WO2014087948A1 - Protective-membrane-forming film - Google Patents
Protective-membrane-forming film Download PDFInfo
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- WO2014087948A1 WO2014087948A1 PCT/JP2013/082290 JP2013082290W WO2014087948A1 WO 2014087948 A1 WO2014087948 A1 WO 2014087948A1 JP 2013082290 W JP2013082290 W JP 2013082290W WO 2014087948 A1 WO2014087948 A1 WO 2014087948A1
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- protective film
- film
- forming
- acrylic polymer
- meth
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a protective film forming film used for protecting the back surface of a semiconductor chip, for example.
- semiconductor devices are manufactured using a mounting method called a face-down method.
- the semiconductor chip is protected by a protective film because the chip surface on which electrodes such as bumps are formed is opposed to and bonded to the substrate and the back surface of the chip is exposed.
- the protective film hereinafter referred to as “chip with protective film”.
- the protective film has been formed by, for example, resin coating.
- a protective film forming sheet is attached to ensure uniformity of the film thickness. What is formed is being put into practical use.
- This protective film-forming sheet is obtained by providing a protective film-forming film containing a thermosetting component made of an epoxy resin or the like and a binder polymer component made of an acrylic polymer or the like on a support sheet. .
- Patent Document 2 discloses an elastic film having an elastic modulus of 3500 to 3 that is phase-separated in a B-stage state as an adhesive film used for semiconductor packages and the like.
- a material comprising a mixture of a resin A of 10,000 GPa and a resin B having an elastic modulus of 1 to 3000 MPa is disclosed.
- an epoxy resin is used as the resin A
- an acrylic rubber that is a copolymer of methacrylic acid ester and acrylonitrile is used as the resin B.
- the chip with the protective film may float or peel off at the joint between the chip and the protective film due to long-term use. Problems such as the generation of cracks in the protective film are likely to occur, and the reliability may be poor. Further, as disclosed in Patent Document 2, if a composition in which two kinds of components are phase-separated is diverted to a protective film for a chip, the reliability of the chip with the protective film may be improved. Another problem arises that the recognizability of characters and the like tends to deteriorate.
- the present invention has been made in view of the above-mentioned problems, and can provide a highly reliable chip with a protective film and can form a protective film having excellent character recognition by laser printing. It is an object to provide a protective film-forming film.
- the present inventors have paid attention to an acrylic polymer of a protective film-forming resin, and an epoxy group-containing monomer as a monomer constituting the acrylic polymer.
- the above-mentioned problems can be solved by adjusting the glass transition temperature of the acrylic polymer to a predetermined range while adjusting the blending ratio to a predetermined range, and the following invention has been completed. . That is, the present invention provides the following (1) to (8).
- a protective film-forming film for forming a protective film for protecting a semiconductor chip contains (A) an acrylic polymer, (B) an epoxy-based curable component, and (C) a filler, (A) The monomer constituting the acrylic polymer 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 ° C or higher, A protective film-forming film having a gloss value of 20 or more as measured by JIS Z 8741 on at least one surface of a protective film obtained by curing the protective film-forming film.
- the above (A) monomer comprising an acrylic polymer contains a (meth) acrylic acid alkyl ester having an alkyl group with 4 or more carbon atoms in a proportion of 12% by mass or less of the total monomer ( The film for forming a protective film according to any one of 1) to (3).
- a chip with a protective film comprising a semiconductor chip and a protective film provided on the semiconductor chip
- the protective film is formed by curing a protective film-forming film
- the protective film-forming film comprises (A) an acrylic polymer, (B) an epoxy-based curable component, and (C ) Contains filler, (A) The monomer constituting the acrylic polymer 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 ° C or higher
- the protective film is a chip with a protective film in which a surface opposite to the surface on the semiconductor chip side has a gloss value of 20 or more as measured by JIS Z 8741.
- a highly reliable chip with a protective film can be obtained, and a protective film-forming film capable of forming a protective film having excellent character recognition by laser printing can be provided.
- 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 includes at least (A) an acrylic polymer, (B) an epoxy curable component, and (C). It contains a filler.
- An acrylic polymer is a component that imparts flexibility and film-forming properties to a protective film and a protective film-forming film, and is a copolymer of an epoxy group-containing monomer and another monomer.
- the ratio of the epoxy group-containing monomer is 8% by mass or less in the total monomer constituting the (A) acrylic polymer.
- the monomer constituting the (A) acrylic polymer contains one or more epoxy groups selected from epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers. It consists of a monomer and various (meth) acrylic acid ester which does not have an epoxy group, and / or a non-acrylic epoxy group-free monomer.
- the epoxy group-containing monomer when the epoxy group-containing monomer is composed only of a non-acrylic epoxy group-containing monomer, the monomer constituting the acrylic polymer is various (meth) acrylic acids having no epoxy group. Contains esters.
- the proportion of the epoxy group-containing monomer is more than 8% by mass, the compatibility with the cured product of the component (B) is improved, the later-described phase separation structure is hardly formed, and the reliability of the chip with the protective film is improved. Decreases.
- the acrylic polymer (A) does not contain any epoxy group-containing monomer as a constituent monomer, the reduction in the gloss value of the protective film due to the progress of phase separation becomes excessive. It becomes difficult to keep the value within the range described below.
- the content of the epoxy group-containing monomer is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total mass of all monomers. Furthermore, in order to further improve the reliability while improving the gloss value, it is particularly preferably 3% by mass or more. Moreover, it is preferable that content of an epoxy-group-containing monomer is 6 mass% or less of the total monomer of (A) acrylic copolymer.
- Examples of the epoxy group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-
- Examples of the non-acrylic epoxy group-containing monomer such as hydroxypropyl (meth) acrylate include glycidyl crotonate and allyl glycidyl ether.
- an epoxy group-containing (meth) acrylic acid ester is preferable.
- (A) Other monomers in the acrylic polymer include (meth) acrylic acid alkyl esters and other (meth) acrylic acid derivatives.
- the monomer which comprises an acrylic polymer contains (meth) acrylic-acid alkylester as said other monomer. This makes it easy to adjust the glass transition temperature of the (A) acrylic polymer by increasing or decreasing the number of carbon atoms of the (meth) acrylic acid alkyl ester or by combining (meth) acrylic acid alkyl esters having different carbon numbers.
- the (meth) acrylic acid alkyl ester is preferably 50% by mass or more, and more preferably 70% by mass or more of the total monomer constituting the (A) acrylic polymer.
- (meth) acrylic-acid alkylester is 92 mass% or less of all the monomers which comprise (A) acrylic polymer.
- (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic acid.
- the monomer constituting the acrylic polymer is a (meth) acrylic acid alkyl ester having 4 or more alkyl groups in the above (meth) acrylic acid alkyl ester. It is preferable to contain it in an amount of 12% by mass or less of the total monomer constituting the coalescence. This makes it easier to make the gloss value better while keeping the glass transition temperature at ⁇ 3 ° C. or higher.
- the content of the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is more preferably 1 to 12% by mass, and further preferably 5%. ⁇ 12% by mass.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group butyl (meth) acrylate is preferable.
- the monomer which comprises (A) acrylic polymer contains the (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 3 or less among the said (meth) acrylic-acid alkylester. .
- the glass transition temperature of the (A) acrylic polymer is ⁇ 3 as described later, while improving the thermal stability and the like. It becomes easy to be over °C.
- the (meth) acrylic acid alkyl ester having 3 or less carbon atoms in the alkyl group is preferably 50% by mass or more of the total monomers constituting the (A) acrylic polymer, and is 60% by mass. % Or more is more preferable. Moreover, it is preferable that (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 3 or less is 90 mass% or less of the total monomer which comprises (A) acrylic polymer.
- methyl (meth) acrylate or ethyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
- the monomer which comprises (A) acrylic polymer contains a hydroxyl-containing (meth) acrylic acid ester as another (meth) acrylic acid derivative.
- a hydroxyl-containing (meth) acrylic acid ester as another (meth) acrylic acid derivative.
- the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
- the hydroxyl group-containing (meth) acrylic acid ester is preferably 1 to 30% by mass, more preferably 5 to 25% by mass of the total monomers constituting the (A) acrylic polymer. More preferably, it is 20 mass%.
- the monomer constituting the (A) acrylic polymer includes, as other monomers, non-acrylic epoxy group-free monomers such as styrene, ethylene, vinyl ether, and vinyl acetate as described above. You may go out.
- the weight average molecular weight (Mw) of the acrylic polymer can give flexibility and film-forming properties to the protective film-forming film, and in order to make the gloss value described later easily 20 or more, 10,000. The above is preferable.
- the weight average molecular weight is more preferably 15,000 to 1,000,000, still more preferably 20,000 to 500,000.
- a weight average molecular weight (Mw) can be measured according to the method of the Example mentioned later.
- the (A) acrylic polymer has a glass transition temperature (Tg) of ⁇ 3 ° C. or higher.
- Tg glass transition temperature
- the glass transition temperature of the acrylic polymer (A) is a theoretical value obtained from the Fox equation.
- the glass transition temperature of (A) acrylic polymer is 6 degrees C or less.
- the epoxy group-containing monomer is suppressed to a small amount, so that the phase rich in the component (A) and the phase rich in the cured product of the component (B) described later in the protective film are phase-separated.
- This improves the reliability of the chip with the protective film. This is because even when the temperature changes after chip mounting, the stress due to the deformation due to the temperature change is relaxed by the flexible (A) rich phase, so that the protective film is hardly peeled off due to the stress. It is estimated that.
- the phase rich in (A) forms the continuous phase about the phase separation in the film for protective film formation (namely, protective film) after thermosetting.
- phase rich in (A) and the phase rich in the cured product of (B) observe what substance is the main component of the phase from, for example, a measurement chart of a phase by Raman scattering spectrometry. Can be determined. If the size of the phase separation structure is less than the resolution of Raman spectroscopy, the hardness of the tapping mode measurement of SPM (scanning probe microscope) is used as an index, and the harder phase is rich in the cured product of component (B). It can be estimated that the softer phase is richer in the component (A). Therefore, in this invention, it can be confirmed whether the phase-separation structure is formed by Raman scattering spectroscopy measurement or SPM observation of the protective film obtained by hardening
- the proportion of the (A) acrylic polymer in the total mass (in terms of solid content) of the protective film-forming film is usually 10 to 80% by mass, preferably 15 to 50% by mass.
- the epoxy-based curable component is a component for forming a hard protective film on the semiconductor chip by curing, and usually comprises an epoxy-based compound and a thermosetting agent.
- the (B) epoxy-based curable component is preferably 250 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 with respect to 100 parts by mass of the (A) acrylic polymer. It is below mass parts.
- the (B) epoxy-based curable component is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 60 parts by mass or more with respect to 100 parts by mass of the (A) acrylic polymer. .
- (B) By making content of an epoxy-type curable component into the said range, sufficient adhesiveness with respect to adherends, such as a semiconductor chip, is obtained, and peeling force with the support sheet mentioned later becomes appropriate, and supports. It is also possible to prevent peeling failure when the sheet is peeled from the protective film-forming film. Furthermore, as described above, by limiting the blending amount of the component (B) to a range below a predetermined upper limit value, the phase rich in the component (A) is likely to be a continuous phase, and the reliability of the semiconductor chip can be improved. Moreover, it becomes easy to improve the gloss value.
- the proportion of the (B) epoxy-based curable component in the total mass (in terms of solid content) of the protective film-forming film is usually about 5 to 60% by mass, preferably about 10 to 40% by mass.
- epoxy compound a conventionally known epoxy compound can be used. Specifically, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene
- An epoxy compound having two or more functional groups in the molecule, such as a skeleton type epoxy resin, can be given. These can be used individually by 1 type or in combination of 2 or more types.
- thermosetting agent functions as a curing agent for the epoxy compound.
- a preferable thermosetting agent includes a compound having two or more functional groups capable of reacting with an epoxy group in one molecule.
- 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.
- phenolic curing agent having a phenolic hydroxyl group examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zyloc type phenolic resins, and aralkylphenolic resins.
- a specific example of the amine curing agent having an amino group is dicyandiamide. These can be used individually by 1 type or in mixture of 2 or more types.
- the content of the thermosetting agent is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, with respect to 100 parts by weight of the epoxy compound. More preferably, it is a part.
- (B) component hardens
- 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.
- the filler is a component that gives the protective film moisture resistance, dimensional stability, and the like, and specifically includes an inorganic filler.
- the filler is a component that gives the protective film moisture resistance, dimensional stability, and the like, and specifically includes an inorganic filler.
- laser marking a method in which the surface of the protective film is scraped and printed by laser light
- the portion (printed part) scraped by the laser light is exposed to the (C) filler material and reflected light. Is diffused, the contrast with the non-printing portion is improved and recognition becomes possible.
- 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.
- silica filler and alumina filler are particularly preferable.
- 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 ⁇ m. If the thickness is 0.1 ⁇ m or more, the protective film-forming composition tends to be suitable for coating when the protective film-forming composition is applied and dried on a support sheet to obtain a protective film-forming film.
- the average particle diameter of the filler is more preferably 0.2 to 10 ⁇ m, and further preferably 0.3 to 6 ⁇ m.
- the average particle diameter is measured with a particle size distribution meter using a dynamic light scattering method. Examples of the particle size distribution meter include Nanotrac 150 manufactured by Nikkiso Co., Ltd.
- the content of the (C) filler in the protective film-forming film is preferably 10% by mass or more, and preferably 30% by mass or more, as a proportion of the total mass (in terms of solid content) of the protective film-forming film. More preferably, it is more preferably 50% by mass or more.
- content of (C) filler is 80 mass% or less with respect to the total mass of the film for protective film formation, It is more preferable that it is 70 mass% or less, It is 63 mass% or less. More preferably it is.
- (C) By making content of a filler into these ranges, it becomes easy to exhibit the effect of an above-described filler. Further, by setting the content of the (C) filler to 50% by mass or more, the contrast between the laser-marked printed portion and the non-printed portion is improved, and the print recognizability is improved. Moreover, it becomes easy to improve a gross value by setting it as the said upper limit or less.
- the protective film-forming film according to the present invention includes the following (D) colorant, (E) coupling agent, (F) curing accelerator, and ( G) Any one or more of the other additives may be contained.
- the protective film-forming film contains (D) a colorant because when the semiconductor chip is incorporated in a device, it can shield infrared rays generated from surrounding devices and prevent malfunction of the semiconductor chip. It is preferable.
- the colorant (D) it is possible to improve the character distinguishability when a product number, a mark, or the like is printed on the protective film obtained by curing the protective film-forming film. That is, on the back surface of the semiconductor chip on which the protective film is formed, the product number or the like is usually printed by the laser marking method, but the protective film contains the (D) colorant, so that the contrast between the printed part and the non-printed part is The difference is increased and the discrimination is improved.
- An organic or inorganic pigment or dye is used as the colorant.
- 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.
- the black pigment which has favorable shielding property of electromagnetic waves and infrared rays, and can improve the discriminability by a laser marking method is more preferable.
- 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 chip.
- a coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the blending amount of the colorant (D) is preferably 0.01 to 25% by mass, more preferably 0.03 to 15% by mass as a proportion of the total mass (converted to solid content) of the protective film-forming film. .
- a coupling agent may be mix
- the silane coupling agent which has alkoxy groups, such as a methoxy group and an ethoxy group, is preferable.
- the coupling agent (E) a compound having a reactive functional group other than an alkoxy group that reacts with a functional group of (A) an acrylic polymer or (B) an epoxy curable component is preferably used. Is done.
- reactive functional groups examples include glycidoxy groups, epoxy groups other than glycidoxy groups, amino groups, (meth) acryloxy groups, vinyl groups other than (meth) acryloxy groups, mercapto groups, and the like. In these, a glycidoxy group and an epoxy group are preferable.
- silane coupling agent a low molecular weight silane coupling agent having a molecular weight of less than 300 may be used, an oligomer type silane coupling agent having a molecular weight of 300 or more may be used, and these are used in combination. May be.
- the low molecular weight silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacrylopropyl) trimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, N-6- (aminoethyl) - ⁇ -Aminopropylmethyldiethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, vinyltriacetoxysilane and the like.
- the oligomer type silane coupling agent is preferably an organopolysiloxane having a siloxane skeleton and an alkoxy group directly bonded to a silicon atom.
- the content of the coupling agent is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 3.% by mass as a ratio to the total mass (in terms of solid content) of the protective film-forming film. 0% by mass.
- the curing accelerator may be contained in the protective film-forming 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, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate.
- the (F) curing accelerator 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 (B) epoxy-based curable component.
- the protective film-forming film has excellent adhesive properties even when exposed to high temperatures and high humidity, and is exposed to severe conditions. Even high reliability can be achieved.
- additives that may be included in the protective film-forming film are not particularly limited to these, but include crosslinking agents, compatibilizers, leveling agents, plasticizers, antistatic agents, antioxidants, Examples thereof include an ion scavenger, a gettering agent, a chain transfer agent, an energy beam polymerizable compound, and a photopolymerization initiator.
- the protective film-forming film is prepared by appropriately adjusting the compatibility of the phase rich in the component (A) and the phase rich in the cured product of the component (B) by adding a compatibilizing agent, for example.
- a separation structure can be designed.
- the gloss value measured by JIS Z 8741 of at least one surface of the protective film obtained by curing is 20 or more.
- the surface to be printed by laser marking of the protective film has a gloss value of 20 or more by attaching and curing the surface opposite to the surface having a gloss value of 20 or more on the wafer.
- the gloss value is preferably 27 or more in order to further improve the contrast and improve the character discrimination.
- the gloss value is not particularly limited, but is preferably 45 or less.
- the gloss value is not particularly limited.
- the thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, and still more preferably 7 to 200 ⁇ m.
- the protective film-forming film of the present invention is usually formed on a support sheet so as to be peelable and used as a protective film-forming composite sheet as a laminate.
- the protective film-forming film can have the same shape as the support sheet.
- the protective film-forming composite sheet is prepared by making the protective film-forming film substantially the same shape as the wafer or including the shape of the wafer, and having a larger size than the protective film-forming film. A so-called pre-molded configuration laminated on the supporting sheet may be adopted.
- the support sheet is for supporting a protective film-forming film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate.
- a protective film-forming 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
- a film such as a film, a polystyrene film, a polycarbonate film, a polyimide film, or a fluororesin film is used. These crosslinked films are also used. Furthermore, two or more laminated films selected from these may be used. Moreover, the film which colored these can also be used.
- the surface of the support sheet on which the protective film-forming film is formed may be appropriately subjected to a peeling treatment.
- release agent used for the release treatment examples include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax, but alkyd, silicone, and fluorine release agents are heat resistant. It is preferable because of its properties.
- a light-peelable release sheet is bonded to the surface opposite to the surface on which the support sheet of the protective film-forming film is provided, and the protective sheet is formed by the release sheet. The film may be protected.
- the protective film-forming film is obtained by applying and drying a protective film-forming composition obtained by mixing the above-described components in an appropriate ratio in an appropriate solvent or without a solvent.
- the protective film-forming composition may be applied onto a process film different from the support sheet, dried and formed into a film, and then transferred to a support sheet or the like as appropriate. You may use a process film as a peeling sheet mentioned above, without removing after that.
- 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 of the support sheet in contact with the protective film forming film is such that the surface is in contact with the protective film forming film.
- a laminate laminated with another film may be manufactured and used as a support sheet.
- an adhesive sheet having an adhesive layer formed on the film may be used as a support sheet.
- the protective film-forming film is laminated on the pressure-sensitive adhesive layer provided on the support sheet.
- the pressure-sensitive adhesive layer is a re-peelable pressure-sensitive adhesive layer because the protective film-forming film or the protective film can be easily separated from the support sheet.
- the re-peelable pressure-sensitive adhesive layer may be a weak-adhesive layer having an adhesive strength sufficient to peel off the protective film-forming film, or an energy-ray curable one whose adhesive strength is reduced by energy beam irradiation May be used.
- the re-peelable pressure-sensitive adhesive layer is made of various conventionally known pressure-sensitive adhesives (for example, general-purpose pressure-sensitive adhesives such as rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based, and pressure-sensitive adhesives with surface irregularities). , Energy ray curable adhesive, thermal expansion component-containing adhesive, etc.).
- 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. .
- a re-peelable pressure-sensitive adhesive layer having substantially the same shape as the protective film-forming film was further laminated in the region where the protective film-forming film on the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet was laminated. It is good also as a structure.
- the film for the releasable pressure-sensitive adhesive the same film as described above can be used.
- a separate adhesive layer or double-sided pressure-sensitive adhesive tape may be provided. If the protective film-forming film has a pre-molded configuration, a separate adhesive is used to fix other jigs such as a ring frame to the outer periphery of the support sheet where the protective film-forming film is not laminated. Layers and double-sided adhesive tapes may be provided.
- the protective film-forming film is affixed to an adherend such as a semiconductor wafer or a semiconductor chip, and then thermally cured and used as a protective film.
- an adherend such as a semiconductor wafer or a semiconductor chip
- thermally cured and used as a protective film when the protective film-forming film is attached to the adherend as a protective film-forming composite sheet, first, when the protective film is protected by the release sheet, the release sheet is peeled off, and then the protective film After the laminate of the forming film and the support film is attached to the adherend, the support sheet is peeled off from the protective film forming film.
- the protective film-forming film is laminated on the back surface of the semiconductor wafer.
- a laminate of the protective film-forming film and the base sheet is attached to the back surface of the semiconductor wafer.
- the support sheet is peeled from the protective film-forming film, and then the protective film-forming film laminated on the semiconductor wafer is thermally cured to form a protective film on the entire surface of the wafer.
- the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Further, the semiconductor wafer has a circuit formed on the front surface thereof, and the back surface thereof is appropriately ground or the like to have a thickness of about 50 to 500 ⁇ m.
- 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 that the wafer and the protective film are cut together, and the laminated body of the semiconductor wafer and the protective film is divided into a plurality of chips by dicing.
- the wafer is diced by a conventional method using a dicing sheet.
- 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 (chip with protective film).
- 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 the thermosetting of a protective film, and may be performed after dicing. In addition, when peeling of a support sheet is performed after dicing, a support sheet can serve as a dicing sheet. Moreover, the thermosetting of the protective film-forming film may be performed after dicing.
- the chip with a protective film of the present invention is obtained, for example, by the above-described 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 protective film-forming film described above.
- the back surface of the chip is protected.
- the surface of the protective film opposite to the surface on the semiconductor chip side has a gloss 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 by a face-down method. Further, the semiconductor device can also be manufactured by bonding the chip with protective film to another member (on the chip mounting part) such as a die pad part or another semiconductor chip.
- the measurement method and evaluation method in the present invention are as follows.
- Weight average molecular weight (Mw) The weight average molecular weight Mw in terms of standard polystyrene was measured by gel permeation chromatography (GPC).
- Measuring device Tosoh's high-speed GPC device "HLC-8120GPC", high-speed column “TSK guard column H XL -H", “TSK Gel GMH XL “, “TSK Gel G2000 H XL “ ) In this order and measured.
- liquid feed rate 1.0 mL / min
- detector differential refractometer
- a protective film forming film of a composite sheet for forming a protective film having a release sheet peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, thickness 280 ⁇ m) is a tape mounter (manufactured by Lintec Corporation). Adwill RAD-3600 F / 12) was applied while heating to 70 ° C. Next, after peeling off the support sheet, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to form a protective film on the silicon wafer. The specular glossiness of 60 degrees on the surface of the protective film was measured with the following measuring apparatus and measurement conditions, and the gloss value was obtained. Measuring device: VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd. Measuring conditions: conforming to JIS Z 8741
- a tape mounter (Adwill RAD-3600 F, manufactured by Lintec Co., Ltd.) is used to form a protective film forming film of a composite sheet for forming a protective film with a release sheet peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, 280 ⁇ m thick). / 12) was applied while heating to 70 ° C. Next, after peeling off the support sheet, the film for forming a protective film was cured by heating at 130 ° C. for 2 hours, thereby forming a protective film on the silicon wafer.
- a tape mounter (manufactured by Lintec Corporation) is used to form a protective film forming film of a composite sheet for forming a protective film on which a release sheet is peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, 280 ⁇ m thick).
- Adwill RAD-3600 F / 12 was applied while heating to 70 ° C.
- the protective film-forming film was cured by heating at 130 ° C. for 2 hours to form a protective film on the silicon wafer.
- the protective film side is affixed to a dicing tape (Adwill D-676H manufactured by Lintec Corporation), and dicing into 3 mm ⁇ 3 mm size using a dicing apparatus (DFD Co., Ltd., DFD651) for reliability evaluation.
- a dicing tape Adwill D-676H manufactured by Lintec Corporation
- DFD651 a dicing apparatus
- the chip with a protective film for reliability evaluation was first processed under conditions (preconditions) imitating a process in which a semiconductor chip was actually mounted. Specifically, the chip with a protective film is baked at 125 ° C. for 20 hours, and then left to stand for 168 hours under conditions of 85 ° C. and 85% RH to immediately absorb moisture, followed by preheating at 160 ° C., peak temperature at 260 ° C., and heating. It was passed 3 times through an IR reflow oven for 30 seconds. Twenty-five protective film-coated chips treated with these preconditions were placed in a thermal shock apparatus (TSE-11-A, manufactured by ESPEC Corporation), held at ⁇ 65 ° C. for 10 minutes, and then held at 150 ° C. for 10 minutes.
- TSE-11-A thermal shock apparatus
- the cycle was repeated 1000 times. Thereafter, 25 chips with protective films were taken out of the thermal shock apparatus and evaluated for reliability. Specifically, the presence or absence of floating / peeling at the joint between the chip and the protective film or cracks in the protective film is determined by scanning ultrasonic flaw detector (Hy-Focus manufactured by Hitachi Construction Machinery Finetech Co., Ltd.) and cross-sectional observation. It was evaluated as NG if any of floating, peeling and cracking was found. Table 4 shows the number of NGs out of 25 chips.
- Example 1 the components forming the protective film-forming film were as follows.
- Copolymer having a weight average molecular weight (Mw) of 370,000 and a glass transition temperature (Tg) of 7 ° C.
- Epoxy curable component Epoxy compound Bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., BPA-328) And dicyclopentadiene type epoxy resin (Dainippon Ink and Chemicals, Epicron HP-7200HH)
- Thermosetting agent Dicyandiamide (manufactured by ADEKA Corporation, Adeka Hardener 3636AS)
- Silane coupling agent 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.) and ⁇ -glycidoxyprop
- Polyethylene terephthalate film obtained by diluting a composition for forming a protective film, blended in the proportions shown in Table 1 with methyl ethyl ketone, and subjecting one surface to peeling treatment
- the film was applied to the release-treated surface of the support sheet so that the thickness after drying was 25 ⁇ m, and dried at 100 ° C. for 3 minutes to form a protective film-forming film on the support sheet.
- a separate release sheet (SP-PET3811, thickness 38 ⁇ m, manufactured by Lintec Corporation) was superimposed on the protective film-forming film to obtain a protective film-forming composite sheet of Example 1.
- Example 2 and Comparative Examples 1-6 (A) The same procedure as in Example 1 was carried out except that the acrylic copolymer shown in Table 2 was used. In addition, about the (A) acrylic copolymer of each Example and a comparative example, it shows in Table 2 together with a weight average molecular weight (Mw) and a glass transition temperature (Tg).
- Mw weight average molecular weight
- Tg glass transition temperature
- Example 3 It implemented similarly to Example 2 except having used the silica filler (made by Tokuyama Corporation, UF310) with an average particle diameter of 3 micrometers instead of the silica filler with an average particle diameter of 8 micrometers.
- Example 4 It implemented similarly to Example 2 except having used the silica filler (manufactured by Admatechs, SC2050MA) having an average particle diameter of 0.5 ⁇ m instead of the silica filler having an average particle diameter of 8 ⁇ m.
- Examples 5 and 6 It implemented similarly to Example 2 except the point which changed the compounding quantity of the component as shown in Table 3.
- Examples 7 and 8 It implemented similarly to Example 2 except the point which changed the compounding quantity of (A) and (B) component as shown in Table 3.
- (A) the acrylic polymer contains an epoxy group-containing monomer of 8% by mass or less as a constituent monomer, and the glass transition temperature is ⁇ 3 ° C. or higher.
- the phase separation between the phase rich in the component (A) and the phase rich in the cured product of the component (B) can be improved and the gloss value can be set to 20 or more. Both sexes could be improved.
- Comparative Example 1 since the (A) acrylic polymer did not contain an epoxy group-containing monomer as a constituent monomer, fine irregularities were formed on the surface of the protective film due to phase separation. The scattering of the reflected light on the film surface was caused.
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Abstract
Description
すなわち、本発明は、以下の(1)~(8)を提供するものである。
(1)半導体チップを保護する保護膜を形成するための保護膜形成用フィルムであって、
前記保護膜形成用フィルムが、(A)アクリル系重合体、(B)エポキシ系硬化性成分、および(C)充填材を含有し、
(A)アクリル系重合体を構成する単量体が、全単量体の8質量%以下の割合でエポキシ基含有単量体を含むとともに、(A)アクリル系重合体のガラス転移温度が-3℃以上であり、
前記保護膜形成用フィルムを硬化して得た保護膜の少なくとも一面のJIS Z 8741により測定されるグロス値が20以上である保護膜形成用フィルム。
(2)(A)アクリル系重合体のガラス転移温度が6℃以下である上記(1)に記載の保護膜形成用フィルム。
(3)(A)アクリル系重合体を構成する単量体が、さらに(メタ)アクリル酸アルキルエステルを含む上記(1)又は(2)に記載の保護膜形成用フィルム。
(4)(A)アクリル系重合体を構成する単量体が、全単量体の12質量%以下の割合でアルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルを含む上記(1)~(3)のいずれかに記載の保護膜形成用フィルム。
(5)前記アルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルが、(メタ)アクリル酸ブチルである上記(4)に記載の保護膜形成用フィルム。
(6)(C)充填材の含有量が、保護膜形成用フィルムの50質量%以上である上記(1)~(5)のいずれかに記載の保護膜形成用フィルム。
(7)さらに(D)着色剤を含有する上記(1)~(6)のいずれかに記載の保護膜形成用フィルム。
(8)半導体チップと、前記半導体チップ上に設けられる保護膜とを備える保護膜付きチップであって、
前記保護膜が、保護膜形成用フィルムを硬化させて形成されたものであるとともに、前記保護膜形成用フィルムが、(A)アクリル系重合体、(B)エポキシ系硬化性成分、及び(C)充填材を含有し、
(A)アクリル系重合体を構成する単量体が、全単量体の8質量%以下の割合でエポキシ基含有単量体を含むとともに、(A)アクリル系重合体のガラス転移温度が-3℃以上であり、
前記保護膜は、前記半導体チップ側の面とは反対の面がJIS Z 8741により測定されるグロス値が20以上である保護膜付きチップ。 As a result of intensive studies to solve the above problems, the present inventors have paid attention to an acrylic polymer of a protective film-forming resin, and an epoxy group-containing monomer as a monomer constituting the acrylic polymer. The above-mentioned problems can be solved by adjusting the glass transition temperature of the acrylic polymer to a predetermined range while adjusting the blending ratio to a predetermined range, and the following invention has been completed. .
That is, the present invention provides the following (1) to (8).
(1) A protective film-forming film for forming a protective film for protecting a semiconductor chip,
The protective film-forming film contains (A) an acrylic polymer, (B) an epoxy-based curable component, and (C) a filler,
(A) The monomer constituting the acrylic polymer 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 ° C or higher,
A protective film-forming film having a gloss value of 20 or more as measured by JIS Z 8741 on at least one surface of a protective film obtained by curing the protective film-forming film.
(2) The film for forming a protective film according to the above (1), wherein the glass transition temperature of the acrylic polymer (A) is 6 ° C. or lower.
(3) The film for forming a protective film according to the above (1) or (2), wherein the monomer constituting the (A) acrylic polymer further contains an alkyl (meth) acrylate.
(4) The above (A) monomer comprising an acrylic polymer contains a (meth) acrylic acid alkyl ester having an alkyl group with 4 or more carbon atoms in a proportion of 12% by mass or less of the total monomer ( The film for forming a protective film according to any one of 1) to (3).
(5) The film for forming a protective film according to (4), wherein the alkyl group (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is butyl (meth) acrylate.
(6) The protective film-forming film according to any one of the above (1) to (5), wherein the content of the (C) filler is 50% by mass or more of the protective film-forming film.
(7) The protective film-forming film as described in any one of (1) to (6), further comprising (D) a colorant.
(8) A chip with a protective film comprising a semiconductor chip and a protective film provided on the semiconductor chip,
The protective film is formed by curing a protective film-forming film, and the protective film-forming film comprises (A) an acrylic polymer, (B) an epoxy-based curable component, and (C ) Contains filler,
(A) The monomer constituting the acrylic polymer 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 ° C or higher,
The protective film is a chip with a protective film in which a surface opposite to the surface on the semiconductor chip side has a gloss value of 20 or more as measured by JIS Z 8741.
なお、本明細書において、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の双方を示す用語として使用し、他の類似用語についても同様である。
[保護膜形成用フィルム]
本発明に係る保護膜形成用フィルムは、半導体チップを保護する保護膜を形成するためのフィルムであって、少なくとも(A)アクリル系重合体、(B)エポキシ系硬化性成分、および(C)充填材を含有するものである。 Hereinafter, the present invention will be specifically described with reference to embodiments thereof.
In this specification, “(meth) acryl” is used as a term indicating both “acryl” and “methacryl”, and the same applies to other similar terms.
[Film for forming a 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 includes at least (A) an acrylic polymer, (B) an epoxy curable component, and (C). It contains a filler.
(A)アクリル系重合体は、保護膜及び保護膜形成用フィルムに可撓性、造膜性を付与する成分であって、エポキシ基含有単量体と、他の単量体とを共重合して得られるとともに、エポキシ基含有単量体の割合が、(A)アクリル系重合体を構成する全単量体中、8質量%以下となるものである。具体的には、(A)アクリル系重合体を構成する単量体は、エポキシ基含有(メタ)アクリル酸エステルおよび非アクリル系エポキシ基含有単量体から選択される1種以上のエポキシ基含有単量体と、エポキシ基を有しない各種の(メタ)アクリル酸エステル、及び/又は非アクリル系エポキシ基非含有単量体とからなる。この場合において、エポキシ基含有単量体が非アクリル系エポキシ基含有単量体のみからなる場合は、アクリル系重合体を構成する単量体は、エポキシ基を有しない各種の(メタ)アクリル酸エステルを含む。
エポキシ基含有単量体の割合が8質量%より多くなると、(B)成分の硬化物との相溶性が向上し、後述の相分離構造が形成されにくくなって、保護膜付きチップの信頼性が低下する。一方で、アクリル系重合体(A)が、エポキシ基含有単量体を構成単量体に全く含まないと、相分離の進行に起因した保護膜のグロス値の低下が過分となるため、グロス値を後述する範囲内にとどめることが難しくなる。すなわち、エポキシ基含有単量体を全く含まないと、保護膜表面には相分離の進行に起因した微小な凹凸ができ、その結果、保護膜表面での反射光の散乱を招くため、グロス値が小さくなり、レーザー印字部の認識性が低下する。
これら観点から、エポキシ基含有単量体の含有量は、全単量体の合計質量中0.1質量%以上であることが好ましく、1質量%以上であることがより好ましい。さらに、グロス値を良好にしつつ信頼性をより高めるためには、3質量%以上であることが特に好ましい。また、エポキシ基含有単量体の含有量は、(A)アクリル系共重合体の全単量体の6質量%以下であることが好ましい。
エポキシ基含有(メタ)アクリル酸エステルとしては、たとえば、グリシジル(メタ)アクリレート、β-メチルグリシジル(メタ)アクリレート、(3,4-エポキシシクロヘキシル)メチル(メタ)アクリレート、3-エポキシシクロ-2-ヒドロキシプロピル(メタ)アクリレート等が、非アクリル系エポキシ基含有単量体としては、たとえば、グリシジルクロトネート、アリルグリシジルエーテル等が挙げられる。エポキシ基含有単量体としては、エポキシ基含有(メタ)アクリル酸エステルが好ましい。 <(A) Acrylic polymer>
(A) An acrylic polymer is a component that imparts flexibility and film-forming properties to a protective film and a protective film-forming film, and is a copolymer of an epoxy group-containing monomer and another monomer. In addition, the ratio of the epoxy group-containing monomer is 8% by mass or less in the total monomer constituting the (A) acrylic polymer. Specifically, the monomer constituting the (A) acrylic polymer contains one or more epoxy groups selected from epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers. It consists of a monomer and various (meth) acrylic acid ester which does not have an epoxy group, and / or a non-acrylic epoxy group-free monomer. In this case, when the epoxy group-containing monomer is composed only of a non-acrylic epoxy group-containing monomer, the monomer constituting the acrylic polymer is various (meth) acrylic acids having no epoxy group. Contains esters.
When the proportion of the epoxy group-containing monomer is more than 8% by mass, the compatibility with the cured product of the component (B) is improved, the later-described phase separation structure is hardly formed, and the reliability of the chip with the protective film is improved. Decreases. On the other hand, if the acrylic polymer (A) does not contain any epoxy group-containing monomer as a constituent monomer, the reduction in the gloss value of the protective film due to the progress of phase separation becomes excessive. It becomes difficult to keep the value within the range described below. In other words, if the epoxy group-containing monomer is not included at all, the surface of the protective film has minute irregularities due to the progress of phase separation, resulting in scattering of reflected light on the surface of the protective film. Becomes smaller and the recognizability of the laser printing part is lowered.
From these viewpoints, the content of the epoxy group-containing monomer is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total mass of all monomers. Furthermore, in order to further improve the reliability while improving the gloss value, it is particularly preferably 3% by mass or more. Moreover, it is preferable that content of an epoxy-group-containing monomer is 6 mass% or less of the total monomer of (A) acrylic copolymer.
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-epoxycyclo-2- Examples of the non-acrylic epoxy group-containing monomer such as hydroxypropyl (meth) acrylate include glycidyl crotonate and allyl glycidyl ether. As the epoxy group-containing monomer, an epoxy group-containing (meth) acrylic acid ester is preferable.
(A)アクリル系重合体を構成する単量体は、上記他の単量体として、(メタ)アクリル酸アルキルエステルを含むことが好ましい。これにより、(メタ)アクリル酸アルキルエステルの炭素数の増減や、異なる炭素数の(メタ)アクリル酸アルキルエステルの組み合わせにより、(A)アクリル系重合体のガラス転移温度を調整することが容易となる。(メタ)アクリル酸アルキルエステルは、(A)アクリル系重合体を構成する全単量体の50質量%以上であることが好ましく、70質量%以上であることがより好ましい。また、(メタ)アクリル酸アルキルエステルは、(A)アクリル系重合体を構成する全単量体の92質量%以下であることが好ましい。
(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ラウリル等、アルキル基の炭素数が1~18の(メタ)アクリル酸アルキルエステルが挙げられる。 (A) Other monomers in the acrylic polymer include (meth) acrylic acid alkyl esters and other (meth) acrylic acid derivatives.
(A) It is preferable that the monomer which comprises an acrylic polymer contains (meth) acrylic-acid alkylester as said other monomer. This makes it easy to adjust the glass transition temperature of the (A) acrylic polymer by increasing or decreasing the number of carbon atoms of the (meth) acrylic acid alkyl ester or by combining (meth) acrylic acid alkyl esters having different carbon numbers. Become. The (meth) acrylic acid alkyl ester is preferably 50% by mass or more, and more preferably 70% by mass or more of the total monomer constituting the (A) acrylic polymer. Moreover, it is preferable that (meth) acrylic-acid alkylester is 92 mass% or less of all the monomers which comprise (A) acrylic polymer.
Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic acid. 2-ethylhexyl, isooctyl (meth) 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 having an alkyl group with 1 to 18 carbon atoms.
水酸基含有(メタ)アクリル酸エステルは、(A)アクリル系重合体を構成する全単量体の1~30質量%であることが好ましく、5~25質量%であることがより好ましく、10~20質量%であることがさらに好ましい。 Furthermore, it is preferable that the monomer which comprises (A) acrylic polymer contains a hydroxyl-containing (meth) acrylic acid ester as another (meth) acrylic acid derivative. When the hydroxyl group is introduced into the acrylic copolymer by the hydroxyl group-containing (meth) acrylic acid ester, it becomes easy to control the adhesion to the semiconductor chip and the adhesive property. Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
The hydroxyl group-containing (meth) acrylic acid ester is preferably 1 to 30% by mass, more preferably 5 to 25% by mass of the total monomers constituting the (A) acrylic polymer. More preferably, it is 20 mass%.
また、(A)アクリル系重合体のガラス転移温度は、6℃以下であることが好ましい。ガラス転移温度が6℃以下であることにより、後述するグロス値を向上させ、印字認識性を良好にすることができる。この理由は、必ずしも明らかではないが、アクリル系重合体(A)が適度に運動性を有することに起因して、硬化後の保護膜の表面形状が平滑化するためと推定される。 In the present invention, the (A) acrylic polymer has a glass transition temperature (Tg) of −3 ° C. or higher. When the glass transition temperature is less than −3 ° C., the mobility of the (A) acrylic polymer is not sufficiently suppressed, and the protective film is likely to be deformed due to the thermal history, thereby improving the reliability of the chip with the protective film. It cannot be improved sufficiently. In the present invention, the glass transition temperature of the acrylic polymer (A) is a theoretical value obtained from the Fox equation.
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 gloss value described later can be improved and the print recognizability can be improved. Although this reason is not necessarily clear, it is presumed that the surface shape of the protective film after curing is smoothed because the acrylic polymer (A) has moderate mobility.
なお、(A)アクリル系重合体は、保護膜形成用フィルムの全質量(固形分換算)に占める割合として、通常10~80質量%、好ましくは15~50質量%である。 For the phase rich in (A) and the phase rich in the cured product of (B), observe what substance is the main component of the phase from, for example, a measurement chart of a phase by Raman scattering spectrometry. Can be determined. If the size of the phase separation structure is less than the resolution of Raman spectroscopy, the hardness of the tapping mode measurement of SPM (scanning probe microscope) is used as an index, and the harder phase is rich in the cured product of component (B). It can be estimated that the softer phase is richer in the component (A). Therefore, in this invention, it can be confirmed whether the phase-separation structure is formed by Raman scattering spectroscopy measurement or SPM observation of the protective film obtained by hardening | curing the film for protective film formation.
The proportion of the (A) acrylic polymer in the total mass (in terms of solid content) of the protective film-forming film is usually 10 to 80% by mass, preferably 15 to 50% by mass.
(B)エポキシ系硬化性成分は、硬化により硬質の保護膜を半導体チップ上に形成させるための成分であり、通常、エポキシ系化合物および熱硬化剤からなる。
保護膜形成用フィルムにおいて、(B)エポキシ系硬化性成分は、(A)アクリル系重合体100質量部に対して、好ましくは250質量部以下、より好ましくは150質量部以下、さらに好ましくは100質量部以下である。また、(B)エポキシ系硬化性成分は、(A)アクリル系重合体100質量部に対して、好ましくは20質量部以上、より好ましくは40質量部以上、さらに好ましくは60質量部以上である。
(B)エポキシ系硬化性成分の含有量が上記範囲とすることにより、半導体チップ等の被着体に対する十分な接着性が得られ、また、後述する支持シートとの剥離力が適切となり、支持シートを保護膜形成用フィルムから剥離する際の剥離不良等も防止できる。さらに、上記したように(B)成分の配合量を所定の上限値以下の範囲に制限することで、(A)成分に富む相が連続相となりやすく、半導体チップの信頼性を高めることができ、また、グロス値を向上させやすくなる。
なお、(B)エポキシ系硬化性成分は、保護膜形成用フィルムの全質量(固形分換算)に占める割合として、通常5~60質量%、好ましくは10~40質量%程度である。 <(B) Epoxy curable component>
(B) The epoxy-based curable component is a component for forming a hard protective film on the semiconductor chip by curing, and usually comprises an epoxy-based compound and a thermosetting agent.
In the protective film-forming film, the (B) epoxy-based curable component is preferably 250 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 with respect to 100 parts by mass of the (A) acrylic polymer. It is below mass parts. The (B) epoxy-based curable component is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 60 parts by mass or more with respect to 100 parts by mass of the (A) acrylic polymer. .
(B) By making content of an epoxy-type curable component into the said range, sufficient adhesiveness with respect to adherends, such as a semiconductor chip, is obtained, and peeling force with the support sheet mentioned later becomes appropriate, and supports. It is also possible to prevent peeling failure when the sheet is peeled from the protective film-forming film. Furthermore, as described above, by limiting the blending amount of the component (B) to a range below a predetermined upper limit value, the phase rich in the component (A) is likely to be a continuous phase, and the reliability of the semiconductor chip can be improved. Moreover, it becomes easy to improve the gloss value.
The proportion of the (B) epoxy-based curable component in the total mass (in terms of solid content) of the protective film-forming film is usually about 5 to 60% by mass, preferably about 10 to 40% by mass.
(C)充填材は、保護膜に耐湿性、寸法安定性などを与える成分であって、具体的には無機フィラー等が挙げられる。また、保護膜にレーザーマーキング(レーザー光により保護膜表面を削り取り印字を行う方法)を施すことにより、レーザー光により削り取られた部分(印字部分)は、(C)充填材が露出して反射光を拡散させるため、非印字部分とのコントラストが向上し認識可能になる。
好ましい無機フィラーとしては、シリカ、アルミナ、タルク、炭酸カルシウム、酸化チタン、酸化鉄、炭化珪素、窒化ホウ素等の粉末、これらを球形化したビーズ、単結晶繊維およびガラス繊維等が挙げられる。これらのなかでは、シリカフィラーおよびアルミナフィラーが特に好ましい。また、上記無機フィラーは、単独でまたは2種以上を混合して使用することができる。
また、充填材の平均粒径は、特に限定されないが、0.1~20μmが好ましい。0.1μm以上であれば、保護膜形成用組成物を、支持シート上に塗布乾燥して保護膜形成用フィルムを得る場合などに、保護膜形成用組成物を塗布に適した性状となる傾向がある。また、20μm以下であればグロス値がより向上しやすくなる。
また、これら観点から、充填材の平均粒径は、0.2~10μmがより好ましく、0.3~6μmがさらに好ましい。
なお、平均粒径は、動的光散乱法を用いた粒度分布計によって測定されたものである。粒度分布計としては、たとえば、日機装社製のNanotrac150等が挙げられる。
保護膜形成用フィルムにおける(C)充填材の含有量は、保護膜形成用フィルムの全質量(固形分換算)に占める割合として、10質量%以上であることが好ましく、30質量%以上であることがより好ましく、50質量%以上であることがさらに好ましい。また、(C)充填材の含有量は、保護膜形成用フィルムの全質量に対して、80質量%以下であることが好ましく、70質量%以下であることがより好ましく、63質量%以下であることがさらに好ましい。(C)充填材の含有量をこれら範囲とすることで、上記した充填材の効果を発揮しやすくなる。また、(C)充填材の含有量を50質量%以上とすることで、レーザーマーキングされた印字部と非印字部のコントラストが向上し、印字の認識性が良好となる。また、上記上限値以下とすることで、グロス値を向上させやすくなる。 <(C) Filler>
(C) The filler is a component that gives the protective film moisture resistance, dimensional stability, and the like, and specifically includes an inorganic filler. In addition, by applying laser marking to the protective film (a method in which the surface of the protective film is scraped and printed by laser light), the portion (printed part) scraped by the laser light is exposed to the (C) filler material and reflected light. Is diffused, the contrast with the non-printing portion is improved and recognition becomes possible.
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. Of these, silica filler and alumina filler are particularly preferable. Moreover, 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. If the thickness is 0.1 μm or more, the protective film-forming composition tends to be suitable for coating when the protective film-forming composition is applied and dried on a support sheet to obtain a protective film-forming film. There is. Moreover, if it is 20 micrometers or less, it will become easy to improve a gross value.
From these viewpoints, the average particle diameter of the filler is more preferably 0.2 to 10 μm, and further preferably 0.3 to 6 μm.
The average particle diameter is measured with a particle size distribution meter using a dynamic light scattering method. Examples of the particle size distribution meter include Nanotrac 150 manufactured by Nikkiso Co., Ltd.
The content of the (C) filler in the protective film-forming film is preferably 10% by mass or more, and preferably 30% by mass or more, as a proportion of the total mass (in terms of solid content) of the protective film-forming film. More preferably, it is more preferably 50% by mass or more. Moreover, it is preferable that content of (C) filler is 80 mass% or less with respect to the total mass of the film for protective film formation, It is more preferable that it is 70 mass% or less, It is 63 mass% or less. More preferably it is. (C) By making content of a filler into these ranges, it becomes easy to exhibit the effect of an above-described filler. Further, by setting the content of the (C) filler to 50% by mass or more, the contrast between the laser-marked printed portion and the non-printed portion is improved, and the print recognizability is improved. Moreover, it becomes easy to improve a gross value by setting it as the said upper limit or less.
保護膜形成用フィルムは、半導体チップを機器に組み込んだ際、周囲の装置から発生する赤外線等を遮蔽して、半導体チップの誤作動を防止することができるため、(D)着色剤を含有することが好ましい。また、(D)着色剤を含有することで、保護膜形成用フィルムを硬化して得た保護膜に、製品番号やマーク等を印字した際の文字の識別性を向上させることができる。すなわち、半導体チップの保護膜を形成した背面には、品番等が通常レーザーマーキング法により印字されるが、保護膜が(D)着色剤を含有することで、印字部分と、非印字部分のコントラスト差が大きくなり識別性が向上する。 <(D) Colorant>
The protective film-forming film contains (D) a colorant because when the semiconductor chip is incorporated in a device, it can shield infrared rays generated from surrounding devices and prevent malfunction of the semiconductor chip. It is preferable. In addition, by containing the colorant (D), it is possible to improve the character distinguishability when a product number, a mark, or the like is printed on the protective film obtained by curing the protective film-forming film. That is, on the back surface of the semiconductor chip on which the protective film is formed, the product number or the like is usually printed by the laser marking method, but the protective film contains the (D) colorant, so that the contrast between the printed part and the non-printed part is The difference is increased and the discrimination is improved.
これらの中では、電磁波や赤外線の遮蔽性が良好で、かつレーザーマーキング法による識別性をより向上させることが可能な黒色顔料がより好ましい。黒色顔料としては、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が用いられるが、これらに限定されることはない。半導体チップの信頼性を高める観点からは、カーボンブラックが特に好ましい。(D)着色剤は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
(D)着色剤の配合量は、保護膜形成用フィルムの全質量(固形分換算)に占める割合として、好ましくは0.01~25質量%、より好ましくは0.03~15質量%である。 (D) An organic or inorganic pigment or dye is used as the colorant. 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.
In these, the black pigment which has favorable shielding property of electromagnetic waves and infrared rays, and can improve the discriminability by a laser marking method is more preferable. 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 chip. (D) A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The blending amount of the colorant (D) is preferably 0.01 to 25% by mass, more preferably 0.03 to 15% by mass as a proportion of the total mass (converted to solid content) of the protective film-forming film. .
保護膜形成用フィルムには、(E)カップリング剤が配合されていてもよい。
(E)カップリング剤としては、メトキシ基、エトキシ基等のアルコキシ基を有するシランカップリング剤が好ましい。また、(E)カップリング剤としては、(A)アクリル系重合体や(B)エポキシ系硬化性成分などが有する官能基と反応する、アルコキシ基以外の反応性官能基を有する化合物が好ましく使用される。反応性官能基としては、グリシドキシ基、グリシドキシ基以外のエポキシ基、アミノ基、(メタ)アクリロキシ基、(メタ)アクリロキシ基以外のビニル基、メルカプト基等が挙げられる。これらの中では、グリシドキシ基、エポキシ基が好ましい。 <(E) Coupling agent>
(E) A coupling agent may be mix | blended with the film for protective film formation.
(E) As a coupling agent, the silane coupling agent which has alkoxy groups, such as a methoxy group and an ethoxy group, is preferable. In addition, as the coupling agent (E), a compound having a reactive functional group other than an alkoxy group that reacts with a functional group of (A) an acrylic polymer or (B) an epoxy curable component is preferably used. Is done. Examples of reactive functional groups include glycidoxy groups, epoxy groups other than glycidoxy groups, amino groups, (meth) acryloxy groups, vinyl groups other than (meth) acryloxy groups, mercapto groups, and the like. In these, a glycidoxy group and an epoxy group are preferable.
低分子量シランカップリング剤としては、具体的にはγ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-(メタクリロプロピル)トリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、γ-ウレイドプロピルトリエトキシシラン、N-6-(アミノエチル)-γ-アミノプロピルメチルジエトキシシラン、γ-メルカプトプロピルトリエトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、ビニルトリアセトキシシランなどが挙げられる。
オリゴマータイプのシランカップリング剤は、シロキサン骨格を有するオルガノポリシロキサンであるとともに、ケイ素原子に直接結合するアルコキシ基を有するものが好ましい。
(E)カップリング剤の含有量は、保護膜形成用フィルムの全質量(固形分換算)に占める割合として、好ましくは0.01~10.0質量%、より好ましくは0.1~3.0質量%である。 As the silane coupling agent, a low molecular weight silane coupling agent having a molecular weight of less than 300 may be used, an oligomer type silane coupling agent having a molecular weight of 300 or more may be used, and these are used in combination. May be.
Specific examples of the low molecular weight silane coupling agent 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.
The oligomer type silane coupling agent is preferably an organopolysiloxane having a siloxane skeleton and an alkoxy group directly bonded to a silicon atom.
(E) The content of the coupling agent is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 3.% by mass as a ratio to the total mass (in terms of solid content) of the protective film-forming film. 0% by mass.
(F)硬化促進剤は、保護膜形成層の硬化速度を調整するために、保護膜形成用フィルムに含有されてもよい。
好ましい硬化促進剤としては、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノールなどの3級アミン類;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールなどのイミダゾール類;トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィンなどの有機ホスフィン類;テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレートなどのテトラフェニルボロン塩などが挙げられる。これらは1種単独で、または2種以上混合して使用することができる。
(F)硬化促進剤は、(B)エポキシ系硬化性成分100質量部に対して、好ましくは0.01~10質量部、さらに好ましくは0.1~5質量部の量で含まれる。(F)硬化促進剤を上記範囲の量で含有することにより、保護膜形成用フィルムは高温度高湿度下に曝されても優れた接着特性を有し、厳しい条件に曝された場合であっても高い信頼性を達成することができる。 <(F) Curing accelerator>
(F) The curing accelerator may be contained in the protective film-forming 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, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine and 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 (F) curing accelerator 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 (B) epoxy-based curable component. (F) By containing the curing accelerator in an amount within the above range, the protective film-forming film has excellent adhesive properties even when exposed to high temperatures and high humidity, and is exposed to severe conditions. Even high reliability can be achieved.
保護膜形成用フィルムに含まれてもよいその他の添加剤としては、特にこれらに限定されるわけではないが、架橋剤、相溶化剤、レベリング剤、可塑剤、帯電防止剤、酸化防止剤、イオン捕捉剤、ゲッタリング剤、連鎖移動剤、エネルギー線重合性化合物、光重合開始剤等が挙げられる。保護膜形成用フィルムは、例えば、相溶化剤が配合されることにより、(A)成分に富む相と、(B)成分の硬化物に富む相の相溶性を適宜調整して、適切な相分離構造が設計可能となる。 <(G) Other additives>
Other additives that may be included in the protective film-forming film are not particularly limited to these, but include crosslinking agents, compatibilizers, leveling agents, plasticizers, antistatic agents, antioxidants, Examples thereof include an ion scavenger, a gettering agent, a chain transfer agent, an energy beam polymerizable compound, and a photopolymerization initiator. The protective film-forming film is prepared by appropriately adjusting the compatibility of the phase rich in the component (A) and the phase rich in the cured product of the component (B) by adding a compatibilizing agent, for example. A separation structure can be designed.
保護膜形成用フィルムは、上記配合を有することにより、硬化されて得られる保護膜の少なくとも一方の面のJIS Z 8741により測定されるグロス値が20以上となるものである。本発明では、グロス値が20以上となる面と反対側の面を、ウエハに貼付して硬化することで、保護膜のレーザーマーキングによる被印字面がグロス値20以上を有することになる。そのため、本発明では、印字部と非印字部のコントラストが向上し、印字部分の識別性が良好になる。
上記グロス値は、コントラストをより向上させて、文字の識別性を上げるために、27以上であることが好ましい。また、グロス値は、特に限定されないが、45以下であることが好ましい。
なお、グロス値は、特に限定されるわけではないが、例えば、エポキシ基含有単量体やアルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステル等の量の調整、(A)成分に対する(B)成分の含有量の調整、充填剤の種類の選択、充填剤の含有量若しくは粒径の調整、又は、その他の添加剤の添加により適宜調整可能である。
保護膜形成用フィルムの厚さは、特に限定されないが、好ましくは3~300μm、よりに好ましくは5~250μm、さらに好ましくは7~200μmである。 <Gross value>
When the protective film-forming film has the above composition, the gloss value measured by JIS Z 8741 of at least one surface of the protective film obtained by curing is 20 or more. In the present invention, the surface to be printed by laser marking of the protective film has a gloss value of 20 or more by attaching and curing the surface opposite to the surface having a gloss value of 20 or more on the wafer. For this reason, in the present invention, the contrast between the printed portion and the non-printed portion is improved, and the distinguishability of the printed portion is improved.
The gloss value is preferably 27 or more in order to further improve the contrast and improve the character discrimination. The gloss value is not particularly limited, but is preferably 45 or less.
The gloss value is not particularly limited. For example, adjustment of the amount of an epoxy group-containing monomer or an alkyl group (meth) acrylic acid alkyl ester having 4 or more carbon atoms, (A) component, etc. It is possible to adjust appropriately by adjusting the content of component (B) relative to the above, selecting the type of filler, adjusting the content or particle size of the filler, or adding other additives.
The thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and still more preferably 7 to 200 μm.
本発明の保護膜形成用フィルムは,通常、支持シート上に剥離可能に形成され、積層体である保護膜形成用複合シートとして使用される。保護膜形成用フィルムは、支持シートと同形状とすることができる。また、保護膜形成用複合シートは、保護膜形成用フィルムが、ウエハと略同形状又はウエハの形状をそっくり含むことのできる形状に調製されたものであり、保護膜形成用フィルムよりも大きなサイズの支持シート上に積層されている、いわゆる事前成形構成をとっていてもよい。
支持シートは、保護膜形成用フィルムを支持するものであって、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルムなどのフィルムが用いられる。またこれらの架橋フィルムも用いられる。さらに、これらから選択された2以上の積層フィルムであってもよい。また、これらを着色したフィルムも用いることができる。
支持シートの保護膜形成用フィルムが形成される側の面は、適宜剥離処理が施されていてもよい。剥離処理に用いられる剥離剤としては、例えば、アルキッド系、シリコーン系、フッ素系、不飽和ポリエステル系、ポリオレフィン系、ワックス系などが挙げられるが、アルキッド系、シリコーン系、フッ素系の剥離剤が耐熱性を有するので好ましい。
また、保護膜形成用複合シートにおいて、保護膜形成用フィルムの支持シートが設けられる側の面とは反対の面には、軽剥離性の剥離シートが貼り合わされ、その剥離シートによって保護膜形成用フィルムが保護されてもよい。 [Composite sheet for protective film formation]
The protective film-forming film of the present invention is usually formed on a support sheet so as to be peelable and used as a protective film-forming composite sheet as a laminate. The protective film-forming film can have the same shape as the support sheet. In addition, the protective film-forming composite sheet is prepared by making the protective film-forming film substantially the same shape as the wafer or including the shape of the wafer, and having a larger size than the protective film-forming film. A so-called pre-molded configuration laminated on the supporting sheet may be adopted.
The support sheet is for supporting a protective film-forming 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 A film such as a film, a polystyrene film, a polycarbonate film, a polyimide film, or a fluororesin film is used. These crosslinked films are also used. Furthermore, two or more laminated films selected from these may be used. Moreover, the film which colored these can also be used.
The surface of the support sheet on which the protective film-forming film is formed may be appropriately subjected to a peeling treatment. Examples of the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax, but alkyd, silicone, and fluorine release agents are heat resistant. It is preferable because of its properties.
Further, in the composite sheet for forming a protective film, a light-peelable release sheet is bonded to the surface opposite to the surface on which the support sheet of the protective film-forming film is provided, and the protective sheet is formed by the release sheet. The film may be protected.
保護膜形成用フィルムは、半導体ウエハ、半導体チップ等の被着体に貼付され、その後熱硬化されて保護膜として使用される。ここで、保護膜形成用フィルムが、保護膜形成用複合シートとして被着体に貼付される場合には、まず、剥離シートで保護されている場合には剥離シートが剥離され、次いで、保護膜形成用フィルムと支持フィルムの積層体が、被着体に貼付された後、支持シートが保護膜形成用フィルムから剥離される。 [How to use protective film-forming film]
The protective film-forming film is affixed to an adherend such as a semiconductor wafer or a semiconductor chip, and then thermally cured and used as a protective film. Here, when the protective film-forming film is attached to the adherend as a protective film-forming composite sheet, first, when the protective film is protected by the release sheet, the release sheet is peeled off, and then the protective film After the laminate of the forming film and the support film is attached to the adherend, the support sheet is peeled off from the protective film forming film.
本方法では、まず、上記保護膜形成用フィルムを半導体ウエハの裏面に積層する。例えば、保護膜形成用複合シートを使用する場合には、保護膜形成用フィルムと基材シートの積層体を半導体ウエハの裏面に貼付する。その後、保護膜形成用フィルムから支持シートを剥離した後、半導体ウエハ上に積層された保護膜形成用フィルムを熱硬化し、ウエハの全面に保護膜を形成する。
なお、半導体ウエハは、シリコンウエハであってもよく、またガリウム・砒素などの化合物半導体ウエハであってもよい。また、半導体ウエハは、その表面に回路が形成されているとともに、裏面が適宜研削等され、厚みが50~500μm程度とされるものである。 Hereinafter, an example in which a protective film-forming film is used for protecting a back surface of a semiconductor chip and a chip with a protective film is manufactured will be described as to how to use the protective film-forming film, but is limited to the examples shown below. I don't mean.
In this method, first, the protective film-forming film is laminated on the back surface of the semiconductor wafer. For example, when a composite sheet for forming a protective film is used, a laminate of the protective film-forming film and the base sheet is attached to the back surface of the semiconductor wafer. Thereafter, the support sheet is peeled from the protective film-forming film, and then the protective film-forming film laminated on the semiconductor wafer is thermally cured to form a protective film on the entire surface of the wafer.
The semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Further, the semiconductor wafer has a circuit formed on the front surface thereof, and the back surface thereof is appropriately ground or the like to have a thickness of about 50 to 500 μm.
本発明の保護膜付きチップは、例えば上記製造方法により得られ、半導体チップと、該半導体チップの裏面に積層される保護膜とを備え、該保護膜は、上述の保護膜形成用フィルムを硬化させて形成され、チップ裏面を保護するものである。保護膜は、半導体チップ側の面とは反対の面が、JIS Z 8741により測定されるグロス値が20以上となるものである。
保護膜付きチップを、フェースダウン方式で基板等の上に実装することで半導体装置を製造することができる。また、保護膜付きチップは、ダイパッド部または別の半導体チップなどの他の部材上(チップ搭載部上)に接着することにより、半導体装置を製造することもできる。 [Chip with protective film]
The chip with a protective film of the present invention is obtained, for example, by the above-described 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 protective film-forming film described above. The back surface of the chip is protected. The surface of the protective film opposite to the surface on the semiconductor chip side has a gloss 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 by a face-down method. Further, the semiconductor device can also be manufactured by bonding the chip with protective film to another member (on the chip mounting part) such as a die pad part or another semiconductor chip.
(1)重量平均分子量(Mw)
ゲルパーミエーションクロマトグラフィー(GPC)法により、標準ポリスチレン換算の重量平均分子量Mwを測定した。
測定装置:東ソー社製の高速GPC装置「HLC-8120GPC」に、高速カラム「TSK guard column HXL-H」、「TSK Gel GMHXL」、「TSK Gel G2000 HXL」(以上、全て東ソー社製)をこの順序で連結して測定した。
カラム温度:40℃、送液速度:1.0mL/分、検出器:示差屈折率計 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 in terms of standard polystyrene was measured by gel permeation chromatography (GPC).
Measuring device: Tosoh's high-speed GPC device "HLC-8120GPC", high-speed column "TSK guard column H XL -H", "TSK Gel GMH XL ", "TSK Gel G2000 H XL " ) In this order and measured.
Column temperature: 40 ° C., liquid feed rate: 1.0 mL / min, detector: differential refractometer
#2000研磨したシリコンウエハ(200mm径、厚さ280μm)の研磨面に、剥離シートを剥離した保護膜形成用複合シートの保護膜形成用フィルムを、テープマウンター(リンテック株式会社製、Adwill RAD-3600 F/12)を用いて70℃に加熱しながら貼付した。次いで、支持シートを剥離した後、130℃で2時間加熱を行うことにより、保護膜形成用フィルムを硬化して、シリコンウエハ上に保護膜を形成した。下記測定装置及び測定条件で、保護膜表面の60度の鏡面光沢度を測定し、グロス値とした。
測定装置:VG 2000 日本電色工業株式会社製
測定条件:JIS Z 8741に準じた (2) Gloss value A protective film forming film of a composite sheet for forming a protective film having a release sheet peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, thickness 280 μm) is a tape mounter (manufactured by Lintec Corporation). Adwill RAD-3600 F / 12) was applied while heating to 70 ° C. Next, after peeling off the support sheet, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to form a protective film on the silicon wafer. The specular glossiness of 60 degrees on the surface of the protective film was measured with the following measuring apparatus and measurement conditions, and the gloss value was obtained.
Measuring device: VG 2000 manufactured by Nippon Denshoku Industries Co., Ltd. Measuring conditions: conforming to JIS Z 8741
#2000研磨したシリコンウエハ(200mm径、厚さ280μm)の研磨面に、剥離シートを剥離した保護膜形成用複合シートの保護膜形成用フィルムをテープマウンター(リンテック株式会社製, Adwill RAD-3600 F/12)を用いて70℃に加熱しながら貼付した。次いで、支持シートを剥離した後、130℃で2時間加熱を行うことにより、保護膜形成用フィルムを硬化して、シリコンウエハに保護膜を形成した。保護膜表面に、レーザー印字装置(パナソニックデバイスSUNX株式会社製 LP-V10U、レーザー波長:1056nm)を用いて、一文字の幅が300μm以下である文字を4文字印字した。得られた印字済みの保護膜面をデジタル顕微鏡で確認し、印字が読み取り可能かを画像で確認した。判断基準は、デジタル顕微鏡の観察時に、直射光で印字部を照らしているとき、十分に読取可能を“A”、読み取り可能だが不鮮明を“B”、読み取り不可能を“F”と表現した。 (3) Character recognition (printability)
A tape mounter (Adwill RAD-3600 F, manufactured by Lintec Co., Ltd.) is used to form a protective film forming film of a composite sheet for forming a protective film with a release sheet peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, 280 μm thick). / 12) was applied while heating to 70 ° C. Next, after peeling off the support sheet, the film for forming a protective film was cured by heating at 130 ° C. for 2 hours, thereby forming a protective film on the silicon wafer. Using a laser printing device (LP-V10U, manufactured by Panasonic Device Sunx Co., Ltd., laser wavelength: 1056 nm), four characters having a character width of 300 μm or less were printed on the surface of the protective film. The printed protective film surface thus obtained was confirmed with a digital microscope, and it was confirmed with an image whether the print was readable. Judgment criteria were expressed as “A” for fully readable, “B” for readable but unclear, and “F” for unreadable when the printed part was illuminated with direct light when observing with a digital microscope.
#2000研磨したシリコンウエハ(200mm径、厚さ280μm)の研磨面に、剥離シートを剥離した保護膜形成用複合シートの保護膜形成用フィルムをテープマウンター(リンテック株式会社製、Adwill RAD-3600 F/12)を用いて、70℃に加熱しながら貼付した。次いで、支持シートを剥離した後、130℃で2時間加熱を行うことにより、保護膜形成用フィルムを硬化して、シリコンウエハ上に保護膜を形成した。そして、保護膜側をダイシングテープ(リンテック株式会社製Adwill D-676H)に貼付し、ダイシング装置(株式会社ディスコ製、DFD651)を使用して3mm×3mmサイズにダイシングすることで信頼性評価用の保護膜付きチップを得た。 (4) Reliability evaluation A tape mounter (manufactured by Lintec Corporation) is used to form a protective film forming film of a composite sheet for forming a protective film on which a release sheet is peeled off on a polished surface of a # 2000 polished silicon wafer (200 mm diameter, 280 μm thick). , Adwill RAD-3600 F / 12) was applied while heating to 70 ° C. Next, after peeling off the support sheet, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to form a protective film on the silicon wafer. Then, the protective film side is affixed to a dicing tape (Adwill D-676H manufactured by Lintec Corporation), and dicing into 3 mm × 3 mm size using a dicing apparatus (DFD Co., Ltd., DFD651) for reliability evaluation. A chip with a protective film was obtained.
その後、25個の保護膜付きチップを冷熱衝撃装置から取り出して信頼性を評価した。具体的には、チップと保護膜との接合部での浮き・剥がれや保護膜におけるクラックの有無を、走査型超音波探傷装置(日立建機ファインテック株式会社製 Hye‐Focus)および断面観察により評価し、浮き、剥がれおよびクラックのいずれかがあればNGとした。25個のチップのうちのNGの個数を表4に示す。 The chip with a protective film for reliability evaluation was first processed under conditions (preconditions) imitating a process in which a semiconductor chip was actually mounted. Specifically, the chip with a protective film is baked at 125 ° C. for 20 hours, and then left to stand for 168 hours under conditions of 85 ° C. and 85% RH to immediately absorb moisture, followed by preheating at 160 ° C., peak temperature at 260 ° C., and heating. It was passed 3 times through an IR reflow oven for 30 seconds. Twenty-five protective film-coated chips treated with these preconditions were placed in a thermal shock apparatus (TSE-11-A, manufactured by ESPEC Corporation), held at −65 ° C. for 10 minutes, and then held at 150 ° C. for 10 minutes. The cycle was repeated 1000 times.
Thereafter, 25 chips with protective films were taken out of the thermal shock apparatus and evaluated for reliability. Specifically, the presence or absence of floating / peeling at the joint between the chip and the protective film or cracks in the protective film is determined by scanning ultrasonic flaw detector (Hy-Focus manufactured by Hitachi Construction Machinery Finetech Co., Ltd.) and cross-sectional observation. It was evaluated as NG if any of floating, peeling and cracking was found. Table 4 shows the number of NGs out of 25 chips.
実施例1において、保護膜形成フィルムを形成する成分は以下の通りであった。
(A)アクリル系共重合体:アクリル酸n-ブチル1質量部と、メタクリル酸メチル79質量部と、アクリル酸2-ヒドロキシエチル15質量部と、メタクリル酸グリシジル5質量部とを共重合してなる重量平均分子量(Mw)37万、ガラス転移温度(Tg)7℃の共重合体
(B)エポキシ系硬化性成分
エポキシ系化合物:ビスフェノールA型エポキシ樹脂(日本触媒株式会社製、BPA-328)と、ジシクロペンタジエン型エポキシ樹脂(大日本インキ化学工業株式会社製、エピクロンHP-7200HH)
熱硬化剤:ジシアンジアミド(株式会社ADEKA製、アデカハードナー3636AS)
(C)充填剤:平均粒径8μmの溶融石英フィラー(シリカフィラー、龍森社製、SV-10を物理的に破砕したもの)
(D)着色剤:カーボンブラック(三菱化学株式会社製、MA600、平均粒径:28nm)
(E)シランカップリング剤:オリゴマータイプシランカップリング剤(信越化学工業株式会社製 X-41-1056 メトキシ当量17.1mmol/g、分子量500~1500)と、γ-グリシドキシプロピルトリエトキシシラン(信越化学工業株式会社製 KBE-403 メトキシ当量8.1mmol/g、分子量278.4)と、γ-グリシドキシプロピルトリメトキシシラン(信越化学工業株式会社製 KBM-403 メトキシ当量12.7mmol/g、分子量236.3)
(F)硬化促進剤:2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業株式会社製、キュアゾール2PHZ) Example 1
In Example 1, the components forming the protective film-forming film were as follows.
(A) Acrylic copolymer: copolymerized with 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 having a weight average molecular weight (Mw) of 370,000 and a glass transition temperature (Tg) of 7 ° C. (B) Epoxy curable component Epoxy compound: Bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., BPA-328) And dicyclopentadiene type epoxy resin (Dainippon Ink and Chemicals, Epicron HP-7200HH)
Thermosetting agent: Dicyandiamide (manufactured by ADEKA Corporation, Adeka Hardener 3636AS)
(C) Filler: fused silica filler with an average particle size of 8 μm (silica filler, manufactured by Tatsumori Co., Ltd., physically crushed SV-10)
(D) Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600, average particle size: 28 nm)
(E) Silane coupling agent: 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.) and γ-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. KBE-403 methoxy equivalent 8.1 mmol / g, molecular weight 278.4) and γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-403 methoxy equivalent 12.7 mmol / g, molecular weight 236.3)
(F) Curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curesol 2PHZ)
(A)アクリル系共重合体として、表2に示すものを使用した点を除いては、実施例1と同様に実施した。なお、各実施例、比較例の(A)アクリル共重合体について、重量平均分子量(Mw)及びガラス転移温度(Tg)を合わせて表2に示す。 Example 2 and Comparative Examples 1-6
(A) The same procedure as in Example 1 was carried out except that the acrylic copolymer shown in Table 2 was used. In addition, about the (A) acrylic copolymer of each Example and a comparative example, it shows in Table 2 together with a weight average molecular weight (Mw) and a glass transition temperature (Tg).
(C)成分として、平均粒径8μmのシリカフィラーの代わりに、平均粒径3μmのシリカフィラー(株式会社トクヤマ製、UF310)を使用した以外は実施例2と同様に実施した。
実施例4
(C)成分として、平均粒径8μmのシリカフィラーの代わりに、平均粒径0.5μmのシリカフィラー(アドマテックス社製、SC2050MA)を使用した以外は実施例2と同様に実施した。
実施例5、6
(C)成分の配合量を表3に示すように変更した点を除いて実施例2と同様に実施した。
実施例7、8
(A)及び(B)成分の配合量を表3に示すように変更した点を除いて実施例2と同様に実施した。 Example 3
(C) It implemented similarly to Example 2 except having used the silica filler (made by Tokuyama Corporation, UF310) with an average particle diameter of 3 micrometers instead of the silica filler with an average particle diameter of 8 micrometers.
Example 4
(C) It implemented similarly to Example 2 except having used the silica filler (manufactured by Admatechs, SC2050MA) having an average particle diameter of 0.5 μm instead of the silica filler having an average particle diameter of 8 μm.
Examples 5 and 6
(C) It implemented similarly to Example 2 except the point which changed the compounding quantity of the component as shown in Table 3.
Examples 7 and 8
It implemented similarly to Example 2 except the point which changed the compounding quantity of (A) and (B) component as shown in Table 3.
一方、比較例1では、(A)アクリル系重合体が、構成モノマーとしてエポキシ基含有単量体を含まなかったため、相分離に起因して保護膜表面に微小な凹凸ができ、その結果、保護膜表面での反射光の散乱を招いた。したがって、グロス値が小さくなり、印字認識性が悪くなった。また、比較例2、3、6では、(A)アクリル系重合体のガラス転移温度が-3℃未満となったため、保護膜が熱履歴により変形したと推定され、NGチップの数が多くなり、保護膜付きチップの信頼性を十分に向上させることができなかった。さらに、比較例4、5では、(A)アクリル系重合体が、構成モノマーとしてエポキシ基含有単量体を多量に含んだため、(A)成分と(B)成分の親和性が高く相分離が起こりにくくなり、保護膜付きチップの信頼性は低くなった。 As is apparent from Table 4, in Examples 1 to 8, (A) the acrylic polymer contains an epoxy group-containing monomer of 8% by mass or less as a constituent monomer, and the glass transition temperature is −3 ° C. or higher. As a result, the phase separation between the phase rich in the component (A) and the phase rich in the cured product of the component (B) can be improved and the gloss value can be set to 20 or more. Both sexes could be improved.
On the other hand, in Comparative Example 1, since the (A) acrylic polymer did not contain an epoxy group-containing monomer as a constituent monomer, fine irregularities were formed on the surface of the protective film due to phase separation. The scattering of the reflected light on the film surface was caused. Therefore, the gloss value becomes small and the print recognizability deteriorates. In Comparative Examples 2, 3, and 6, since the glass transition temperature of (A) the acrylic polymer was less than −3 ° C., it was estimated that the protective film was deformed due to thermal history, and the number of NG chips increased. The reliability of the chip with a protective film could not be sufficiently improved. Furthermore, in Comparative Examples 4 and 5, since the (A) acrylic polymer contained a large amount of the epoxy group-containing monomer as a constituent monomer, the affinity between the (A) component and the (B) component is high and phase separation is performed. As a result, the reliability of the chip with the protective film has decreased.
Claims (8)
- 半導体チップを保護する保護膜を形成するための保護膜形成用フィルムであって、
前記保護膜形成用フィルムが、(A)アクリル系重合体、(B)エポキシ系硬化性成分、および(C)充填材を含有し、
(A)アクリル系重合体を構成する単量体が、全単量体の8質量%以下の割合でエポキシ基含有単量体を含むとともに、(A)アクリル系重合体のガラス転移温度が-3℃以上であり、
前記保護膜形成用フィルムを硬化して得た保護膜の少なくとも一面のJIS Z 8741により測定されるグロス値が20以上である保護膜形成用フィルム。 A protective film forming film for forming a protective film for protecting a semiconductor chip,
The protective film-forming film contains (A) an acrylic polymer, (B) an epoxy-based curable component, and (C) a filler,
(A) The monomer constituting the acrylic polymer 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 ° C or higher,
A protective film-forming film having a gloss value of 20 or more as measured by JIS Z 8741 on at least one surface of a protective film obtained by curing the protective film-forming film. - (A)アクリル系重合体のガラス転移温度が6℃以下である請求項1に記載の保護膜形成用フィルム。 (A) The glass transition temperature of an acrylic polymer is 6 degrees C or less, The film for protective film formation of Claim 1.
- (A)アクリル系重合体を構成する単量体が、さらに(メタ)アクリル酸アルキルエステルを含む請求項1又は2に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, wherein the monomer constituting the (A) acrylic polymer further contains a (meth) acrylic acid alkyl ester.
- (A)アクリル系重合体を構成する単量体が、全単量体の12質量%以下の割合でアルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルを含む請求項1~3のいずれかに記載の保護膜形成用フィルム。 The monomer constituting the (A) acrylic polymer contains a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms in a proportion of 12% by mass or less of the total monomer. The film for protective film formation in any one of.
- 前記アルキル基の炭素数が4以上の(メタ)アクリル酸アルキルエステルが、(メタ)アクリル酸ブチルである請求項4に記載の保護膜形成用フィルム。 The protective film-forming film according to claim 4, wherein the alkyl group (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is butyl (meth) acrylate.
- (C)充填材の含有量が、保護膜形成用フィルムの50質量%以上である請求項1~5のいずれかに記載の保護膜形成用フィルム。 6. The protective film-forming film according to claim 1, wherein the content of (C) the filler is 50% by mass or more of the protective film-forming film.
- さらに(D)着色剤を含有する請求項1~6のいずれかに記載の保護膜形成用フィルム。 The protective film-forming film according to claim 1, further comprising (D) a colorant.
- 半導体チップと、前記半導体チップ上に設けられる保護膜とを備える保護膜付きチップであって、
前記保護膜が、保護膜形成用フィルムを硬化させて形成されたものであるとともに、前記保護膜形成用フィルムが、(A)アクリル系重合体、(B)エポキシ系硬化性成分、及び(C)充填材を含有し、
(A)アクリル系重合体を構成する単量体が、全単量体の8質量%以下の割合でエポキシ基含有単量体を含むとともに、(A)アクリル系重合体のガラス転移温度が-3℃以上であり、
前記保護膜は、前記半導体チップ側の面とは反対の面がJIS Z 8741により測定されるグロス値が20以上である保護膜付きチップ。 A chip with a protective film comprising a semiconductor chip and a protective film provided on the semiconductor chip,
The protective film is formed by curing a protective film-forming film, and the protective film-forming film comprises (A) an acrylic polymer, (B) an epoxy-based curable component, and (C ) Contains filler,
(A) The monomer constituting the acrylic polymer 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 ° C or higher,
The protective film is a chip with a protective film in which a surface opposite to the surface on the semiconductor chip side has a gloss value of 20 or more as measured by JIS Z 8741.
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CN201380063150.0A CN104838491B (en) | 2012-12-03 | 2013-11-29 | Diaphragm formation film |
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JP2016213477A (en) * | 2016-06-07 | 2016-12-15 | リンテック株式会社 | Protective film formation sheet |
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KR102487552B1 (en) | 2018-02-05 | 2023-01-11 | 삼성전자주식회사 | Composition for protective film against sawing process and method of manufacturing semiconductor package using the composition |
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