent weight greater than 13 mmol / g.

(7) A chip having a protective film, comprising a semiconductor chip and a protective film formed on the semiconductor chip,

While the protective film is formed by curing the film for forming a protective film, the film for forming a protective film contains (A) an acrylic polymer, (B) an epoxy-based curable component, (C) a filler, and (D1) a silane coupling agent,

(A) The monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer, or contains an epoxy group-containing monomer in a proportion of 8% by mass or less of the total monomers, and the glass transition temperature of the acrylic polymer (A) is -3. ℃ or higher,

(D1) A film for forming a protective film having a molecular weight of 300 or more of a silane coupling agent.

By using the film for forming a protective film of the present invention, it is possible to obtain a chip with a protective film having excellent reliability.

Hereinafter, the present invention will be specifically described using the embodiments.

In addition, in this specification, "(meth) acrylic" is used as a term showing both "acrylic" and "methacryl," and the same applies to other similar terms.

[Film for forming protective film]

The film for forming a protective film according to the present invention is a film for forming a protective film for protecting a semiconductor chip, and comprises at least (A) an acrylic polymer, (B) an epoxy curable component, (C) a filler, and (D1) a silane coupling agent. It contains.

<(A) Acrylic polymer>

(A) The acrylic polymer is a component that provides flexibility and film-forming properties to the protective film and the film for forming a protective film, and the monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer or the total monomer constituting the acrylic polymer. It contains an epoxy group-containing monomer in a proportion of 8% by mass or less.

When the monomer constituting the acrylic polymer contains an epoxy group-containing monomer, the monomer constituting (A) the acrylic polymer contains one or more epoxy groups specifically selected from epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers. Monomers, and various (meth) acrylic acid esters having no epoxy groups and / or non-acrylic epoxy group-free monomers. In this case, when the epoxy group-containing monomer contains only a non-acrylic epoxy group-containing monomer, the monomer constituting the acrylic polymer contains various (meth) acrylic acid esters having no epoxy group.

When the proportion of the epoxy group-containing monomer is more than 8% by mass, the compatibility of the cured product of the component (A) and the component (B) is improved, and the phase-separated structure described later becomes difficult to form, and the reliability of the chip with the protective film is lowered. do. From this viewpoint, the content of the epoxy group-containing monomer is preferably 6% by mass or less of the total monomers of the acrylic copolymer (A).

Examples of the epoxy group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3 Examples of the non-acrylic epoxy group-containing monomers such as epoxycyclo-2-hydroxypropyl (meth) acrylate include glycidyl crotonate, allyl glycidyl ether, and the like. As the epoxy group-containing monomer, an epoxy group-containing (meth) acrylic acid ester is preferable.

In addition, the monomer constituting the acrylic polymer (A) contains an epoxy group-containing monomer, so that it is easy to suppress a decrease in the gross value of the protective film that is caused due to the progress of phase separation, thereby improving the identification of the printing part by laser printing. It is easy to do. Therefore, in applications where good factor identification is required, it is better to contain an epoxy group-containing monomer.

When the epoxy group-containing monomer is contained, the content of the epoxy group-containing monomer is usually 0.1% by mass or more, and preferably 1% by mass or more, and 3% by mass or more of the total monomers, from the viewpoint of satisfactory factor discrimination. It is more preferable.

When the monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer, the monomer constituting (A) the acrylic polymer is specifically, various epoxy groups such as hydroxyl group-containing (meth) acrylic acid ester and (meth) acrylic acid alkyl ester. And various non-acrylic epoxy group-containing monomers such as styrene, ethylene, vinyl ether, and vinyl acetate, which are used together if necessary.

Moreover, it is preferable to include (meth) acrylic-acid alkylester as a monomer which comprises (A) acrylic polymer. This makes it easy to adjust the glass transition temperature of the acrylic polymer (A) by increasing or decreasing the number of carbon atoms of the (meth) acrylic acid alkyl ester, or by combining (meth) acrylic acid alkyl esters of different carbon numbers. It is preferable that (meth) acrylic-acid alkylester is 50 mass% or more of all the monomers which comprise (A) acrylic polymer, and it is more preferable that it is 70 mass% or more. Moreover, it is preferable that (meth) acrylic-acid alkylester is 92 mass% or less of the whole monomer which comprises (A) acrylic polymer.

As the (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) The alkyl group having 1 to 18 carbon atoms, such as isooctyl acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc. And (meth) acrylic acid alkyl esters.

In addition, the monomers constituting the acrylic polymer (A) are (meth) acrylic acid alkyl esters having 4 or more carbon atoms in the alkyl group among the (meth) acrylic acid alkyl esters, and (A) 12% by mass of the total monomers constituting the acrylic polymer. It is better to contain it in the following amounts. Thereby, it becomes easy to make a gross value favorable, making glass transition temperature more than -3 degreeC. In order to improve the gross value while maintaining reliability, the content of the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably 1 to 12% by mass, more preferably 5 to 12% by mass. As the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group, butyl (meth) acrylate is preferable.

Moreover, it is preferable that the monomer which comprises (A) acrylic polymer contains (meth) acrylic-acid alkylester whose alkyl group has 3 or less carbon atoms in the said (meth) acrylic-acid alkylester. By containing the (meth) acrylic acid alkyl ester having 3 or less carbon atoms in the alkyl group, it is easy to make the glass transition temperature of the acrylic polymer (A) to -3 ° C or higher, as described later, while improving thermal stability and the like. From this point of view, the (meth) acrylic acid alkyl ester having 3 or less carbon atoms in the alkyl group is preferably 50% by mass or more, and more preferably 60% by mass or more, of all monomers constituting the acrylic polymer (A). Moreover, it is preferable that (meth) acrylic-acid alkylester whose alkyl group has 3 or less carbon atoms is (A) 90 mass% or less of all the monomers which comprise an acrylic polymer. In addition, as the (meth) acrylic acid alkyl ester having 3 or less carbon atoms in the alkyl group, methyl (meth) acrylate or ethyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.

Further, the monomer constituting the acrylic polymer (A) may contain a hydroxyl group-containing (meth) acrylic acid ester. When a hydroxyl group is introduced into the acrylic copolymer by a hydroxyl group-containing (meth) acrylic acid ester, control of adhesion to a semiconductor chip and adhesion properties becomes easy. Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

The hydroxyl group-containing (meth) acrylic acid ester is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass, of all monomers constituting the acrylic polymer (A). Do.

Further, the monomer constituting the acrylic polymer (A) may contain non-acrylic epoxy group-free monomers such as styrene, ethylene, vinyl ether, and vinyl acetate as described above.

(A) The weight average molecular weight (Mw) of the acrylic polymer is preferably 10,000 or more in order to provide flexibility and film forming properties to the film for forming a protective film. In addition, the weight average molecular weight is more preferably 15,000 to 1,000,000, and more preferably 20,000 to 500,000. The weight average molecular weight (Mw) can be measured according to the method of Examples described later.

In the present invention, the acrylic polymer (A) has a glass transition temperature of -3 ° C or higher. When the glass transition temperature is less than -3 ° C, the mobility of the acrylic polymer (A) is not sufficiently suppressed, and the protective film tends to deform due to thermal history, and the reliability of the chip with the protective film cannot be sufficiently improved. In the present invention, the glass transition temperature of the acrylic polymer (A) is a theoretical value obtained from the equation of Fox.

Moreover, it is preferable that the glass transition temperature of (A) acrylic polymer is 6 degrees C or less. When the glass transition temperature is 6 ° C or less, the gross value to be described later can be improved, and the recognition of the printing section can be improved. Although this reason is not necessarily obvious, it is estimated that it is because the surface shape of the protective film after hardening is smoothed because the acrylic polymer (A) has moderate mobility.

The film for forming a protective film does not contain any component derived from an epoxy group-containing monomer, and its content is suppressed to a small amount, whereby the phase (A) with a large amount of components in the protective film and the cured product of the component (B) described later are many. The phases are easily phase-separated, and the reliability of the chip with the protective film is improved. This is presumed to be because even when the temperature changes after chip mounting, the stress caused by the temperature change is relieved by many phases with a flexible (A), so that the peeling of the protective film due to the stress is less likely to occur. In addition, in the phase separation in the protective film-forming film (that is, the protective film) after thermal curing, it is preferable that the phase with many (A) forms a continuous phase. Thereby, the effect of improving the reliability mentioned above can be further improved.

The phase having many (A) and many phases of the cured product of (B) can be determined by observing which substance is the main component of the phase from a measurement chart of which phase, for example, by Raman scattering spectroscopy. In addition, when the size of the phase-separated structure is less than or equal to the resolution of Raman spectroscopy, the hardness of the tapping mode measurement of the SPM (scanning probe microscope) is used as an index. It can be estimated that this (A) component is a large phase. Therefore, in the present invention, it is possible to confirm whether or not a phase separation structure is formed by performing Raman scattering spectroscopy or SPM observation on the protective film obtained by curing the protective film forming film.

The acrylic polymer (A) is a proportion of the total mass (in terms of solid content) of the film for forming a protective film, and is usually 10 to 80 mass%, preferably 15 to 50 mass%.

<(B) Epoxy-based curable component>

(B) The epoxy-based curable component is a component for forming a hard protective film on a semiconductor chip by curing, and usually contains an epoxy-based compound and a thermosetting agent.

In the film for forming a protective film, the epoxy curable component (B) is preferably 250 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass with respect to 100 parts by mass of the acrylic polymer (A). Less than wealth. Moreover, (B) epoxy-type curable component is (A) It is 20 mass parts or more with respect to 100 mass parts of acrylic polymers, More preferably, it is 40 mass parts or more, More preferably, it is 60 mass parts or more.

(B) By setting the content of the epoxy-based curable component in the above range, sufficient adhesiveness to an adherend such as a semiconductor chip is obtained, and the peeling force with the supporting sheet described later becomes appropriate, and the supporting sheet is used for forming a protective film. A peeling defect or the like when peeling from the film can also be prevented. In addition, as described above, by limiting the compounding amount of the component (B) to a range equal to or less than a predetermined upper limit, the phase with many components (A) tends to become a continuous phase, and the reliability of the semiconductor chip can be enhanced, and the gross value is also increased. It becomes easy to improve.

In addition, (B) The epoxy-based curable component is a proportion of the total mass (in terms of solid content) of the film for forming a protective film, and is usually about 5 to 60% by mass, preferably about 10 to 40% by mass.

As an epoxy compound, a conventionally well-known epoxy compound can be used. Specifically, a biphenyl compound, bisphenol A diglycidyl ether or a hydrogenated product thereof, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type Epoxy resins, phenylene skeleton-type epoxy resins, and the like, and epoxy compounds having two or more functionalities in the molecule. These can be used alone or in combination of two or more.

The thermosetting agent functions as a curing agent for the epoxy compound. As a preferable thermosetting agent, the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned. Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups and acid anhydrides. Among these, phenolic hydroxyl group, amino group, acid anhydride, etc. are mentioned preferably, and phenolic hydroxyl group and amino group are more preferable.

Specific examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, xylotype-type phenolic resins, and aralkylphenolic resins. Dicyandiamide is mentioned as a specific example of the amine-type hardener which has an amino group. These can be used individually by 1 type or in mixture of 2 or more types.

Moreover, it is preferable that content of a thermosetting agent is 0.1-100 mass parts with respect to 100 mass parts of epoxy compounds, It is more preferable that it is 0.5-50 mass parts, It is still more preferable that it is 1-20 mass parts. By making the content of the thermosetting agent more than the above lower limit, the component (B) is cured, and the adhesion with the adherend becomes easy to be obtained. Moreover, by setting it below the said upper limit, the moisture absorption rate of the film for protective film formation is suppressed, and it becomes easy to make the reliability of a semiconductor device favorable.

<(C) Filler>

(C) The filler is a component that imparts moisture resistance, dimensional stability, and the like to the protective film, and examples thereof include inorganic fillers. In addition, in the case of performing laser marking on the protective film (a method of printing the surface of the protective film by cutting off the laser light), the part (factor part) cut out by the laser light, (C) the filler is exposed to diffuse the reflected light Therefore, the contrast with the non-factor part is improved, and recognition becomes possible.

Preferable inorganic fillers include powders such as silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, and boron nitride, beads spheroidizing them, single crystal fibers, and glass fibers. Of these, silica fillers and alumina fillers are particularly preferred. In addition, the said inorganic filler can be used individually or in mixture of 2 or more types.

The average particle diameter of the filler is not particularly limited, but is preferably 0.1 to 20 μm. When it is 0.1 micrometer or more, when the composition for forming a protective film is applied and dried on a support sheet to obtain a film for forming a protective film, the composition for forming a protective film tends to be a property suitable for application. Moreover, if it is 20 micrometers or less, a gross value will become easy to improve more.

Moreover, from these viewpoints, the average particle diameter of the filler is more preferably 0.2 to 10 μm, and even more preferably 0.3 to 6 μm.

In addition, the average particle diameter was measured by the particle size distribution system using the dynamic light scattering method. Examples of the particle size distribution system include Nanotrac 150 manufactured by Nikkiso Co., Ltd., and the like.

The content of the filler (C) in the film for forming a protective film is a proportion of the total mass (in terms of solid content) of the film for forming a protective film, preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass % Is more preferable. The content of the filler (C) is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 63% by mass or less, based on the total mass of the film for forming a protective film. (C) By making content of a filler into these ranges, it becomes easy to exhibit the effect of the said filler. In addition, by setting the content of the filler (C) to 50% by mass or more, the contrast between the laser-marked printing portion and the non-printing portion is improved, and the recognition performance of the printing is improved. Moreover, it becomes easy to improve a gross value by setting it below the said upper limit.

<(D1) Silane coupling agent>

(D1) The silane coupling agent is a so-called oligomeric type silane coupling agent, has a molecular weight of 300 or more, and has a reactive functional group capable of bonding to the surface of an inorganic material and a reactive functional group capable of bonding with an organic compound.

The oligomeric type (D1) silane coupling agent is susceptible to a hydrolysis reaction, and is also easy to bond a polymer component forming a protective film with a physically-deposited adherend surface. Therefore, the (D1) silane coupling agent easily causes a chemical reaction with the surface of the adherend (semiconductor wafer or chip) upon heating and curing of the film for forming a protective film, and also has a dipole interaction with the surface of the adherend. It is easy to bond to the surface of the adherend. Therefore, the adhesion between the protective film and the semiconductor chip can be improved, thereby improving the reliability of the chip with the protective film. Among these oligomeric type silane coupling agents, it is an organopolysiloxane having a siloxane backbone, and having an alkoxy group directly bonded to a silicon atom as a reactive functional group capable of bonding to the surface of an inorganic material, the adhesion between the protective film and the semiconductor chip The tendency to improve is strong and is preferred.

(D1) It is preferable that a silane coupling agent has an alkoxy group as a reactive functional group capable of bonding to the surface of an inorganic material, and that the alkoxy equivalent is larger than 13 mmol / g. The alkoxy equivalent is more preferably 15 mmol / g or more. In the present invention, by increasing the alkoxy equivalent, the adhesion of the adherend is improved, and the reliability of the semiconductor chip is easily enhanced. Further, the alkoxy equivalent is not particularly limited, but in terms of its structure, it is preferably 22 mmol / g or less, and more preferably 20 mmol / g or less. In addition, the alkoxy equivalent represents the absolute number of alkoxy groups contained per unit mass of the compound.

Moreover, it is preferable that an alkoxy group has a C1-C6 aliphatic hydrocarbon group, Specifically, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned, and a methoxy group and an ethoxy group are more preferable.

(D1) The molecular weight of the silane coupling agent is preferably 400 or more, and more preferably 500 or more. Moreover, the molecular weight of the (D1) silane coupling agent is preferably 5000 or less, and more preferably 2000 or less.

(D1) As a reactive functional group capable of bonding with an organic compound having a silane coupling agent, it is preferable to react with a functional group possessed by (A) an acrylic copolymer or (B) an epoxy-based curable component, and a glycidoxy group and a glycidoxy group. And epoxy groups other than the period, amino groups, (meth) acryloxy groups, and vinyl groups other than (meth) acryloxy groups, mercapto groups, and the like. Among these, a glycidoxy group and an epoxy group are preferable.

These reactive functional groups may be directly bonded to the silicon atom, but may also be bonded to the silicon atom via a hydrocarbon group or the like, for example, as a glycidoxy C1 to C4 alkyl group such as γ-glycidoxypropyl group, to the silicon atom. It can also be combined directly.

Further, the (D1) silane coupling agent may have an alkyl group having 1 to 4 carbon atoms such as a methyl group directly bonded to a silicon atom, or an aryl group such as a phenyl group.

(D1) As a silane coupling agent, specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- (methacrylo Propyl) a low molecular silane compound having two or three alkoxy groups such as trimethoxysilane and at least one reactive functional group; Low molecular silane compounds having two or three alkoxy groups and no reactive functional groups; Low molecular weight silane compounds having four alkoxy groups such as tetramethoxysilane and tetraethoxysilane; The oligomer type thing which is the product condensed by hydrolysis and dehydration condensation of an alkoxy group is mentioned.

In the film for forming a protective film, the content of the (D1) silane coupling agent is a proportion of the total mass (in terms of solid content) of the film for forming a protective film, preferably 0.01 to 7.0 mass%, more preferably 0.1 to 2.0 mass %to be.

By setting the content to the lower limit or higher, the (D1) silane coupling agent sufficiently bonds to the surface of the adherend during heat curing of the film for forming a protective film, and as a result, high adhesiveness can be exhibited. When the content is equal to or less than the above upper limit, the surface tension of the film for forming a protective film can be prevented from rising, and when the film is formed, cratering or the like can be prevented. In addition, it is possible to easily peel the supporting sheet, which will be described later, from the film for forming a protective film while the film for forming a protective film remains adhered to the adherend, so that problems in manufacturing and processing are less likely to occur.

The film for forming a protective film according to the present invention includes, in addition to the components (A) to (C) and (D1) described above, (D2) a low molecular weight silane coupling agent described below, (E) a colorant, (F) a curing accelerator, and (G) It may contain any one or more of the other additives.

<(D2) Low molecular weight silane coupling agent>

The film for forming a protective film may contain a (D2) low molecular weight silane coupling agent having a molecular weight of less than 300, in addition to the (D1) silane coupling agent having a molecular weight of 300 or more.

(D2) The low molecular weight silane coupling agent has a reactive functional group capable of bonding to the surface of an inorganic material and a reactive functional group capable of bonding with an organic compound. (D2) The low molecular weight silane coupling agent preferably contains an alkoxy group as a reactive functional group capable of binding to the surface of the inorganic material, and preferably has an alkoxy equivalent of 13 mmol / g or less. Further, as the reactive functional group capable of bonding with the organic compound possessed by the (D2) low molecular weight silane coupling agent, it is preferable to react with functional groups of the (A) acrylic polymer or (B) epoxy-based curable component, and the glycidoxy group. , Epoxy groups other than the glycidoxy group, amino groups, (meth) acryloxy groups, vinyl groups other than (meth) acryloxy groups, mercapto groups, and the like. Among these, a glycidoxy group and an epoxy group are preferable.

(D2) As a low molecular weight silane coupling agent, specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacrylopropyl) trimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N And -6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and vinyl triacetoxysilane.

In the present invention, by blending the (D2) low molecular weight silane coupling agent, it becomes possible to secure a high adhesion even after long-term storage, and excellent storage stability.

That is, the low molecular weight silane coupling agent (D2) has low reactivity and is difficult to undergo a hydrolysis reaction, and therefore, the alkoxy group is likely to remain even after storage for a period of time. In addition, after a certain storage period has elapsed after forming the film for forming a protective film, (D2) the alkoxy group of the low molecular weight silane coupling agent is partially polymerized by causing a condensation reaction between molecules. Therefore, the (D2) low-molecular-weight silane coupling agent is difficult to increase the adhesion immediately after production, but after storage for a period of time, as with the high-molecular-weight (D1) silane coupling agent, it is possible to firmly bond to the adherend surface. have. Therefore, even when the adhesive strength of the (D1) silane coupling agent decreases after a long period of time (D2), by blending the low-molecular-weight silane coupling agent, it is possible to maintain an appropriate adhesive strength as a whole film for forming a protective film.

In order to exert such an effect, the (D2) low molecular weight silane coupling agent is preferably 0.1 to 10 in a mass ratio (D2 / D1) with respect to the (D1) silane coupling agent having a molecular weight of 300 or more, more preferably 0.2 to 5 And 1.1 to 3 are more preferable.

<(E) Coloring agent>

The film for forming a protective film preferably contains a colorant (E) because the semiconductor chip can be prevented from malfunctioning of the semiconductor chip by shielding infrared rays or the like generated from surrounding devices when the semiconductor chip is embedded in the device. In addition, by containing the colorant (E), character identification when printing a product number, mark, or the like on the protective film obtained by curing the protective film-forming film can be improved. That is, although the product number or the like may be printed on the back surface of the semiconductor chip formed with the protective film, in this case, the contrast difference between the printed part and the non-factor part is caused by the protective film containing the colorant (E). It becomes large and the discrimination is improved.

(E) As a colorant, an organic or inorganic pigment or dye is used. As the dye, any dye such as an acid dye, a reaction dye, a direct dye, a disperse dye, and a cationic dye can be used. Further, the pigment is not particularly limited, and may be appropriately selected from known pigments and used.

Among these, a black pigment that is capable of further improving the discrimination by a laser marking method while having good shielding properties of electromagnetic waves and infrared rays is more preferable. Carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like are used as the black pigment, but are not limited to these. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor chip. (E) The coloring agent may be used individually by 1 type, or may be used in combination of 2 or more type.

(E) The blending amount of the colorant is a proportion of the total mass (in terms of solid content) of the film for forming a protective film, preferably 0.01 to 25% by mass, more preferably 0.03 to 15% by mass.

<(F) Curing accelerator>

(F) The curing accelerator may be contained in the film for forming a protective film in order to adjust the curing rate of the protective film forming layer.

Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethyl imidazole; Organic phosphine such as tributylphosphine, diphenylphosphine, and triphenylphosphine; And tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate. These can be used individually by 1 type or in mixture of 2 or more types.

The curing accelerator (F) is contained in an amount of preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the epoxy curable component (B). (F) By containing the curing accelerator in an amount in the above range, the film for forming a protective film has excellent adhesion properties even when exposed to high temperature and high humidity, and high reliability can be achieved even when exposed to strict conditions.

<(G) Other additives>

Other additives that may be included in the film for forming a protective film are not particularly limited, but crosslinking agents, compatibilizers, leveling agents, plasticizers, antistatic agents, antioxidants, ion trapping agents, gettering agents, chain transfer agents, energy rays Polymerizable compounds, photopolymerization initiators, and the like. For the film for forming a protective film, for example, by mixing a compatibilizer, the compatibility between the phases with many (A) components and the phases with many cured products of (B) components is appropriately adjusted, and an appropriate phase separation structure can be designed.

<Gross value>

It is preferable that the gross value measured by JIS Z 8741 of at least one surface of the protective film obtained by hardening the film for protective film formation is 20 or more. In the film for forming a protective film, when a surface having a gross value of 20 or more and a surface on the opposite side adheres to the wafer and is cured, the surface of the object by laser marking of the protective film has a gross value of 20 or more. As a result, the surface to be laser printed becomes smooth, the contrast between the printing portion and the non-printing portion is improved, and the discrimination of the printing portion is improved.

The gloss value is more preferably 27 or more, since the contrast is further improved and the discrimination of characters is increased. Moreover, although a gross value is not specifically limited, It is preferable that it is 45 or less.

In addition, although the gross value is not specifically limited, For example, adjustment of the amount of the epoxy group containing monomer or the alkyl group (meth) acrylic acid alkyl ester having 4 or more carbon atoms, the content of the component (B) to the component (A) It can be appropriately adjusted according to adjustment, selection of the type of filler, adjustment of the content or particle size of the filler, or addition of other additives.

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

[Composite sheet for forming a protective film]

The film for forming a protective film of the present invention is usually formed to be peelable on a support sheet, and is used as a composite sheet for forming a protective film as a laminate. The film for forming a protective film can be made into the same shape as a support sheet. In addition, the composite sheet for forming a protective film is produced in a shape in which the film for forming a protective film can have a shape substantially the same as a wafer or a shape of a wafer, and is laminated on a support sheet having a size larger than the film for forming a protective film. It may be taking a configuration (hereinafter also referred to as "pre-molding configuration").

The support sheet supports a film for forming a protective film, 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 films, polycarbonate films, polyimide films, films such as fluororesin films are used. In addition, these crosslinked films are also used. It may also be a laminated film of these. Moreover, the film which colored these can also be used.

The surface on the side of the support sheet on which the film for forming a protective film is formed may be appropriately subjected to a peeling treatment. Examples of the peeling agent used in the peeling treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based adhesives, but the alkyd-based, silicone-based, and fluorine-based peeling agents are preferred because they have heat resistance.

In addition, in the composite sheet for forming a protective film, a light-peelable release sheet is bonded to a surface opposite to the side on which the support sheet of the film for forming a protective film is formed, and the release film may be protected by the release sheet. have.

The film for forming a protective film is obtained by applying and drying the composition for forming a protective film formed by mixing the above components in an appropriate ratio in a suitable solvent or without a solvent. In addition, a protective film forming composition may be applied onto a process film different from the support sheet, dried and formed into a film, and appropriately transferred to a support sheet or the like to form the film. The process film can also be used as the above-mentioned release sheet without being removed thereafter.

In addition, the surface tension of the support sheet can also be adjusted by laminating the film by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion, or the like. That is, the film in which the surface tension of at least one surface is within a preferred range as that of the surface contacting the film for forming a protective film of the support sheet described above is laminated with another film so that the surface becomes a surface contacting the film for forming a protective film. A laminate can also be produced and used as a support sheet.

Moreover, the adhesive sheet which formed the adhesive layer on the said film can also be used as a support sheet. In this case, the film for forming a protective film is laminated on the pressure-sensitive adhesive layer formed on the support sheet. By setting it as such a structure, it is preferable because the fixing performance of a wafer or a chip becomes excellent especially when a wafer is divided into chips for every film or protective film for forming a protective film on a composite sheet for forming a protective film. It is preferable to use the pressure-sensitive adhesive layer as a releasable pressure-sensitive adhesive layer because it is easy to separate the protective film forming film or protective film from the support sheet. As the releasable pressure-sensitive adhesive layer, a weakly adhesive substance having an adhesive strength sufficient to release the protective film-forming film may be used, or an energy ray-curable substance having reduced adhesive strength by energy ray irradiation may be used. Specifically, the releasable pressure-sensitive adhesive layer is a variety of pressure-sensitive adhesives conventionally known (for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose adhesives, adhesives with surface irregularities, energy ray curable adhesives, thermal expansion) Component-containing adhesives, and the like).

In the case of using the energy ray-curable releasable pressure-sensitive adhesive layer, when the composite sheet for forming a protective film has a preformed configuration, energy ray irradiation is performed in advance on the region where the film for forming a protective film is laminated to reduce the adhesiveness. On the other hand, other regions may not be irradiated with energy rays, and for example, for the purpose of adhesion to a jig, the adhesive force may be kept high. In order not to perform energy ray irradiation only in other regions, an energy ray shielding layer may be formed, for example, by printing or the like in a region corresponding to other regions of the support sheet, and energy ray irradiation may be performed from the support sheet side. In addition, in order to obtain the same effect, a structure in which a film for forming a protective film and a removable pressure-sensitive adhesive layer having a substantially the same shape as the film for forming a protective film are further laminated on a region where the film for forming a protective film on the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet is laminated may be used. have. As the film for the removable pressure-sensitive adhesive, the same ones as described above can be used.

When the film for forming a protective film does not take a pre-formed configuration, a separate adhesive layer or double-sided adhesive tape is provided on the outer circumference of the surface of the film for forming a protective film (the surface in contact with the adherend) to fix other jigs such as ring frames. It may be formed. When the film for forming a protective film takes a preformed configuration, a separate adhesive layer or double-sided adhesive tape is used to fix another jig such as a ring frame in a region where the film for forming a protective film is not laminated on the outer periphery of the support sheet. May be formed.

[How to use the film for forming a protective film]

The film for forming a protective film is adhered to an adherend such as a semiconductor wafer or a semiconductor chip, and then thermally cured to be used as a protective film. Here, when the film for forming a protective film is a composite sheet for forming a protective film and adheres to an adherend, first, when it is protected by a release sheet, the release sheet is peeled off, and then, a laminate of the film for protecting film formation and a supporting film After the body is attached to the adherend, the support sheet is peeled from the film for forming a protective film.

Hereinafter, the method of using the film for forming a protective film will be described as an example in which the film for forming a protective film is used for protecting the back surface of a semiconductor chip, and a chip with a protective film is produced, but is not limited to the examples shown below.

In this method, first, the film for forming a protective film is laminated on the back surface of a semiconductor wafer. For example, when a composite sheet for forming a protective film is used, a laminate of a film for forming a protective film and a base sheet is attached to the back surface of the semiconductor wafer. Then, after peeling the support sheet from the film for forming a protective film, the film for forming a protective film laminated on a semiconductor wafer is thermally cured to form a protective film on the entire surface of the wafer.

Further, the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium arsenide. In addition, the semiconductor wafer has a circuit formed on its surface, the back surface is appropriately ground, and the like, and has a thickness of about 50 to 500 µm.

Subsequently, the laminate 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, and the dicing of the semiconductor wafer and the protective film is divided into a plurality of chips by dicing. In addition, dicing of a wafer is performed by the usual method using a dicing sheet. Subsequently, the diced chip is picked up by a general-purpose means such as collet to obtain a semiconductor chip (a chip with a protective film) having a protective film on the back surface.

In addition, the manufacturing method of a semiconductor chip is not limited to the above example, For example, peeling of a support sheet may be performed after thermosetting of a protective film, or after dicing. Moreover, when peeling of a support sheet is performed after dicing, the support sheet can serve as a dicing sheet. Moreover, the thermosetting of the film for protective film formation can also be performed after dicing.

[Chip with protective film]

The chip provided with the protective film of the present invention is obtained, for example, by the above manufacturing method, and includes a semiconductor chip and a protective film laminated on the back surface of the semiconductor chip, and the protective film cures the film for forming the protective film described above. It is formed to protect the back side of the chip. The protective film preferably has a surface opposite to the semiconductor chip side having a gross value of 20 or more as measured by JIS Z 8741.

A semiconductor device can be manufactured by mounting a chip with a protective film on a substrate or the like in a face-down method. In addition, the semiconductor device can also be manufactured by adhering a chip with a protective film onto another member (on a chip mounting portion) such as a die pad portion or a separate semiconductor chip.

<Example>

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

The measurement method and evaluation method in the present invention are as follows.

(1) Weight average molecular weight (Mw)

The weight average molecular weight Mw of standard polystyrene conversion was measured by the gel permeation chromatography (GPC) method.

Measuring device: Tosoh's high-speed GPC device `` HLC-8120GPC '', the high-speed column `` TSK guard column (guard column) H _XL- H '', `` TSK gel (Gel) GMH <sub>XL</sub> '', `` TSK gel G2000 H _XL '' ( As described above, all manufactured by Tosoh Corporation) were connected and measured in this order.

Column temperature: 40 ° C, feeding rate: 1.0 mL / min, detector: differential refractive index meter

(2) Reliability evaluation

A film for forming a protective film of a composite sheet for forming a protective film obtained by peeling a release sheet on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, 280 μm thick), a tape mounter (Adwill, manufactured by Lintec Co., Ltd.) ) RAD-3600 F / 12) was used while heating to 70 ° C. Subsequently, after peeling a support sheet, the film for protective film formation was hardened by heating at 130 degreeC for 2 hours, and the protective film was formed on the silicon wafer. Reliability by attaching the protective film side to a dicing tape (AdWill D-676H manufactured by Lintec Co., Ltd.) and dicing to a size of 3 mm x 3 mm using a dicing device (manufactured by Disco Co., Ltd., DFD651) A chip with a protective film for evaluation was obtained.

The chip provided with the protective film for reliability evaluation was first processed under conditions (preconditions) that mimic the process in which the semiconductor chip is actually mounted. Specifically, the chip with the protective film was baked at 125 ° C for 20 hours, and then left to stand for 168 hours under the conditions of 85 ° C and 85% RH to absorb moisture, and then immediately preheat 160 ° C, peak temperature 260 ° C, and heating It was passed through the IR reflow furnace three times under the condition of time 30 seconds. Twenty-five chips with protective films treated with these pre-conditions were installed in a cold heat shock device (ESPEC manufactured by TSE-11-A), held at -65 ° C for 10 minutes, and thereafter. The cycle of holding at 150 ° C for 10 minutes was repeated 1000 times.

Thereafter, chips with 25 protective films were taken out from the cold heat shock device to evaluate reliability. Specifically, the presence or absence of excitation / exfoliation at the junction between the chip and the protective film or the presence or absence of cracks in the protective film is observed by a scanning ultrasonic inspection device (Hye-Focus manufactured by Hitachi Genki Fine Tech Co., Ltd.) and cross-section. Evaluated by, it was referred to as NG if any of the lifting, peeling and cracking. Table 3 shows the number of NGs among the 25 chips.

(3) Gross value

# 2000 A film for forming a protective film of a composite sheet for forming a protective film obtained by peeling a release sheet on a polished surface of a polished silicon wafer (200 mm diameter, 280 μm thick), a tape mounter (made by Lintec Co., Ltd., Adwill RAD- 3600 F / 12) while heating to 70 ° C. Subsequently, after peeling a support sheet, the film for protective film formation was hardened by heating at 130 degreeC for 2 hours, and the protective film was formed on the silicon wafer. Under the following measurement apparatus and measurement conditions, the mirror surface glossiness of 60 degrees of the protective film surface was measured, and it was set as the gross value.

Measuring device: VG 2000 Nippon Denshoku Kogyo Co., Ltd.

Measurement conditions: According to JIS Z 8741.

Example 1

In Example 1, the components forming the protective film-forming film were as follows.

(A) Acrylic copolymer: weight average obtained by copolymerizing 1 part by mass of n-butyl acrylate, 79 parts by mass of methyl methacrylate, 15 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of glycidyl methacrylate Copolymer with molecular weight (Mw) of 370,000 and glass transition temperature (Tg) of 7 ° C

(B) Epoxy-based curable component

Epoxy-based compounds: bisphenol A-type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., BPA-328) and dicyclopentadiene-type epoxy resin (manufactured by Dai Nippon Ink Chemical Co., Ltd., Epiclon HP-7200HH)

Heat curing agent: Dicyandiamide (made by ADEKA, Adeka Hardner 3636AS)

(C) Filler: Fused quartz filler with an average particle diameter of 8 µm (silica filler, manufactured by Tatsumori, physically crushed SV-10)

(D1) Silane coupling agent: Oligomer type silane coupling agent (X-41-1056 methoxy equivalent of Shin-Etsu Chemical Co., Ltd. 17.1 mmol / g, molecular weight 500 to 1500, having a glycidoxy alkyl group as a reactive functional group) )

(D2) Low molecular weight silane coupling agent: γ-glycidoxypropyl triethoxysilane (KBE-403 methoxy equivalent of 8.1 mmol / g, molecular weight 278.4, manufactured by Shin-Etsu Chemical Co., Ltd.), and γ-glycine Doxypropyl trimethoxysilane (KBM-403 methoxy equivalent of 12.7 mmol / g, molecular weight 236.3 manufactured by Shin-Etsu Chemical Co., Ltd.)

(E) Coloring agent: Carbon black (Mitsubishi Chemical Co., Ltd., MA600, average particle diameter: 28 nm)

(F) Curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Co., Ltd., Cursol 2PHZ)

A polyethylene terephthalate film (SP-PET5011 manufactured by Lintec Co., Ltd., 50 µm thick) obtained by diluting the composition for forming a protective film blended with each of the materials in the ratio shown in Table 1 with methyl ethyl ketone and peeling treatment on one side. On the peeling treatment surface of the support sheet containing, the thickness after drying and removal was applied to be 25 µm, and dried at 100 ° C for 3 minutes to form a film for forming a protective film on the support sheet. Subsequently, another release sheet (made by Lintec Co., Ltd., SP-PET3811, thickness 38 µm) was superimposed on the film for forming a protective film to obtain a composite sheet for forming a protective film of Example 1.

Examples 2 and 3 and Comparative Examples 1 to 5

(A) It carried out similarly to Example 1 except having used what was shown in Table 2 as an acrylic copolymer. Table 2 also shows the weight average molecular weight (Mw) and glass transition temperature (Tg) for the acrylic copolymer (A) of each of the Examples and Comparative Examples.

Comparative Example 6

As is apparent from Tables 1 and 2, as a silane coupling agent, (D) a silane coupling agent having a molecular weight of 300 or more is not compounded, and (D2) a low molecular weight silane coupling agent (KBM- manufactured by Shin-Etsu Chemical Co., Ltd.) 403) It carried out similarly to Example 2 except having mixed only 1 mass part.

Reliability was evaluated for each of Examples 1 to 3 and Comparative Examples 1 to 6, and the gross value was also measured. Table 3 shows the results.

As is apparent from Table 3, in Examples 1 to 3, (A) the acrylic polymer contained 8% by mass or less of an epoxy group-containing monomer as a constituent monomer, or did not include an epoxy group-containing monomer, and had a glass transition temperature. When it became -3 degreeC or more, the phase separation property of the hardened | cured material of (A) component and (B) component became favorable, and the reliability of the chip provided with a protective film could be made favorable. Moreover, in Examples 1 and 2, since the (A) acrylic polymer contained 8 mass% or less of an epoxy group-containing monomer as a constituent monomer, the gross value became 20 or more, and the discrimination of the factor by laser printing was also good. I can do it.

On the other hand, in Comparative Examples 1, 2, and 5, since the glass transition temperature of the acrylic polymer (A) was less than -3 ° C, it was estimated that the protective film was deformed by thermal history, thereby sufficiently improving the reliability of the chip with the protective film. I couldn't let it. Moreover, in Comparative Examples 3 and 4, since the acrylic polymer (A) contained a large amount of the epoxy group-containing monomer as a constituent monomer, the phase separation property was lowered, and the reliability of the chip with the protective film was lowered. Further, in Comparative Example 6, since the film for forming a protective film did not contain a (D) silane coupling agent having a molecular weight of 300 or more, the adhesiveness with the semiconductor chip could not be sufficiently increased, and reliability could not be sufficiently improved.

Claims (7)

A film for forming a protective film for forming a protective film for protecting a semiconductor chip,
The film for forming a protective film contains (A) an acrylic polymer, (B) an epoxy-based curable component, (C) a filler, and (D1) a silane coupling agent,
(A) The monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer, or contains an epoxy group-containing monomer in a proportion of 8% by mass or less of the total monomers, and (A) the glass transition temperature of the acrylic polymer is -3. ℃ or higher,
(D1) the molecular weight of the silane coupling agent is 300 or more,
(A) The monomer constituting the acrylic polymer further includes (meth) acrylic acid alkyl ester, and among the (meth) acrylic acid alkyl esters, (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group, (A) acrylic polymer A film for forming a protective film, which is contained in a proportion of 12% by mass or less of all monomers constituting. The film for forming a protective film according to claim 1, wherein the alkyl group has a (meth) acrylic acid alkyl ester having 4 or more carbon atoms (butyl meth) acrylate. The film for forming a protective film according to claim 1 or 2, further comprising a colorant (E). The film for forming a protective film according to claim 1 or 2, wherein the (D1) silane coupling agent is a compound having an alkoxy equivalent weight greater than 13 mmol / g. A semiconductor chip and a chip having a protective film, the protective film being formed on the semiconductor chip,
While the protective film is formed by curing the film for forming a protective film, the film for forming a protective film contains (A) an acrylic polymer, (B) an epoxy-based curable component, (C) a filler, and (D1) a silane coupling agent,
(A) The monomer constituting the acrylic polymer does not contain an epoxy group-containing monomer, or contains an epoxy group-containing monomer in a proportion of 8% by mass or less of the total monomers, and the glass transition temperature of the acrylic polymer (A) is -3. ℃ or higher,
(D1) the molecular weight of the silane coupling agent is 300 or more,
(A) The monomer constituting the acrylic polymer further includes (meth) acrylic acid alkyl ester, and among the (meth) acrylic acid alkyl esters, (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group, (A) acrylic polymer A chip with a protective film, which contains at a rate of 12% by mass or less of all monomers constituting. delete delete