CN104838491B - Diaphragm formation film - Google Patents
Diaphragm formation film Download PDFInfo
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- CN104838491B CN104838491B CN201380063150.0A CN201380063150A CN104838491B CN 104838491 B CN104838491 B CN 104838491B CN 201380063150 A CN201380063150 A CN 201380063150A CN 104838491 B CN104838491 B CN 104838491B
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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
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- 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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- 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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- 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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- 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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- 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
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- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- H01—ELECTRIC ELEMENTS
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
The present invention relates to a kind of diaphragm formation film, it is used for the diaphragm to form protection semiconductor chip, the diaphragm formation film contains (A) acrylic polymer, (B) epoxies curability composition and (C) packing material, the monomer for forming (A) acrylic polymer includes the monomer containing epoxide group with below the 8 mass % of whole monomers ratio, and the glass transition temperature of (A) acrylic polymer is more than 3 DEG C, the gloss number that at least one side of diaphragm obtained from the diaphragm formation film solidifies determines according to JIS Z8741 is more than 20.
Description
Technical field
The present invention relates to the diaphragm formation film for being protected to the back side of such as semiconductor chip.
Background technology
In the past, the manufacture of semiconductor device had been carried out using the Method for Installation for being referred to as upside-down mounting mode.In upside-down mounting mode, half
The formation of conductor chip has the chip surface of the electrodes such as projection opposed with substrate etc. and engaged, and on the other hand, chip back exposes,
Therefore, protected with diaphragm.Moreover, (hereinafter referred to as " carry diaphragm in the semiconductor chip protected by diaphragm
Chip ") the back side, by laser printing etc. on diaphragm franking, word etc..
Said protection film is formed such as being applied by resin, but in recent years, such as disclosed in Patent Document 1 that
Sample, in order to ensure uniformity of thickness etc., bonding protective film formation piece and the chip with diaphragm that is formed is practical
Change.The diaphragm formation sets diaphragm formation to be formed with film with piece on support chip, and the diaphragm formation is contained with film
There are the thermosetting component comprising epoxy resin etc. and the binder polymer composition comprising acrylic polymer etc..
On the other hand, as the adhesive film used in the semiconductors, it is known to various films, for example, as in semiconductor package
The adhesive film used in dress etc., Patent Document 2 discloses occur to be separated and with springform each other under B scalariform states
The mixture for measuring 3500~10000GPa 1~3000MPa of Resin A and modulus of elasticity resin B is the adhesive film of essential component.
The copolymerization that it is epoxy resin that the adhesive film of patent document 2, which has used such as Resin A, resin B is methacrylate and acrylonitrile
The acrylic rubber of thing.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-280329 publications
Patent document 2：Japanese Unexamined Patent Publication 2001-220556 publications
The content of the invention
The invention problem to be solved
The diaphragm disclosed in patent document 1 is formed with piece come in the case of forming the diaphragm of semiconductor chip, the band
The chip for having diaphragm easily causes to produce at the junction surface of chip and diaphragm sometimes due to long-term use of to be floated, shells
From, or cracked on diaphragm a problem that, poor reliability.In addition, if will be 2 kinds as disclosed in patent document 2
The composition that composition is separated is converted in chip diaphragm, then is possible to although with the reliability of the chip of diaphragm
To raising, but other problems as the easy variation of identity that the word that laser printing obtains etc. can be produced.
The present invention in view of problem above and carry out, its problem be to provide can obtain reliability it is high with guarantor
The chip of cuticula while the diaphragm of the excellent diaphragm of identity of the word that laser printing obtains etc. can be formed formed and use
Film.
The method solved the problems, such as
Further investigation has been repeated in order to solve above-mentioned problem in the present inventor etc., as a result finds, is protected by being conceived to
The acrylic polymer of cuticula formation resin, make to include containing epoxide group in the monomer of composition acrylic polymer
Monomer, and adjust its mixing ratio as given scope, at the same make acrylic polymer glass transition temperature be to
Fixed scope, can solve above-mentioned problem, so as to complete the following present invention.
That is, the present invention provides following (1)~(8).
(1) a kind of diaphragm formation film, it is used for the diaphragm to form protection semiconductor chip,
The diaphragm formation film contains (A) acrylic polymer, (B) epoxies curability composition and (C) filling
Material,
The monomer for forming (A) acrylic polymer contains epoxy with below the 8 mass % of whole monomers ratio
The monomer of group, and the glass transition temperature of (A) acrylic polymer is more than -3 DEG C,
The light that at least one side of diaphragm obtained from the diaphragm formation film solidifies determines according to JIS Z 8741
Pool value is more than 20.
(2) the diaphragm formation film described in above-mentioned (1), wherein, the glass transition temperature of (A) acrylic polymer
For less than 6 DEG C.
(3) the diaphragm formation film described in above-mentioned (1) or (2), wherein, the monomer of composition (A) acrylic polymer
Also contain (methyl) alkyl acrylate.
(4) the diaphragm formation film any one of above-mentioned (1)~(3), wherein, form (A) acrylic
The monomer of thing contains atomic number of alkyl carbon as more than 4 (methyl) alkyl acrylate using below the 12 mass % of whole monomers ratio
Base ester.
(5) the diaphragm formation film described in above-mentioned (4), wherein, the atomic number of alkyl carbon is more than 4 (methyl) third
Olefin(e) acid Arrcostab is (methyl) butyl acrylate.
(6) the diaphragm formation film any one of above-mentioned (1)~(5), wherein, the content of (C) packing material is
More than the 50 mass % of diaphragm formation film.
(7) the diaphragm formation film any one of above-mentioned (1)~(6), it also contains (D) colouring agent.
(8) a kind of chip with diaphragm, it possesses semiconductor chip and the guarantor being arranged on the semiconductor chip
Cuticula, wherein,
The diaphragm makes diaphragm formation be solidified to form with film, also, the diaphragm formation film contains
(A) acrylic polymer, (B) epoxies curability composition and (C) packing material,
The monomer for forming (A) acrylic polymer contains epoxy with below the 8 mass % of whole monomers ratio
The monomer of group, and the glass transition temperature of (A) acrylic polymer is more than -3 DEG C,
The gloss that the face of the side opposite with the face of the semiconductor chip side of the diaphragm determines according to JIS Z 8741
It is worth for more than 20.
The effect of invention
The present invention, which can provide, can obtain the high chip with diaphragm of reliability while can form laser printing
The diaphragm formation film of the excellent diaphragm of the identity of obtained word.
Embodiment
Hereinafter, the present invention is specifically described using embodiments thereof.
It should be noted that in this manual, " (methyl) acrylate " is intended to indicate that " acrylate " and " methyl
The term of both acrylate ", other similar terms are also identical.
[diaphragm formation film]
The present invention diaphragm formation with film be for formed protect semiconductor chip diaphragm film, it at least contains
(A) acrylic polymer, (B) epoxies curability composition and (C) packing material.
＜ (A) acrylic polymers ＞
(A) acrylic polymer is that flexible, film forming composition is assigned to diaphragm and diaphragm formation film, its by
Monomer containing epoxide group and other monomer copolymerizations and obtain, also, form (A) acrylic polymer whole monomers
In, the ratio of the monomer containing epoxide group is below 8 mass %.Specifically, the monomer of (A) acrylic polymer is formed
By selected from one or more of (methyl) acrylate containing epoxide group and the non-acrylic monomer containing epoxide group
Monomer containing epoxide group and various (methyl) acrylate without epoxide group and/or without epoxide group
Non- acrylic monomer is formed.In this case, the monomer containing epoxide group is only by the non-acrylic compounds containing epoxide group
When monomer is formed, the monomer for forming acrylic polymer includes various (methyl) acrylate without epoxide group.
If the ratio of the monomer containing epoxide group is more than 8 mass %, carried with the compatibility of the solidfied material of (B) composition
It is high, it is difficult to form phase separation structure described later, the reliability decrease of the chip with diaphragm.On the other hand, if acrylic acid
The composition monomer of compound (A) of birdsing of the same feather flock together is entirely free of the monomer containing epoxide group, then makes diaphragm due to the progress of phase separation
Gloss number excessively reduce, therefore, gloss number is difficult to rest in scope described later.That is, if it is entirely free of containing epoxy radicals
The monomer of group, then form small bumps, as a result, causing on diaphragm surface on diaphragm surface because of the progress of phase separation
Reflected light scattering, therefore gloss number diminishes, and the identity in laser printing portion declines.
Consider from above-mentioned viewpoint, in the gross mass of whole monomers, the content of the monomer containing epoxide group is preferably 0.1 matter
More than % is measured, more preferably more than 1 mass %.And then in order that gloss number is good and further improve reliability, particularly preferably
For more than 3 mass %.In addition, the content of the monomer containing epoxide group is preferably whole monomers of (A) acrylic copolymer
Below 6 mass %.
As (methyl) acrylate containing epoxy radicals, for example,：(methyl) glycidyl acrylate,
(methyl) propenoic acid beta-methylglycidyl esters, (3,4- epoxycyclohexyls) methyl (methyl) acrylate, 3- epoxide ring -2- hydroxyls
Base propyl group (methyl) acrylate etc., as the non-acrylic monomer containing epoxide group, for example,：Butenoic acid contracts
Water glyceride, allyl glycidyl ether etc..As the monomer containing epoxide group, (methyl) third of epoxy radicals is preferably comprised
Olefin(e) acid ester.
As other monomers in (A) acrylic polymer, (methyl) alkyl acrylate, other (first can be enumerated
Base) acrylic acid derivative.
The monomer for forming (A) acrylic polymer preferably comprises (methyl) alkyl acrylate as above-mentioned other lists
Body.Thus, by increasing and decreasing the carbon number of (methyl) alkyl acrylate, combining (methyl) alkyl acrylate of different carbon numbers
Base ester, the glass transition temperature of (A) acrylic polymer can be easily adjusted.(methyl) alkyl acrylate is preferably
More than the 50 mass % of whole monomers of (A) acrylic polymer are formed, more preferably more than 70 mass %.In addition, (first
Base) alkyl acrylate be preferably form (A) acrylic polymer whole monomers below 92 mass %.
As (methyl) alkyl acrylate, can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) 2-EHA, (methyl)
Isooctyl acrylate monomer, (methyl) n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl)
The carbon number of the alkyl such as decyl acrylate, (methyl) dodecylacrylate is 1~18 (methyl) alkyl acrylate.
The monomer of (A) acrylic polymer is formed preferably with the 12 of whole monomers of composition (A) acrylic polymer
(methyl) propylene that the carbon number that below quality % amount contains the alkyl in above-mentioned (methyl) alkyl acrylate is more than 4
Acid alkyl ester.Thus, it is more than -3 DEG C that can make glass transition temperature, and gloss number is become good.In order that light
Damp value is good and keeps reliability, and the carbon number of alkyl is that the above-mentioned content of more than 4 (methyl) alkyl acrylate is preferred
For 1~12 mass %, more preferably 5~12 mass %.In addition, (methyl) third that the carbon number as the alkyl is more than 4
Olefin(e) acid Arrcostab, preferably (methyl) butyl acrylate.
In addition, the monomer for forming (A) acrylic polymer preferably comprises the alkane in above-mentioned (methyl) alkyl acrylate
The carbon number of base is less than 3 (methyl) alkyl acrylate.Pass through (methyl) that the carbon number containing alkyl is less than 3
Alkyl acrylate, heat endurance etc. can be made to become good, and easily make (A) acrylic as being described below
The glass transition temperature of thing is more than -3 DEG C.Consider from above-mentioned viewpoint, the carbon number of alkyl is less than 3 (methyl) propylene
Acid alkyl ester is preferably more than the 50 mass %, more preferably 60 mass % for the whole monomers for forming (A) acrylic polymer
More than.In addition, (methyl) alkyl acrylate that the carbon number of alkyl is less than 3 is preferably to form (A) acrylic
Below the 90 mass % of whole monomers of thing.In addition, (methyl) acrylic acid alkyl that the carbon number as the alkyl is less than 3
Ester, preferably (methyl) methyl acrylate or (methyl) ethyl acrylate, more preferably (methyl) methyl acrylate.
In addition, the monomer for forming (A) acrylic polymer preferably comprises (methyl) the acrylate conduct for containing hydroxyl
Other (methyl) acrylic acid derivatives.If imported using (methyl) acrylate containing hydroxyl in acrylic copolymer
Hydroxyl, then adaptation, adhesion characteristic is controlled to become easy semiconductor chip.As (methyl) acrylate containing hydroxyl,
(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters etc. can be enumerated.
(methyl) acrylate containing hydroxyl is preferably the 1~30 of the whole monomers for forming (A) acrylic polymer
Quality %, more preferably 5~25 mass %, more preferably 10~20 mass %.
In addition, the monomer for forming (A) acrylic polymer can also contain the benzene as other monomers as described above
Ethene, ethene, vinyl ethers, vinyl acetate etc. are free of the non-acrylic monomer of epoxide group.
In order to assign flexible, film forming with film to diaphragm formation, and easily make gloss number described later for 20 with
On, the weight average molecular weight (Mw) of (A) acrylic polymer is preferably 10, more than 000.In addition, above-mentioned weight average molecular weight is more excellent
Elect 15,000~1,000,000, more preferably 20 as, 000~500,000.Weight average molecular weight (Mw) can be according to below
The method of the embodiment of narration determines.
In the present invention, the glass transition temperature (Tg) of (A) acrylic polymer is more than -3 DEG C.If vitrifying
Transition temperature is less than -3 DEG C, then the motility of (A) acrylic polymer will not be adequately suppressed, and diaphragm is easily because heated
Journey and deform, it is impossible to the reliability of chip with diaphragm is fully improved.In the present invention, (A) acrylic polymer
Glass transition temperature be the theoretical value obtained using Fox formulas.
In addition, the glass transition temperature of (A) acrylic polymer is preferably less than 6 DEG C.By making glass transition
Temperature is less than 6 DEG C, improves gloss number described later, so as to so that printing identity becomes good.Although its reason is not
Clearly, but presumption is as follows：Because acrylic polymer (A) moderately has motility, the surface shape of the diaphragm after solidification
Shape is smoothened.
Diaphragm formation film is by suppressing, in less amount, in diaphragm easily to make the monomer containing epoxide group
Phase rich in (A) composition is mutually separated with the solidfied material rich in (B) composition described later, the chip with diaphragm can
Improved by property.In the case of speculating this is because, changing after chip installation through excess temperature, (A) is rich in due to softness
Mitigation of meeting due to stress caused by deformation caused by temperature change, therefore be not likely to produce the diaphragm caused by stress
Stripping.In addition, the diaphragm after heat cure is formed with preferably mutually the foring rich in (A) of the phase separation in film (i.e. diaphragm)
Continuous phase.Thus, it is possible to further improve the effect of above-mentioned raising reliability.
Phase rich in (A) and the phase of the solidfied material rich in (B) can judge as follows：It is divided and surveys for example, by Raman scattering
It is fixed, the principal component which kind of material is the phase is observed by a certain molybdenum determination spectrogram.In addition, the size of phase separation structure is Raman
In the case of below the resolution ratio of optical spectroscopy, the hardness determined using SPM (scanning probe microscopy) contact mode, can as index
To estimate phase of the harder person of hardness as the solidfied material rich in (B) composition, more soft person is the phase rich in (A) composition.Therefore, at this
In invention, can the diaphragm as obtained from being solidified to diaphragm formation with film carry out Raman scattering spectral photometry or SPM and see
Examine to determine whether to form phase separation structure.
It should be noted that (it is converted into solid as gross mass of (A) acrylic polymer in diaphragm formation film
Composition) in shared ratio, usually 10~80 mass %, preferably 15~50 mass %.
＜ (B) epoxies curability composition ＞
(B) epoxies curability composition be for by solidification and formed on a semiconductor die the diaphragm of hard into
Point, generally it is made up of epoxy compounds and thermal curing agents.
In diaphragm formation film, relative to the mass parts of (A) acrylic polymer 100, (B) epoxies curability into
Divide is preferably below 250 mass parts, more preferably below 150 mass parts, more preferably below 100 mass parts.In addition, phase
For the mass parts of (A) acrylic polymer 100, (B) epoxies curability composition is preferably more than 20 mass parts, more preferably
More than 40 mass parts, more preferably more than 60 mass parts.
It is above range by making the content of (B) epoxies curability composition, can obtains and semiconductor chip etc. is attached
The sufficient cementability of thing, in addition, the peeling force between support chip described later is suitable, it is also prevented from support chip from protection
Stripping when being peeled off on film formation film is bad etc..It is in addition, given as described above by the use level of (B) composition is limited in
Scope below higher limit, the reliability for mutually easily becoming continuous phase, semiconductor chip being improved rich in (A) composition, and
And easily improve gloss number.
It should be noted that (it is converted into solid as gross mass of (B) the epoxies curability composition in diaphragm formation film
Body composition) in shared ratio, usually 5~60 mass %, preferably 10~40 mass % or so.
As epoxy compounds, known epoxide can be used.It can specifically enumerate：Biphenyl chemical combination
Thing, bisphenol A diglycidyl ether and its hydride, o-cresol formaldehyde epoxy resin, bicyclopentadiene phenol-type epoxy resin, biphenyl type
Epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin, phenoxy resin decile
There are the epoxy compounds of more than 2 functional groups in son.These compounds can be used alone, or combination 2 kinds with
Upper use.
Thermal curing agents play a part of curing agent for epoxide.As preferable thermal curing agents, can enumerate
There is the compound of more than 2 functional groups that can be reacted with epoxide group in one molecule.As its functional group, Ke Yiju
Go out：Phenolic hydroxyl group, alcoholic extract hydroxyl group, amino, carboxyl and acid anhydrides etc..Wherein, phenolic hydroxyl group, amino, acid anhydrides etc. are preferably enumerated, further preferably
Enumerate phenolic hydroxyl group, amino.
As the specific example of the phenols curing agent with phenolic hydroxyl group, can enumerate：Multifunctional phenolic resin, xenol,
Novolak phenolics, bicyclopentadiene class phenolic resin, XYLOK types phenolic resin, aralkyl phenolic resin etc..As
The specific example of amine curing agent with amino, dicyandiamide can be enumerated.These thermal curing agents can be used alone, or
Person mixes two or more use.
In addition, relative to the mass parts of epoxide 100, the content of thermal curing agents is preferably 0.1~100 mass parts, more
Preferably 0.5~50 mass parts, more preferably 1~20 mass parts.By making the content of thermal curing agents be above-mentioned lower limit
More than, easily solidify (B) composition and obtain the cementability with adherend.In addition, by making the content of thermal curing agents to be upper
State below higher limit, diaphragm formation is inhibited with the hydroscopicity of film, easily makes the reliability of semiconductor device become good.
＜ (C) packing materials ＞
(C) packing material is the composition that moisture-proof, dimensional stability etc. are assigned to diaphragm, can specifically enumerate inorganic filler
Deng.In addition, by implementing laser labelling (to prune diaphragm surface using laser to be printed method) to diaphragm, utilize
The part (printing portion) that laser is pruned exposes (C) packing material and makes reflection light diffusing, is carried with the contrast of non-print part
Height, so as to be identified.
As preferable inorganic filler, can enumerate：Silica, aluminum oxide, talcum, calcium carbonate, titanium oxide, oxidation
The powder of iron, carborundum, boron nitride etc., they are subjected to spheroidizations obtained from pearl, mono-crystlling fibre and glass fibre etc..These
It is central, particularly preferred silica filler and alumina packing.In addition, above-mentioned inorganic filler can be used alone or mix 2
Kind is used above.
In addition, the average grain diameter of packing material is not particularly limited, preferably 0.1~20 μm.If more than 0.1 μm,
Then be coated on diaphragm formation on support chip with composition and be dried and when obtaining diaphragm formation film,
The tendency that diaphragm formation composition forms the character for being suitable for coating be present.In addition, if for less than 20 μm, then gloss number
Easily improve.
In addition, considering from above-mentioned viewpoint, the average grain diameter of packing material is more preferably 0.2~10 μm, more preferably
0.3~6 μm.
It should be noted that average grain diameter is the value measured by using the particles distribution instrument of dynamic light scattering method.Make
For particles distribution instrument, for example, Nanotrac150 of Nikkiso Company Limited's manufacture etc..
For the content of (C) packing material in diaphragm formation film, with total matter of diaphragm formation film
Ratio meter shared in (being converted into solid constituent) is measured, preferably more than 10 mass %, more preferably more than 30 mass %, enters one
Step is preferably more than 50 mass %.It is in addition, preferred relative to the gross mass of diaphragm formation film, the content of (C) packing material
For below 80 mass %, more preferably below 70 mass %, more preferably below 63 mass %.By making (C) to fill material
The content of material is above range, has easily given play to the effect of above-mentioned packing material.In addition, by making containing for (C) packing material
Measure as more than 50 mass %, the contrast of printing portion and non-print portion by laser labelling improves, and the identity of printing becomes
Well.In addition, by making the content of (C) packing material be below above-mentioned higher limit, easily improve gloss number.
The diaphragm formation film of the present invention can also contain following in addition to (A) described above~(C) compositions
(D) more than any one in colouring agent, (E) coupling agent, (F) curing accelerator and (G) other additives.
＜ (D) colouring agents ＞
Diaphragm formation preferably comprises (D) colouring agent with film, this is because, being installed to by semiconductor chip in machine
When, infrared ray etc. as caused by the device of surrounding can be shielded and prevent the malfunction of semiconductor chip.In addition, by containing
(D) colouring agent, in diaphragm printed product numbering, mark etc. obtained from solidifying to diaphragm formation film, text can be made
The identity of word improves.That is, production is printed at the back side that the formation of semiconductor chip has diaphragm sometimes through laser-marking method etc.
Product numbering etc., by making diaphragm contain (D) colouring agent, printing portion and the poor contrast of non-print part increase, identity
Improve.
As (D) colouring agent, the pigment or dyestuff of organic or inorganic can be used.As dyestuff, can use acid dyes,
The arbitrary dyestuff such as reactive dye, direct dyes, disperse dyes, the dye of positive ion.In addition, pigment is it is not also specifically limited, can
With the appropriate selection use from known pigment.
Among these, preferred pair electromagnetic wave, the shielding of infrared ray is good and can improve the knowledge brought by laser-marking method
The black pigment of other property.As black pigment, carbon black, iron oxide, manganese dioxide, nigrosine, activated carbon etc. can be used, but simultaneously
It is not limited to these.From the viewpoint of the reliability for improving semiconductor chip, particularly preferred carbon black.(D) colouring agent can be single
Solely using one kind, two or more use can also be combined.
For the use level of (D) colouring agent, with its diaphragm formation film gross mass (be converted into solid into
Point) in shared ratio meter, preferably 0.01~25 mass %, more preferably 0.03~15 mass %.
＜ (E) coupling agents ＞
(E) coupling agent can also be coordinated in diaphragm formation film.
As (E) coupling agent, the preferably silane coupler with alkoxies such as methoxyl group, ethyoxyls.In addition, as (E)
Coupling agent, preferably using have with (A) acrylic polymer, (B) epoxies curability composition etc. possessed by functional group it is anti-
The compound of reactive functional groups beyond deserved alkoxy.As reactive functional groups, can enumerate：Glycidoxy, ring
The vinyl beyond epoxy radicals, amino, (methyl) acryloxy, (methyl) acryloxy, sulfydryl beyond oxygen propoxyl group
Deng.Among these, preferably glycidoxy, epoxy radicals.
As silane coupler, the low-molecular-weight silicon alkane coupling agent that molecular weight can be used to be less than 300, it can also use and divide
Son amount is the silane coupler of more than 300 oligomeric, and they can also be applied in combination.
As low-molecular-weight silicon alkane coupling agent, can specifically enumerate：γ-glycidoxypropyltrime,hoxysilane, γ-
Glycidoxypropyl group triethoxysilane, γ-glycidoxypropyl diethoxy silane, β-(3,4- epoxy hexamethylenes
Base) ethyl trimethoxy silane, γ-(methacryl propyl group) trimethoxy silane, N- phenyl-gamma-amino propyl group trimethoxy
Base silane, γ-urea propyl-triethoxysilicane, N-6- (amino-ethyl)-gamma-amino hydroxypropyl methyl diethoxy silane, γ-mercapto
Propyl-triethoxysilicane, γ-mercapto hydroxypropyl methyl dimethoxysilane, vinyltriacetoxy silane etc..
The silane coupler of oligomeric is the organopolysiloxane for having siloxane backbone, and preferably has direct key
Close the silane coupler of alkoxy on the silicon atoms.
For the content of (E) coupling agent, with the gross mass of diaphragm formation film (being converted into solid constituent)
Shared ratio meter, preferably 0.01~10.0 mass %, more preferably 0.1~3.0 mass %.
＜ (F) curing accelerators ＞
In order to adjust the cambial curing rate of diaphragm, (F) solidification rush can be contained also in diaphragm formation film
Enter agent.
As preferable curing accelerator, can enumerate：Triethylenediamine, benzyl dimethylamine, triethanolamine, dimethylamino
The tertiary amines such as ethanol, three (dimethylaminomethyl) phenol；2-methylimidazole, 2- phenylimidazoles, 2- phenyl -4-methylimidazole,
The imidazoles such as 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles；Tributylphosphine, hexichol
Organic phosphine such as base phosphine, triphenylphosphine；TetraphenylThe tetraphenyl boron salts such as tetraphenyl borate salts, triphenylphosphine tetraphenyl borate salts
Deng.They can be used alone, or mix two or more use.
Relative to the mass parts of (B) epoxies curability composition 100, preferably with 0.01~10 mass parts, more preferably with 0.1~
The amount of 5 mass parts contains (F) curing accelerator.(F) curing accelerator is contained by the amount with above range, diaphragm, which is formed, to be used
Film is if exposed under high-temperature high humility, it may have excellent adhesion properties, even in the situation exposed to harsh condition
Under, high reliability can also be realized.
The other additive ＞ of ＜ (G)
As the other additives optionally contained in diaphragm formation film, it is not particularly limited, crosslinking can be enumerated
Agent, bulking agent, levelling agent, plasticizer, antistatic agent, antioxidant, ion capturing agent, getter, chain-transferring agent, energy line polymerization
Property compound, Photoepolymerizationinitiater initiater etc..Diaphragm formation film can suitably adjust by coordinating such as bulking agent and be rich in (A)
Compatibility between the phase of composition and the phase of the solidfied material rich in (B) composition, so as to the phase separation structure of appropriate design.
＜ gloss numbers ＞
By containing above-mentioned cooperation, diaphragm obtained from being solidified based on the diaphragm formation films determined of JIS Z 8741
At least one side gloss number be more than 20.In the present invention, by make with the face of the opposite side in face that gloss number is more than 20 with
Chip is pasted and solidify, diaphragm using laser labelling come the face that is printed with more than 20 gloss number.Therefore, at this
In invention, printing portion and the contrast in non-print portion improve, and the identity of printing portion becomes good.
In order that contrast further improves and improves the identity of word, above-mentioned gloss number is preferably more than 27.In addition,
Gloss number is not particularly limited, but preferably less than 45.
It should be noted that gloss number is not particularly limited, can for example, by adjust the monomer containing epoxide group and
The carbon number of alkyl is the amount of more than 4 (methyl) alkyl acrylate etc., adjustment (B) composition containing relative to (A) composition
Amount, the selection of species of filler, the adjustment of the content of filler or particle diameter or the other additives of addition are suitably adjusted
It is whole.
Diaphragm formation is not particularly limited with the thickness of film, preferably 3~300 μm, more preferably 5~250 μm, enters one
Step is preferably 7~200 μm.
[diaphragm formation composite sheet]
The diaphragm formation of the present invention is generally strippingly formed on support chip with film, using the diaphragm as laminated body
The form of formation composite sheet uses.Diaphragm formation can be same shape with support chip with film.Used in addition, diaphragm is formed
The diaphragm formation of composite sheet is prepared to the shape essentially identical with chip with film or can completely include the shape of chip,
It can take and be stacked in than so-called preshaped structure of the diaphragm formation on the larger-sized support chip of film.
Support chip is the sheet material for supporting diaphragm formation film, can be used for example：Polyethylene film, polypropylene screen,
Polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate
Ester film, poly (ethylene naphthalate) film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene-vinyl acetate c
Thing film, ionomer resin film, ethene-(methyl) acrylic copolymer film, ethene-(methyl) acrylate copolymer film, polyphenyl
The films such as vinyl film, polycarbonate membrane, polyimide film, fluororesin film.Alternatively, it is also possible to use their cross linking membrane.In addition, also
It can be the stack membrane of two or more film selected from above-mentioned film.Furthermore it is also possible to the film formed using they are coloured.
The face of the diaphragm formation film side to be formed of support chip can also suitably implement lift-off processing.As stripping
Remover used in processing, for example,：Alcohol acids, polysiloxane-based, fluorinated, unsaturated polyester (UP) class, polyolefin
Class, wax class etc., because alcohol acids, polysiloxane-based, fluorinated remover have heat resistance, therefore preferably.
In addition, in diaphragm formation composite sheet, can be in diaphragm formation film with setting support chip side phase
The stripping film of light fissility is bonded on anti-face, diaphragm formation is protected with film using the stripping film.
Diaphragm formation is obtained as below with film：Above-mentioned each composition is mixed into suitable ratio in appropriate solvent or
Do not add solvent and mix, form diaphragm formation composition, then diaphragm formation is coated on the support chip with composition
Go up and be dried.Alternatively, it is also possible to which diaphragm formation is coated on the engineering film different from support chip with composition, dry
And film forming, then be suitably transferred to support chip etc. and above form diaphragm formation film.Engineering film can not have to remove behind
And used as above-mentioned stripping film.
Alternatively, it is also possible to pass through wet method lamination or dry lamination, hot melt lamination, melting extrusion lamination, coextrusion processing etc.
Carrying out the lamination of film, thus the surface tension of support chip is adjusted.That is, the surface tension of at least one side can also be in and made
For the film in the preferred scope in the face to be connected with diaphragm formation with film of above-mentioned support chip lamination is manufactured with other film laminations
Body, and make it that the face is the face to connect with diaphragm formation film, so as to which support chip be made.
Alternatively, it is also possible to using on above-mentioned film the bonding sheet formed with adhesive phase used as support chip.In this case,
Diaphragm formation is layered on the adhesive phase on support chip with film.By the way that such structure is made, particularly protecting
Cuticula formation is with the feelings that chip is cut into chip one by one in composite sheet together with diaphragm formation with film or diaphragm
Under condition, the fixed performance of chip and chip becomes excellent, therefore it is preferred that.By regarding adhesive phase as releasable adhesive phase,
Easily diaphragm formation can be separated with film or diaphragm from support chip, therefore it is preferred that.Releasable adhesive phase can make
With weak cohesive adhesive, the weak cohesive adhesive is with the bonding force that can peel off the cambial degree of diaphragm
Adhesive, the energy ray-curable adhesive for reducing bonding force by energy line irradiation can also be used.Specifically, then shell
Can be by currently known various adhesives (for example, rubber-like, acrylic compounds, polysiloxane-based, polyurethane from property adhesive phase
The general purpose adhesives such as class, vinyl ethers, there is the adhesive of concave-convex surface, energy line solidification type adhesive, contain thermal expansion
Adhesive of composition etc.) formed.
In the case of using the releasable adhesive phase of energy ray-curable, diaphragm forms pre- with compound piece collection
When being shaped structure, energy line irradiation is carried out with the region of film to the formation of lamination diaphragm in advance, reduces cohesive, and at it
Its region is irradiated without energy line, such as in order to be adhered on fixture, can also keep the high state of bonding force.Will be only to it
When its region is irradiated without energy line, as long as such as being set in region corresponding with other regions of support chip by printing etc.
Energy line shielding layer, and carry out energy line irradiation from support chip side.In addition, in order to obtain same effect, can also make
The formation of lamination diaphragm is wanted with the further lamination in the region of film and diaphragm formation film on the adhesive phase of bonding sheet
The structure of the releasable adhesive phase of essentially identical shape.As releasable adhesive film, can use and above-mentioned phase
Same film.
In the case that diaphragm formation does not take preshaped structure with film, in order on the surface of diaphragm formation film
Other fixtures such as the peripheral part stationary ring framework in (face to connect with adherend), bond layer or double can also be set in addition
Face adhesive tape., can for other fixtures such as stationary ring framework in the case that diaphragm formation takes preshaped structure with film
Bond layer or double-faced adhesive tape are set with the non-lamination diaphragm formation in support chip peripheral part in addition with the region of film.
[application method of diaphragm formation film]
Diaphragm formation is secured in the adherends such as semiconductor wafer, semiconductor chip with film, then heat cure and
Used as diaphragm.Here, diaphragm formation is pasted onto adherend with film and the feelings of diaphragm formation composite sheet is made
Under condition, first, when being protected by by stripping film, stripping film is peeled off, then, diaphragm formation film is formed with support film
Laminated body is secured in adherend, then from diaphragm formation with peeling off support chip on film.
Hereinafter, for the application method of diaphragm formation film, with the diaphragm formation back of the body of the film for semiconductor chip
Face protects purposes to be illustrated to manufacture exemplified by the chip with diaphragm, but is not limited to example as shown below.
In the method, first by said protection film formation film lamination at the back side of semiconductor wafer.For example, using
In the case of diaphragm formation composite sheet, the laminated body that diaphragm formation is formed with film and substrate sheets is pasted onto semiconductor die
The back side of piece.Then, from diaphragm formation with support chip is peeled off on film, the then diaphragm shape by lamination on the semiconductor wafer
Heat cure is carried out into film, diaphragm is formed in the entire surface of chip.
It should be noted that semiconductor wafer can be silicon wafer, and, or the compound semiconductor such as gallium-arsenic
Chip.In addition, semiconductor wafer on its surface formed with circuit, and the back side made by suitably grinding etc. thickness for 50~
500 μm or so.
Then, the laminated body that semiconductor wafer and diaphragm are formed is cut according to the circuit that wafer surface is formed
Cut.Cutting is carried out in a manner of chip and resin film are cut off together, and by cutting, semiconductor wafer and diaphragm are formed folded
Layer body is divided into multiple chips.It should be noted that cutting through for chip has used the usual method of dicing tape to enter
OK.Then, the chip after cutting is picked up using fexible units such as opening folders, thus obtaining the back side has the semiconductor of diaphragm
Chip (chip for carrying diaphragm).
It should be noted that the manufacture method of semiconductor chip is not limited to the example of the above, for example, the stripping of support chip
From can be carried out after diaphragm heat cure, can also carry out after dicing.In addition, be supported the stripping of piece after dicing
In the case of, support chip can play a part of dicing tape.In addition, the heat cure of diaphragm formation film can also be after dicing
Carry out.
[chip for carrying diaphragm]
The present invention the chip with diaphragm can be obtained for example, by above-mentioned manufacture method, it possess semiconductor chip,
And the diaphragm at the semiconductor chip back side is stacked in, the diaphragm is above-mentioned diaphragm formation is solidified to form with film
Be used for protect the film of chip back.The face of the side opposite with the face of semiconductor chip side of diaphragm determines according to JIS Z 8741
Gloss number be more than 20.
Can be by the way that the chip with diaphragm be installed on substrate etc. to manufacture semiconductor device in a manner of upside-down mounting.Separately
Outside, can also by by the die bonding with diaphragm on other components such as brilliant pad portion or other semiconductor chips (chip
On equipped section) manufacture semiconductor device.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, but the present invention is not limited by these examples.
Assay method, evaluation method in the present invention is as follows.
(1) weight average molecular weight (Mw)
The weight average molecular weight Mw for being converted into polystyrene standard is determined by gel permeation chromatography (GPC) method.
Determine device：High-efficiency column is sequentially connected on the efficient GPC devices " HLC-8120GPC " of TOSOH Co., Ltd's manufacture
“TSK guard column HXL-H”、“TSK Gel GMHXL”、“TSK Gel G2000 HXL" (it is eastern Cao's strain formula meeting above
Society manufactures) and be determined.
Column temperature：40 DEG C, liquor charging speed：1.0mL/ points, detector：Differential refraction rate instrument
(2) gloss number
Shelled using Tape Mounter (Lindeke Co., Ltd manufactures, Adwill RAD-3600 F/12), by stripping film
The diaphragm formation film of diaphragm formation composite sheet from after is heated to 70 DEG C and ground while being pasted onto by #2000
Silicon wafer (280 μm of diameter 200mm, thickness) abradant surface on.Then, after support chip is peeled off, by being carried out at 130 DEG C
Heat within 2 hours, diaphragm formation is solidified with film, forms diaphragm on silicon.With following measure devices and measure bar
Part is measured to 60 degree of mirror surface lusters on diaphragm surface, as gloss number.
Determine device：The electricity Se Industrial Co., Ltd of Japan system of VG 2000 makes
Condition determination：Based on the standards of JIS Z 8741
(3) identity (printing) of word
Shelled using Tape Mounter (Lindeke Co., Ltd manufactures, Adwill RAD-3600 F/12), by stripping film
The diaphragm formation film of diaphragm formation composite sheet from after is heated to 70 DEG C and ground while being pasted onto by #2000
Silicon wafer (280 μm of diameter 200mm, thickness) abradant surface on.Then, after support chip is peeled off, by being carried out at 130 DEG C
Heat within 2 hours, diaphragm formation is solidified with film, forms diaphragm on silicon.Use laser print apparatus
(Panasonic Industrial Devices SUNX Co., Ltd.s manufacture, LP-V10U, optical maser wavelength：1056nm), protecting
The width of one word of cuticula printout surface is less than 300 μm of 4 words.With digit microscope to resulting printing after
Protection film surface confirmed, with image confirm that printing character can be read.Judgment standard is as follows：Carrying out digit microscope
During observation, during with direct projection light irradiation printing portion, fully reading person " A " can be expressed as, can be read but the person's of not knowing table
Be shown as " B ", can not the person of reading be expressed as " F ".
(4) reliability evaluation
Shelled using Tape Mounter (Lindeke Co., Ltd manufactures, Adwill RAD-3600 F/12), by stripping film
The diaphragm formation film of diaphragm formation composite sheet from after is heated to 70 DEG C and ground while being pasted onto by #2000
Silicon wafer (280 μm of diameter 200mm, thickness) abradant surface on.Then, after support chip is peeled off, by being carried out at 130 DEG C
Heat within 2 hours, diaphragm formation is solidified with film, forms diaphragm on silicon.Then, diaphragm side is pasted onto and cut
On rubber tapping band (Lindeke Co., Ltd manufacture, Adwill D-676H), using cutter device (DISCO Inc. are manufactured,
DFD651 3mm × 3mm size) is cut into, has obtained chip of the reliability evaluation with diaphragm.
Above-mentioned reliability evaluation is imitating the technique of actual installation semiconductor chip first with the chip with diaphragm
Handled under condition (preconditioning, precondition).Specifically, the chip with diaphragm is dried at 125 DEG C
Roasting 20 hours, then, being placed 168 hours under conditions of 85 DEG C, 85%RH makes its moisture absorption, is preheating 160 DEG C immediately after, is adding
Pass through 3 times in hot 260 DEG C of temperature, the IR reflow ovens of the condition of 30 seconds heat times.After being handled with above-mentioned preconditioning
25 chips with diaphragm are arranged in thermal shock device (ESPEC companies manufacture, TSE-11-A), are protected at -65 DEG C
Hold 10 minutes, then kept for 10 minutes at 150 DEG C, the circulation has been repeated 1000 times.
Then, 25 chips with diaphragm are taken out from thermal shock device, reliability is evaluated.Tool
For body, by scanning ultrasonic flaw detecting device (Hitachi Kenki Fine Tech companies manufacture, Hye-Focus) and cutting
Face, which is observed, to be floated to the junction surface of chip and diaphragm whether there is, has flawless to be evaluated in stripping and diaphragm, will be deposited
Float, peel off and crackle in any situation person be set as NG.NG number in 25 chips is shown in table 4.
Embodiment 1
In embodiment 1, it is as follows for forming the composition of diaphragm formation film.
(A) acrylic copolymer：By the mass parts of n-butyl acrylate 1, the mass parts of methyl methacrylate 79, acrylic acid
The mass parts of 2- hydroxy methacrylates 15, the mass parts of GMA 5 are copolymerized the weight average molecular weight (Mw) 370,000 formed, glass
The copolymer of 7 DEG C of glass transition temperature (Tg)
(B) epoxies curability composition
Epoxy compounds：Bisphenol A type epoxy resin (Nippon Shokubai Co., Ltd manufactures, BPA-328) and two rings penta
Diene type epoxy resin (Dainippon Ink. ＆ Chemicals Inc manufactures, Epiclon HP-7200HH)
Thermal curing agents：Dicyandiamide (ADEKA companies manufacture, Adeka Hardener 3636AS)
(C) filler：(silica filler, the manufacture of Long Sen Co., Ltd. will for the vitreous silica filler of 8 μm of average grain diameter
SV-10 carries out physical crushing and formed)
(D) colouring agent：(Mitsubishi chemical Co., Ltd manufactures carbon black, MA600, average grain diameter：28nm)
(E) silane coupler：(Shin-Etsu Chemial Co., Ltd manufactures oligomeric silane coupler, X-41-1056 first
Epoxide equivalent 17.1mmol/g, molecular weight 500~1500), γ-epoxypropoxy triethoxysilane (SHIN-ETSU HANTOTAI's chemical industry
Co., Ltd. manufactures, KBE-403 methoxyl group equivalents 8.1mmol/g, molecular weight 278.4) and γ-epoxypropoxy trimethoxy
Base silane (Shin-Etsu Chemial Co., Ltd manufactures, KBM-403 methoxyl group equivalents 12.7mmol/g, molecular weight 236.3)
(F) curing accelerator：2- phenyl -4,5- bishydroxymethyls imidazoles (Shikoku Chem manufactures,
CUREZOL 2PHZ)
With the ratio shown in table 1 diaphragm formation obtained from above-mentioned each material will be coordinated to be carried out with composition with MEK
Dilution, is coated on polyethylene terephthalate film (Lindeke Co., Ltd's system that lift-off processing is implemented by one side
Make, 50 μm of SP-PET5011, thickness) formed support chip lift-off processing face on, and cause dried thickness be 25 μm,
Dried 3 minutes at 100 DEG C, diaphragm formation film is formd on support chip.Then, by another stripping film (Lin get Ke strain formulas
Commercial firm manufactures, 38 μm of SP-PET3811, thickness) it is superimposed on the diaphragm formation film, obtain the diaphragm shape of embodiment 1
Into with composite sheet.
Embodiment 2, comparative example 1~6
In addition to using the material shown in table 2 to be used as this point of (A) acrylic copolymer, carry out same with embodiment 1
The operation of sample.It should be noted that for each embodiment, (A) acrylic copolymer of comparative example, by its weight average molecular weight
(Mw) and glass transition temperature (Tg) is shown in table 2 in the lump.
[table 1]
※ it should be noted that mass parts on the basis of solid constituent, quality % is with the gross mass of diaphragm formation film
On the basis of (solid constituent benchmark)
[table 2]
※ ratio of components is the ratio of components for the monomer for forming (A) acrylic copolymer, and expression is n-butyl acrylate
(BA), the matter of methyl methacrylate (MA), acrylic acid 2- hydroxy methacrylates (HEA) and GMA (GMA)
Amount ratio
Embodiment 3
Except silica filler (Tokuyama Corporation are manufactured, UF310) conduct using 3 μm of average grain diameter
(C) composition replaces beyond the silica filler of 8 μm of average grain diameter, has carried out operation similarly to Example 2.
Embodiment 4
Except silica filler (Admatechs Co., Ltd.s manufacture, UF310) conduct using 0.5 μm of average grain diameter
(C) composition replaces beyond the silica filler of 8 μm of average grain diameter, has carried out operation similarly to Example 2.
Embodiment 5,6
Except change as shown in table 3 (C) composition use level this point in addition to, carried out operation similarly to Example 2.
Embodiment 7,8
Except change as shown in table 3 (A) and (B) composition use level this point in addition to, carried out similarly to Example 2
Operation.
For each embodiment 1~8, comparative example 1~6, gloss number is determined, and printing identity and reliability are carried out
Evaluation.It the results are shown in table 4.
[table 4]
| Gloss number | Print identity | Reliability | |
| Embodiment 1 | 21 | B | 0/25 |
| Embodiment 2 | 32 | A | 0/25 |
| Embodiment 3 | 25 | B | 0/25 |
| Embodiment 4 | 36 | A | 0/25 |
| Embodiment 5 | 28 | B | 0/25 |
| Embodiment 6 | 25 | B | 0/25 |
| Embodiment 7 | 30 | A | 0/25 |
| Embodiment 8 | 28 | B | 0/25 |
| Comparative example 1 | 18 | F | 0/25 |
| Comparative example 2 | 38 | A | 12/25 |
| Comparative example 3 | 30 | A | 10/25 |
| Comparative example 4 | 24 | B | 19/25 |
| Comparative example 5 | 26 | B | 23/25 |
| Comparative example 6 | 32 | A | 25/25 |
As shown in Table 4, for embodiment 1~8, by making (A) acrylic polymer contain below 8 mass %
Contain the monomer of epoxide group as forming monomer, and its glass transition temperature is more than -3 DEG C, can make rich in (A) into
The phase and the phase separation between the phase of the solidfied material rich in (B) composition divided are good, and gloss number is also more than 20, therefore can
So that printing identity and reliability both of which are good.
On the other hand, for comparative example 1, because (A) acrylic polymer is free of containing as composition monomer
The monomer of epoxide group, therefore, small bumps are formed on diaphragm surface because of phase separation, protected as a result, result in
The scattering of film surface reflection.Therefore, gloss number diminishes, and printing identity is deteriorated.In addition, for comparative example 2,3,6, by
It is less than -3 DEG C in the glass transition temperature of (A) acrylic polymer, therefore speculates that diaphragm is sent out when undergoing heating process
Deformation is given birth to, NG chip-counts increase, and the reliability of the chip with diaphragm can not be made fully to improve.In addition, for comparative example
4th, for 5, largely contain the monomer of epoxide group as monomer is formed because (A) acrylic polymer contains, therefore (A) into
Divide and the compatibility of (B) composition is high, it is difficult to be separated, the reliability of the chip with diaphragm reduces.
Claims (16)
1. a kind of diaphragm formation film, it is used for the diaphragm to form protection semiconductor chip,
The diaphragm formation film contains (A) acrylic polymer, (B) epoxies curability composition and (C) packing material,
The monomer for forming (A) acrylic polymer contains epoxide group with below the 8 mass % of whole monomers ratio
Monomer, and the glass transition temperature of (A) acrylic polymer be more than -3 DEG C,
The gloss number that at least one side of diaphragm obtained from the diaphragm formation film solidifies determines according to JIS Z 8741
For more than 20.
2. diaphragm formation film according to claim 1, wherein, the glass transition temperature of (A) acrylic polymer
Spend for less than 6 DEG C.
3. diaphragm formation film according to claim 1, wherein, the monomer for forming (A) acrylic polymer also contains
There is (methyl) alkyl acrylate.
4. diaphragm formation film according to claim 2, wherein, the monomer for forming (A) acrylic polymer also contains
There is (methyl) alkyl acrylate.
5. diaphragm formation film according to claim 1, wherein, the monomer of (A) acrylic polymer is formed with complete
Below the 12 mass % of portion's monomer ratio contains (methyl) alkyl acrylate that atomic number of alkyl carbon is more than 4.
6. diaphragm formation film according to claim 2, wherein, the monomer of (A) acrylic polymer is formed with complete
Below the 12 mass % of portion's monomer ratio contains (methyl) alkyl acrylate that atomic number of alkyl carbon is more than 4.
7. diaphragm formation film according to claim 3, wherein, the monomer of (A) acrylic polymer is formed with complete
Below the 12 mass % of portion's monomer ratio contains (methyl) alkyl acrylate that atomic number of alkyl carbon is more than 4.
8. diaphragm formation film according to claim 4, wherein, the monomer of (A) acrylic polymer is formed with complete
Below the 12 mass % of portion's monomer ratio contains (methyl) alkyl acrylate that atomic number of alkyl carbon is more than 4.
9. the diaphragm formation film according to any one of claim 5~8, wherein, the atomic number of alkyl carbon be 4 with
On (methyl) alkyl acrylate be (methyl) butyl acrylate.
10. according to diaphragm formation film according to any one of claims 1 to 8, wherein, the content of (C) packing material is
More than the 50 mass % of diaphragm formation film.
11. diaphragm formation film according to claim 9, wherein, the content of (C) packing material is formed for diaphragm to be used
More than the 50 mass % of film.
12. according to diaphragm formation film according to any one of claims 1 to 8, it also contains (D) colouring agent.
13. diaphragm formation film according to claim 9, it also contains (D) colouring agent.
14. diaphragm formation film according to claim 10, it also contains (D) colouring agent.
15. diaphragm formation film according to claim 11, it also contains (D) colouring agent.
16. a kind of chip with diaphragm, it possesses semiconductor chip and the protection being arranged on the semiconductor chip
Film, wherein,
The diaphragm makes diaphragm formation be solidified to form with film, also, the diaphragm formation film contains (A) third
Alkene acids polymers, (B) epoxies curability composition and (C) packing material,
The monomer for forming (A) acrylic polymer contains epoxide group with below the 8 mass % of whole monomers ratio
Monomer, and the glass transition temperature of (A) acrylic polymer be more than -3 DEG C,
The face of the side opposite with the face of the semiconductor chip side of the diaphragm is according to the gloss numbers determined of JIS Z 8741
More than 20.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-264576 | 2012-12-03 | ||
| JP2012264576 | 2012-12-03 | ||
| PCT/JP2013/082290 WO2014087948A1 (en) | 2012-12-03 | 2013-11-29 | Protective-membrane-forming film |
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| Publication Number | Publication Date |
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| CN104838491A CN104838491A (en) | 2015-08-12 |
| CN104838491B true CN104838491B (en) | 2018-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380063150.0A Active CN104838491B (en) | 2012-12-03 | 2013-11-29 | Diaphragm formation film |
Country Status (6)
| Country | Link |
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| JP (1) | JP6334412B2 (en) |
| KR (1) | KR102110105B1 (en) |
| CN (1) | CN104838491B (en) |
| PH (1) | PH12015501197B1 (en) |
| TW (1) | TWI599600B (en) |
| WO (1) | WO2014087948A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6388228B2 (en) * | 2013-12-27 | 2018-09-12 | パナソニックＩｐマネジメント株式会社 | Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
| US10190017B2 (en) | 2014-03-28 | 2019-01-29 | Lintec Corporation | Protective film-forming film and method of manufacturing semiconductor chip with protective film |
| JP7154732B2 (en) | 2016-03-31 | 2022-10-18 | 味の素株式会社 | resin composition |
| JP6353868B2 (en) * | 2016-06-07 | 2018-07-04 | リンテック株式会社 | Protective film forming sheet |
| 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 |
| JP7156335B2 (en) * | 2020-06-03 | 2022-10-19 | 味の素株式会社 | RESIN COMPOSITION, ADHESIVE FILM, COMPONENT-BUILDING CIRCUIT BOARD, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURING SHEET-LIKE RESIN COMPOSITION |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102083932A (en) * | 2008-07-01 | 2011-06-01 | Lg化学株式会社 | Acrylic composition for optical members, protective film for optical members, polarizing plate, and liquid crystal display |
| CN102372826A (en) * | 2010-08-12 | 2012-03-14 | 株式会社Lg化学 | Thermally curable resin composition for protective film |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3601443B2 (en) | 1999-11-30 | 2004-12-15 | 日立化成工業株式会社 | Adhesive film, method of manufacturing the same, wiring board for mounting semiconductor, and semiconductor device |
| JP3544362B2 (en) | 2001-03-21 | 2004-07-21 | リンテック株式会社 | Method for manufacturing semiconductor chip |
| JP2004074472A (en) * | 2002-08-12 | 2004-03-11 | Kanegafuchi Chem Ind Co Ltd | Matting acrylic thermoplastic resin film and acrylic laminate of the film |
| JP4364508B2 (en) * | 2002-12-27 | 2009-11-18 | リンテック株式会社 | Protective film forming sheet for chip back surface and manufacturing method of chip with protective film |
| JP2007250970A (en) * | 2006-03-17 | 2007-09-27 | Hitachi Chem Co Ltd | Film for protecting rear face of semiconductor element, semiconductor device using the same and manufacturing method thereof |
| JP2008006386A (en) * | 2006-06-29 | 2008-01-17 | Furukawa Electric Co Ltd:The | Method for forming protective film using protective-film-forming sheet for chip |
| JP2009130233A (en) * | 2007-11-27 | 2009-06-11 | Furukawa Electric Co Ltd:The | Film for chip protection |
| JP5893250B2 (en) * | 2011-01-31 | 2016-03-23 | リンテック株式会社 | Chip protective film forming sheet, semiconductor chip manufacturing method, and semiconductor device |
-
2013
- 2013-11-29 KR KR1020157014266A patent/KR102110105B1/en active IP Right Grant
- 2013-11-29 WO PCT/JP2013/082290 patent/WO2014087948A1/en active Application Filing
- 2013-11-29 JP JP2014551080A patent/JP6334412B2/en active Active
- 2013-11-29 CN CN201380063150.0A patent/CN104838491B/en active Active
- 2013-12-03 TW TW102144160A patent/TWI599600B/en active
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2015
- 2015-05-28 PH PH12015501197A patent/PH12015501197B1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083932A (en) * | 2008-07-01 | 2011-06-01 | Lg化学株式会社 | Acrylic composition for optical members, protective film for optical members, polarizing plate, and liquid crystal display |
| CN102372826A (en) * | 2010-08-12 | 2012-03-14 | 株式会社Lg化学 | Thermally curable resin composition for protective film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6334412B2 (en) | 2018-05-30 |
| TWI599600B (en) | 2017-09-21 |
| CN104838491A (en) | 2015-08-12 |
| KR20150092133A (en) | 2015-08-12 |
| PH12015501197A1 (en) | 2015-08-17 |
| WO2014087948A1 (en) | 2014-06-12 |
| KR102110105B1 (en) | 2020-05-13 |
| JPWO2014087948A1 (en) | 2017-01-05 |
| PH12015501197B1 (en) | 2015-08-17 |
| TW201433595A (en) | 2014-09-01 |
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