CN104231958A - Adhesive material for semiconductor manufacturing process - Google Patents
Adhesive material for semiconductor manufacturing process Download PDFInfo
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- CN104231958A CN104231958A CN201410246886.8A CN201410246886A CN104231958A CN 104231958 A CN104231958 A CN 104231958A CN 201410246886 A CN201410246886 A CN 201410246886A CN 104231958 A CN104231958 A CN 104231958A
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- resin
- acid
- jointing material
- curable resin
- epoxy resin
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/143—Glass in the substrate
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
The present invention relates to an adhesive material for semiconductor manufacturing process. The adhesive material aims to achieve the goals of fixing and protecting wafers of components in the semiconductor manufacturing process. The convention adhesive material has the problems of being likely to lead to semiconductor wafer warp and damages caused by size changes of the adhesive material in the manufacturing process, especially under high temperature. A sheet formed by allowing solid resin (A) to be permeated in the glass fiber (B) is used as a base material of the adhesive material. The base material is high in size stability, and prevents the semiconductor wafer from warping in the making process.
Description
Technical field
The present invention relates to using by curable resin is infiltrated up in glass fibre and the organo-mineral complexing sheet making it solidify and obtain as the semiconductor fabrication process jointing material of base material.
This jointing material is especially suitable for use as the surface protection jointing material used when grinding semiconductor wafer being become film.
This base material has excellent characteristic in the transparency, thermotolerance, dimensional stability, flexibility, obdurability.
Background technology
In order to practical application, the operation of assembled semiconductor comprises following operation.
(1) adhesive surface protection jointing material (grinding back surface adhesive tape) the back side of semiconductor wafer is carried out to the operation of grinding on the element surface of the semiconductor wafer of composed component;
(2) semiconductor wafer is imported in vacuum chamber the backside metallization operation of carrying out metal evaporation, sputtering;
(3) on dicing tape, fix semiconductor wafer and by surface protection jointing material peel off operation;
(4) cutting action of semi-conductor chip is divided into;
(5) by the bonding die operation that engages with lead frame of semi-conductor chip after segmentation;
(6) by the plastic packaging operation of semi-conductor chip resin seal.
Wherein, overleaf in sputtering of metals operation, due to evaporation, sputtering and being heated, therefore, thermotolerance is required to the surface protection jointing material fitted on semiconductor wafer.
On the other hand, in recent years with in the device of High Density Packaging, the lower thickness of semiconductor wafer.Thereupon, the dimensional stability of surface protection jointing material comes into one's own.Such as; in above-mentioned operation of being heated; when surface protection jointing material, particularly this base material generation thermal contraction, large linear expansion, heat fusing etc., the breakage of the semiconductor wafer after filming can be produced, carrying that the warpage of wafer causes is bad, stripping in stripping process is bad etc.
Based on above-mentioned background, the base material of effects on surface protection jointing material has carried out the design for improving dimensional stability.
Such as, use the sheet be made up of the such polyester resin (patent documentation 1) of polyethylene terephthalate (PET), PEN (PEN), the resin (patent documentation 2) with liquid crystal liquid crystal property as adhesive substrate etc.But, these because of thermogenetic contraction, linear expansion characteristic large, dimensional stability is insufficient.
Have also been attempted polyimide-type materials (patent documentation 3 and 4) for adhesive substrate.Polyimide-type materials has dominance in thermotolerance and dimensional stability, but makes water-absorbent high due to its resin structure.Therefore, the grinding fluid used in the grinding process of semiconductor wafer can be absorbed, thus cause dimensional change.In addition, after process finishing, the water absorbed in drying process evaporates and size is changed, semiconductor wafer generation warpage.
In order to improve thermotolerance, have also been attempted use by reaction resin is processed into sheet and the triggering device the utilizing light and heat such sheet that makes it react and obtain as adhesive substrate (patent documentation 5).The thermotolerance of the sheet obtained although it is so is really excellent, but existing problems in obdurability when making sheet.In addition, the sheet of reaction resin carries out stretch process etc. unlike thermal plasticity slice, therefore, can not reduce by thermogenetic coefficient of linear expansion, warpage can occur in heating process.In addition, in order to improve thermotolerance improve the density of the crosslinking reaction of reaction resin time, the flexibility of sheet and obdurability can be lost, and also there is the protection adhesive substrate problem of breaking, disconnecting when stripping process.
In addition, the base material that have also been attempted the surface protection jointing material used in semiconductor fabrication process uses non-woven fabrics, fabric (patent documentation 6).Non-woven fabrics and fabric do not use to improve dimensional stability as used herein, but use to relax the impact being applied to wafer during grinding overleaf.Therefore, resin can not be completely integrated with resin with non-woven fabrics or fabric, has space between which.In addition, non-woven fabrics or fabric are formed by organism, therefore, few to the contribution of dimensional stability.
In addition, when being peeled off from semiconductor wafer by surface protection jointing material, the method that use ultraviolet etc. makes bounding force change and carries out peeling off also is usual method (patent documentation 7).Now, if not the base material making ultraviolet (uv) transmission, then the method cannot be used.
Therefore, painted large aromatic series quasi-polyimide, the PEN with naphthyl, tinsel etc. cannot be used.
In order to make ultraviolet (uv) transmission, polyolefin resin, vinyl-vinyl acetate copolymer resinoid, polyethylene terephthalate resinoid etc. that to use with polypropylene etc. be representative, but thermotolerance and dimensional stability are all insufficient.
, the transparency high sheet high as dimensional stability, has make to infiltrate in woven fiber glass thermosetting resin and the heat resistant transparent sheet (patent documentation 8) that obtains.Although disclose these characteristics of this materials serve and for the purposes of display element etc., the purposes of the base material of the jointing material used in the open manufacturing process as such semi-conductor.
Patent documentation 1: Japanese Unexamined Patent Publication 2004-311750 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-273723 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-138228 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-339236 publication
Patent documentation 5: No. 2004/065510, International Publication
Patent documentation 6: Japanese Unexamined Patent Publication 2008-143921 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2002-240842 publication
Patent documentation 8: No. 2012/067092, International Publication
Summary of the invention
Problem to be solved by this invention is, obtains the excellent semiconductor fabrication process jointing material having the transparency, thermotolerance, dimensional stability, flexibility, obdurability etc. concurrently.
The present invention finds, the sheet obtained by also solidifying making specific curable resin be infiltrated up in glass fibre is as the base material of semiconductor fabrication process jointing material, there is above-mentioned characteristic, the particularly transparency, thermotolerance, dimensional stability, thus complete the present invention.
That is, the present invention relates to a kind of semiconductor technology jointing material, it comprises by making curable resin (A) be infiltrated up to the sheet obtained in glass fibre (B).
Relate to above-mentioned semiconductor technology jointing material in addition, it possesses the layer with fusible material.
Relate to above-mentioned semiconductor technology jointing material in addition, wherein, the curable resin (A) after solidification is less than 0.005 with the difference of the light refractive index of glass fibre (B).
Relate to above-mentioned semiconductor technology jointing material in addition, wherein, curable resin (A) comprises the epoxy resin (a-1) in the molecule containing more than one epoxy group(ing) and contains the solidifying agent (a-2) of more than one carboxyl or acid anhydride in the molecule.
Relate to above-mentioned semiconductor technology jointing material in addition, wherein, solidifying agent (a-2) is the compound represented by general formula (1),
(in formula, multiple R of existence
1, R
2respective independence, R
1represent alkyl or the carboxyl of hydrogen atom, carbonatoms 1 ~ 6, R
2represent hydrogen atom or methyl, more than one for being selected from the group shown in above-mentioned general formula (1) of P, at * place and methylene radical bonding).
Relate to above-mentioned semiconductor technology jointing material in addition, carboxylic-acid solidifying agent (a-2) is the compound represented by general formula (2).
(in formula, multiple R of existence
3, R
4respective independence, R
3represent alkyl or the carboxyl of hydrogen atom, carbonatoms 1 ~ 6, R
4represent hydrogen atom, carbonatoms 1 ~ 15 alkyl, P as shown in above-mentioned general formula (2), at * place and methylene radical bonding).
Relate to above-mentioned semiconductor technology jointing material in addition, wherein, glass fibre (B) is woven fiber glass (b).
Invention effect
The feature of semiconductor fabrication process jointing material of the present invention is, use by make curable resin and glass fibre Composite and the slide obtained as its base material.By using this slide, the excellent jointing material having dimensional stability, thermotolerance, flexibility, obdurability, the transparency etc. concurrently can be obtained.
Jointing material of the present invention has high dimensional stability, and therefore, carry out various breakage, the warpage adding wafer in man-hour at bonding semiconductor wafer few.
The bonding die adhesive tape of the dicing tape that jointing material of the present invention uses when may be used for diced chip from semiconductor wafer or formation bonding die layer.Fix when using in the surface protection jointing material of semiconductor wafer when ground finish being carried out to the back side in the filming in order to semi-conductor chip, can farthest play effect of the present invention.
Embodiment
Curable resin (A) shown in the present invention is characterised in that the resin utilizing heat or light to be cured, and in the present invention, curable resin (A) is preferably after hardening in water white resin.
As the curable resin utilizing heat to be cured, the resin being referred to as epoxy resin, carbamate resins, (different) cyanate ester resin, resol, melamine resin, urea resin, unsaturated polyester resin, Synolac, Vinylite, amide resins etc. normally meets, and these resins all can use in the present invention.
The curable resin be cured as utilizing light, be referred to as acrylate resin, epoxy resin, vinyl ether resin resin normally meet, these resins all can use in the present invention.
The epoxy resin (a-1) used in the present invention as long as have the compound of epoxy group(ing) in the molecule, then can use arbitrarily.Below, the aromatic type epoxy resin preferably used in the present invention, aliphatics type epoxy resin are described.
Such as, as aromatic type epoxy resin, can enumerate: bisphenol-type epoxy resin, tris-phenol type epoxy resin, the oxalic dialdehyde type epoxy resin, (4 (4 (1 such as cresol novolak type epoxy resin, phenol novolak type epoxy resin, the biphenyl-phenolic resin varnish type epoxy resin such as phenol type epoxy resin, naphthol type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, two (p-hydroxybenzene) ethyl of 1-)-alpha, alpha-dimethylbenzyl) phenol) type epoxy resin etc.Wherein, in the present invention, thermotolerance is considered, preferred bisphenol A type epoxy resin, (4 (4 (two (p-hydroxybenzene) ethyl of 1,1-)-alpha, alpha-dimethylbenzyl) phenol) type epoxy resin.
As aliphatics type epoxy resin, can enumerate: there is the epoxy resin of cycloaliphatic ring structure and not there is the epoxy resin of cycloaliphatic ring structure.The feature with the epoxy resin of cycloaliphatic ring structure is, has at least more than one annular aliphatic structure in a molecule.Can enumerate such as: terpene diphenol, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy-benzene, dihydroxy naphthlene etc.) and aliphatic ring structure diene (dicyclopentadiene or norbornadiene, hexahydroxy-indenes etc.) polycondensate and by the derivative glycidyl etherified thing of their modifier, A Hydrogenated Bisphenol A (dihydroxyphenyl propane, Bisphenol F) type epoxy resin, alicyclic epoxy resins etc. have cyclohexyl structure in molecule, the compound of dicyclopentadiene structure, there is the epoxy resin etc. of triglycidyl group isocyanurate structure.Specifically, can enumerate such as: cyclohexane diol diglycidyl ether, 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane manthanoate, 2,1,2-epoxy-4-(2-Oxyranyle) the hexanaphthene affixture etc. of two (the hydroxymethyl)-n-butyl alcohol of 2-.
As the epoxy resin etc. without cycloaliphatic ring structure, can enumerate: the glycidyl ethers that hexane diglycidyl ether etc. is derived by straight or branched alcohol.
Epoxy resin also has containing the material from the chlorine component of the Epicholorohydrin as its raw material according to method for making.The long-term electrical characteristic of this chlorine component to semiconductor circuit bring detrimentally affect.Total chlorine amount in the material resin of the epoxy resin (a-1) used in the present invention is below 1000ppm, is more preferably below 600ppm.
In the present invention, operable solidifying agent can use generally well-known solidifying agent.Can enumerate such as: there is the carboxylic-acid solidifying agent of carboxyl or acid anhydride, there is amino, the amine curing agent, phenol novolacs etc. of amide group, ketoimine base, imidazolyl, Dyhard RU 100 base etc. have the phenols curing agent etc. of phenolic group.Wherein, carboxylic-acid solidifying agent (a-2) can provide thermotolerance high and the cured article that discolouration is excellent, therefore, preferably uses in the present invention.
Carboxylic-acid solidifying agent (a-2), as long as have more than one, the material of preferred plural carboxyl or more than one acid anhydride in molecule, is not particularly limited, can uses generally well-known solidifying agent.Carboxylic acid anhydride, aliphatic carboxylic acid can be used in the present invention, make to have in molecule the carboxylic acid that the compound of hydroxyl and carboxylic acid anhydride react and obtain, the acid anhydrides with unsaturated ring structure, by the addition reaction of carboxylic acid anhydride and ethoxylated polyhydric alcohol and the carboxylic acid etc. obtained.
As carboxylic acid anhydride, can enumerate such as: 1,2,4-cyclohexanetricarboxylic acid-1,2-acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, hexanaphthene-1,2-dicarboxylic anhydride, 1,2,4,5-cyclopentanetetracarboxylic-1,2,4,5-dianhydride, butane tetracarboxylic acid anhydrides, dicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methyl bicycle [2,2,1] heptane-2,3-dicarboxylic anhydride, hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydride etc.As aliphatic carboxylic acid, can enumerate: the aliphatic carboxylic acid class such as hexanodioic acid, sebacic acid, cyclohexane dicarboxylic acid, cyclohexanetricarboxylic acid.
As the compound with hydroxyl used in the carboxylic acid reacting at the compound and carboxylic acid anhydride that make to have in molecule hydroxyl and obtain, can enumerate: crosslinked many rings glycol such as the polyester glycols such as polyalkylene glycol, polycaprolactone glycol such as hydrocarbon polyalcohols, polyoxyethylene glycol, polypropylene glycol, the polytetramethylene glycols such as hydrocarbon glycols, glycerine, tetramethylolmethane, the Dipentaerythritols such as butyleneglycol, hexylene glycol, nonanediol, cyclohexanediol and silicone glycol, Tricyclodecane Dimethanol, methyl Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol etc.Carboxylic acid anhydride also comprises above-mentioned carboxylic acid anhydride, does not limit.
In addition, also the polyalcohols such as ternary alcohols, tetramethylolmethane, ethoxylated polyhydric alcohol such as glycerine, TriMethylolPropane(TMP), tri hydroxy methyl butane can be used.
Wherein, preferably by making as crosslinked many rings glycol of the compound in molecule with hydroxyl, wherein using the carboxylic acid (a-2a) that the tristane structure represented by following general formula (3), pentacyclopentadecandimethanol structure are reacted as glycol and the above-mentioned carboxylic acid anhydride of main framing and obtained.
(in formula, R
2represent hydrogen atom or methyl)
As mentioned above, as the crosslinked many rings glycol used in the present invention, can enumerate: Tricyclodecane Dimethanol, methyl Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol etc.Wherein, consider from the simplicity obtained and with the balance of amount of functional groups after manufacturing, in the present invention, particularly preferably Tricyclodecane Dimethanol.
The carboxylic acid obtained as the addition reaction by carboxylic acid anhydride and ethoxylated polyhydric alcohol, can enumerate: the carboxylic acid (a-2b) being obtained by the addition reaction of above-mentioned carboxylic acid anhydride and ethoxylated polyhydric alcohol, represented by following general formula (2).
(in general formula (2), R
3be more than 1 and independent separately, R
3represent alkyl or the carboxyl of hydrogen atom, carbonatoms 1 ~ 6, R
4represent the alkyl of hydrogen atom, carbonatoms 1 ~ 15 independently of one another)
As the ethoxylated polyhydric alcohol for obtaining carboxylic acid (a-2b), can enumerate: 2,2 '-bis-(dihydroxymethyl) dipropyl ether, 2,2 '-bis-(dihydroxymethyl) Anaesthetie Ether, 2,2 '-bis-(dihydroxymethyl) dibutyl ether, 2,2 '-bis-(dihydroxymethyl) hexyl ether.
As the acid anhydrides with unsaturated ring structure, can enumerate: Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride etc.
Wherein, preferably the above-mentioned carboxyanhydrides that the transparency is high is used.Wherein, can enumerate: 1,2,4-cyclohexanetricarboxylic acid-1,2-acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, particularly consider from the formedness of thermotolerance and process, preferably that both are used in combination further.
In addition, when forming the sealing material of thermotolerance, the transparency and excellent size stability, the carboxylic acid (a-2a) using compound and carboxylic acid anhydride by making to have in above-mentioned molecule hydroxyl to react and obtain or the carboxylic acid (a-2b) obtained by the addition reaction of above-mentioned carboxylic acid anhydride and ethoxylated polyhydric alcohol.Also can by used in combination for these two kinds of carboxylic acids.Carboxylic acid (a-2a) can provide the sealing material of particularly excellent heat resistance.On the other hand, carboxylic acid (a-2b) can be preferred for except excellent heat resistance, sealing material also be required to the situation of flexibility simultaneously.
Epoxy resin (a-1) is determined by the equivalent of the equivalent of the epoxy group(ing) contained in epoxy resin (a-1) and the carboxyl of carboxylic-acid solidifying agent (a-2) with the optimum ratio of carboxylic-acid solidifying agent (a-2).Relative to epoxy group(ing) 1 equivalent, preferred carboxyl is 0.2 ~ 5 equivalent, is more preferably 0.5 ~ 2 equivalent.When exceeding this scope, curing reaction can not fully carry out, and in addition, superfluous epoxy group(ing), carboxyl produce residual, thus cannot play obdurability, the thermotolerance of cured article fully.
In addition, in order to promote the reaction utilizing heat, usually reaction is promoted by induction heat, or, in order to regulate solidification value, also usual at epoxy resin (a-1) middle interpolation curing catalysts.As long as these curing catalysts have the curing catalysts of the effect promoting above-mentioned curing reaction, then can use generally well-known curing catalysts.
As curing catalysts, can enumerate such as: glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-undecyl imidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-ethyl-4-methylimidazole (1 ')) ethyl s-triazine, 2,4-diamino-6 (2 '-Methylimidazole (1 ')) ethyl s-triazine-isocyanuric acid adduct, the 2:3 affixture of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-bishydroxymethyl imidazoles, 2-phenyl-4-hydroxymethyl-5-Methylimidazole, the various imidazoles of 1-cyano ethyl-2-phenyl-3,5-dicyano ethoxyl methyl imidazoles, and these imidazoles and phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalic acid, toxilic acid, the salt of the polycarboxylic acids such as oxalic acid, the amidess such as Dyhard RU 100, 1,8-diazabicyclo (5,4,0) hendecene-7 diaza compound such as grade and their tetraphenylborate, the salt of phenol novolacs etc., with above-mentioned polycarboxylic acid class, or the salt of phospho acid class, Tetrabutyl amonium bromide, cetyltrimethylammonium bromide, the ammonium salt classes such as tricaprylmethyl brometo de amonio, triphenylphosphine, three (tolyl) phosphine, tetraphenylphosphonibromide bromide
tetraphenyl
tetraphenyl borate salts, hexafluoro-antimonic acid
the phosphine classes such as salt (ヘ キ サ Off ロ ロ ス チ PVC Application ホ ス ホ ニ ウ ム salt) or
the organometallic compounds etc. such as phenols, stannous octoate, cobalt octoate, zinc octoate, zirconium caprylate, nickel octoate, cobalt naphthenate such as compounds, 2,4,6-triamino methylphenols.In addition, can enumerate: make curing catalyst be formed as the microcapsule-type curing catalysts etc. of micro-capsule.
To use in these curing catalysts any should the characteristic required by jointing material suitably select.Curing catalysts uses usually relative to epoxy resin (a-1) 100 mass parts in the scope of 0.001 ~ 15 mass parts.
Also other compositions can be contained in curable resin (A).As these other compositions, can enumerate: antioxidant, UV light absorber etc.
As operable antioxidant in curable resin (A), as long as general known antioxidants such as phenols, sulphur class, phosphorus antioxidants, then do not limit.But, in view of feature of the present invention, preferably select the colourless and not easily painted antioxidant because of heat during solidification.
As phenol antioxidant, can enumerate: single phenols, bisphenols and polymer phenols etc.
As single phenols, can enumerate: 2,6-ditertbutylparacresol, butylated hydroxy anisole (BHA), 2,6-di-t-butyl p-ethyl phenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, iso-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, 2, two (n-octylthio)-6-(the 4-hydroxyl-3 of 4-, 5-di-tert-butyl amido)-1,3,5-triazine, 2,4-two [(octylsulfo) methyl] ortho-cresols etc.
As bisphenols, can enumerate: 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-Ding pitches base two (3 methy 6 tert butyl phenol), triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], 1,6-hexane diol two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2-thiodiethylene two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester-diethyl ester, 3,9-pair [1,1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl] 2,4,8,10-tetra-oxaspiros [5,5] undecane, two (3,5-di-tert-butyl-4-hydroxyl benzyl sulfonic acid) calcium etc.
As polymer phenols, can enumerate: 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester] methane, two [3, 3 '-bis--(4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] glycol ester, three (3, 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1, 3, 5-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) guanamine, 4, 6-(1H, 3H, 5H) triketone, tocopherol etc.
As the concrete example of sulphur class antioxidant, can enumerate: dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate etc.
As phosphorus antioxidants, can enumerate: phosphorous acid esters, oxa-phospho hetero phenanthrene are oxide-based.
As phosphorous acid esters, can enumerate: triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diiso decyl phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, diiso decyl pentaerythritol phosphite, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, two (octadecyl) phosphorous acid ester of ring neopentane four base, ring neopentane four base two (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, ring neopentane four base two (2, 4-di-t-butyl-4-aminomethyl phenyl) phosphorous acid ester, two [the 2-tertiary butyl-6-methyl-4-{2-(octadecane oxygen carbonyl) ethyl } phenyl] H-Phosphonate etc.
Oxide-based as oxa-phospho hetero phenanthrene, can enumerate: 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-(3,5-di-tert-butyl-4-hydroxyl benzyl)-9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-oxygen in last of the ten Heavenly stems base-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide etc.
These antioxidants can individually use, and also can combine and with two or more.The usage quantity of antioxidant, relative to composition epoxy resin 100 mass parts of the present invention, is generally 0.008 ~ 1 mass parts, is preferably 0.01 ~ 0.5 mass parts.In addition, in the present invention, preferred phosphorus antioxidants.
In the scope not damaging the characteristic such as the transparency, hardness, also can add the resinous principles such as butyral resinoid, acetal-based resin, acrylic resin, epoxy-nylon-based resin, NBR-phenolic resin, epoxy-NBR resinoid, polyamide-based resin, polyimide based resin, silicone based resin as required in curable resin (A).
Can add primary particle size in curable resin (A) is the particulate of 1 ~ 200nm.As particulate operable in the present invention, can enumerate such as: glass, silicon-dioxide, zirconium white, stannic oxide, titanium oxide, zinc oxide, tin indium oxide, weisspiessglanz, selenium oxide, yttrium oxide etc.These particulates can with the micro mist not containing dispersion solvent, the form acquisition being scattered in the colloidal solution of solvent.These particulates can use a kind of or used in combination two or more.The solvent that dispersion solvent can select each composition of the dissolving cured property resins (A) such as non-polar solvent such as ester class, toluene, dimethylbenzene such as ketone, ethyl acetate, butylacetate such as methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, dimethylformamide dimethyl yl acetamide uses.
Also silane coupling agent, releasing agent, flow agent, tensio-active agent, dyestuff, pigment, inorganic or organic light diffusion filler etc. can be added in curable resin (A).
General known metal-salt can be added in curable resin (A).Can enumerate such as: the metallic compounds etc. such as carboxylic metallic salt (zinc salt of 2 ethyl hexanoic acid, stearic acid, behenic acid, tetradecanoic acid etc., pink salt, zirconates) or phosphate metal (zinc salt of octylphosphonic acid, stearyl phosphoric acid etc.), metal alkoxides salt (tri-butyl aluminum, tetrapropyl zirconium etc.), acetylacetonate (methyl ethyl diketone zirconium chelate, acetylacetone titanium chelate etc.).These metal-salts can be used alone or use two or more.By adding metal-salt, the thermotolerance of jointing material of the present invention can be improved.
The glass fibre (B) used in the present invention is by glass melting, tractive and be formed as fibrous fiber.High obdurability and dimensional stability is given to the jointing material of the present invention by obtaining with curable resin (A) Composite.
Glass fibre carries out various classification according to the set form of its fiber usually.Its polymeric species should according to required by the jointing material base material in the present invention, the characteristic such as shape, intensity and thickness suitably selects.Can use in the forms such as such as glass non-woven fabric, glass fiber blanket, short-cut original silk silk felt, rove, chopped strand, milled fiber, line yarn, Coarse Mesh Gauze, woven fiber glass, glass bushing, glass rope in the present invention any one.Wherein, if consider purposes of the present invention, then preferred form glass fibre being made tabular or sheet.
In order to make tabular, sheet, the general known methods such as woven, knitting or non-woven fabrics can be used.Particularly from the view point of obdurability, dimensional stability, the glass fibre after by spinning can be most preferably used to form cloth-like, so-called woven fiber glass (b) by weaving.
As the kind of glass fibre (B), be not particularly limited, general known glass can be used.Can enumerate such as: so-called E-glass, S-glass, T-glass, D-glass, UN-glass, NE-glass, Q-glass etc.
Wherein, E-glass not easily introduces cavity when spinning, easily obtains, and alkalimetal oxide is few, is suitable for the present invention as non-alkali glass.On the other hand, from the view point of dimensional stability, although S-glass, T-glass have dominance, expensive, not talkative is preferred.In addition, silane coupling agent can be utilized for controlling to process with the adaptation of resin and capillary glass fibre.
About the diameter of glass fibre preferred in the present invention, if consider the transparency and smoothness etc., then the smaller the better, be preferably less than 10 μm.
In addition, due in middle smoothness requiring height such as grinding wafer operations, therefore, the woven fiber glass (b) after carrying out fibrillation processing is preferably used.The jointing material manufactured by the woven fiber glass carried out after fibrillation processing, comes from the concavo-convex few of texture of fabric, therefore can more preferably use.
In the present invention, about the light refractive index of curable resin (A) with glass fibre (B), roughly the same in the stage usually after resin solidification.Even if light refractive index there are differences, its difference is also less than 0.005, is more preferably less than 0.003.By making curable resin (A) be roughly the same value with the light refractive index of glass fibre (B), the transparency of the jointing material obtained improves.When exceeding this scope, the transparency of jointing material disappears.When the transparency is low, have problems when being introduced in and carrying out the operation of image inspection etc. to semiconductor element under the state of fitting with semiconductor wafer.
The formation of curable resin (A) suitably regulates according to the specific refractory power of woven fiber glass (b).Such as, the curable resin in curable resin (A) is the curable resin only with aliphatic structure, the specific refractory power of curable resin (A) reduces.On the other hand, as a method of the specific refractory power of raising curable resin (A), use and there is the curable resin of aliphatic structure and there is the curable resin of aromatic structure.
When using E-glass in the present invention, as an example of the combination of curable resin (A), can enumerate: the aromatic type epoxy resin as epoxy resin (a-1) and the combination as the carboxylic acid anhydride of solidifying agent (a-2).
As the method being made base material of the present invention by such curable resin (A) and glass fibre (B), such as there is following method: make curable resin (A) be infiltrated up in glass fibre (B), make prepreg, then make it solidify and obtain base material.
In the making of prepreg, generally speaking, if the curable resin of liquid state, then direct impregnated glass fiber (B), such as woven fiber glass (b) wherein, makes solvent evaporates dry, obtain prepreg thus, when high viscosity or solid-state curable resin, to be diluted in solvent etc. and prep solution, wherein impregnated glass fiber (B), such as woven fiber glass (b), make solvent evaporates dry, obtain prepreg thus.
State, i.e. state that is completely uncured or semicure that prepreg does not at least finish with curing reaction use.Now, preferred reactivity (that is, the value that reacting weight when being completed by the reacting weight/curing reaction of prepreg represents) is 0 ~ 0.95, is preferably 0.1 ~ 0.5.When reactivity is lower than above-mentioned value, be difficult to process prepreg, when reactivity is higher than above-mentioned value, produce problems such as bubbling when curing reaction.
The curing of the prepreg obtained is not particularly limited, and can use general known method.Method etc. can be listed below: such as, prepreg is cut into necessary thickness and shape, make it stacked as required, to being provided with the mould of release layer (such as, be smooth plate to obtain the tabular of plane) to keep the mode of shape to pressurize, heat simultaneously, be cured reaction and obtain cured article (curing process), then carry out the demoulding, obtain the cured article of tabular.
If consider drying conditions when making prepreg, then the thickness of woven fiber glass is generally less than 100 μm, is preferably less than 50 μm.When thicker than this thickness, the volatilization of solvent becomes difficulty, occurs the problem of due to residual solvent foaming etc. in curing process.When prepreg does not meet the thickness of necessary base material, can be overlapping and integrated to several pieces prepregs by 2 when solidifying, be cured.
Now, the preferred curable resin (A) of prepreg and the weight ratio of glass fibre (B) are represented by the weight of the weight/prepreg of the curable resin (A) of per unit area, be preferably 30 ~ 65%, be more preferably 40 ~ 55%.When resinous principle is more than this scope, dimensional stability, obdurability are deteriorated, and when being less than this scope, what occur from glass fibre on substrate surface is concavo-convex, and smoothness is impaired.
Semiconductor fabrication process jointing material of the present invention is by having fusible material and formed above-mentioned layers on substrates being folded.There is fusible material as used herein, the known tackiness agent being suitable for respective application target and manufacturing process can be used.Certainly, tackiness agent can be individual layer also can be multilayer.
As representative examples, can enumerate: the acrylic adhesives be made up of (methyl) acrylic acid esters co-polymer and solidifying agent.These tackiness agents can be enumerated: by make linking agent, such as isocyanates linking agent etc. and the compound by making to have (methyl) acryl as the monomer at center and have cause the monomer at the position of crosslinking reaction, the vinylformic acid 2-hydroxyl ethyl ester etc. such as with hydroxyl carries out copolymerization and the polymer reaction obtained and the tackiness agent etc. obtained.
When the irradiation by ultraviolet etc. after operation terminates bounding force is reduced and stripping semiconductor wafer, further and with the material of the ultraviolet hardenings such as polyfunctional acrylic ester in above-mentioned tackiness agent.In addition, the acrylic copolymer introduced and have the functional group of ultraviolet hardening is also usually used.
[embodiment]
Then, by embodiment, the present invention is given the account in greater detail.It should be noted that, the present invention is not limited in any way the following examples.In synthesis example 1 and 2, to terminate as reaction in the moment being confirmed alcohol hydroxyl group disappearance by gel permeation chromatography (hereinafter referred to as " GPC ").
Synthesis example 1: the synthesis of carboxylic-acid solidifying agent (a-2a)
In the flask possessing stirrer, reflux condensing tube, whipping appts, methylethylketone is added (following while enforcement nitrogen purging, MEK) until solids component reaches 70 quality %, the compound (glycol) and carboxylic acid anhydride in the molecule of the amount recorded in following table with hydroxyl is added.Then, at 50 DEG C, heated and stirred is carried out under the condition of 4 hours at 2 hours, 70 DEG C.Reaction end is confirmed by GPC, obtains the MEK solution of (a-2a).The solution obtained is water white transparency.
Table 1
Note) table in write a Chinese character in simplified form
Glycol: Tricyclodecane Dimethanol
Acid anhydrides 1:4-methylcyclohexane-1,2-dicarboxylic anhydride
Acid anhydrides 2: hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydride
Synthesis example 2: the synthesis of carboxylic-acid solidifying agent (a-2b)
In the flask possessing stirrer, reflux condensing tube, whipping appts, methylethylketone is added (following while enforcement nitrogen purging, MEK) until solids component reaches 70 quality %, the compound (ethoxylated polyhydric alcohol) and carboxylic acid anhydride in the molecule of the amount recorded in following table with hydroxyl is added.Then, at 50 DEG C, heated and stirred is carried out under the condition of 4 hours at 2 hours, 70 DEG C.Reaction end is confirmed by GPC, obtains the MEK solution of (a-2b).The solution obtained is water white transparency.
Table 2
Note) table in write a Chinese character in simplified form
Polyvalent alcohol: 2,2 '-bis-(dihydroxymethyl) dibutyl ether
Acid anhydrides 1:4-methylcyclohexane-1,2-dicarboxylic anhydride
Acid anhydrides 2: hexanaphthene-1,3,4-tricarboxylic acid-3,4-acid anhydride
The preparation of thermosetting resin (A) of embodiment 1:E-woven fiber glass
(in table, record amount is solids component scaled value to add record amount in table, addition as the solution of reality is documented in parantheses) synthesis example 1 and 2 in the carboxylic-acid solidifying agent (a-2a) that obtains, (a-2b) MEK solution (solids component 70%), aliphatics type epoxy resin EHPE-3150 (the Daicel chemistry system of record amount in table, epoxy equivalent (weight) 181), aromatic type epoxy resin NC-6300 (Japanese chemical drug system: (4 (4 (two (to the hydroxyphenyl) ethyl of 1,1-)-alpha, alpha-dimethylbenzyl) phenol) type epoxy resin, epoxy equivalent (weight) 206, total chlorine amount 550ppm), aromatic type epoxy resin NC-3000 (Japanese chemical drug system: biphenyl structural polyfunctional epoxy resin, epoxy equivalent (weight) 275, total chlorine amount 550ppm), aromatic type epoxy resin RE-310S (the Japanese chemical drug system: liquid bisphenol A epoxy resin of record amount in table, epoxy equivalent (weight) 185, total chlorine amount 500ppm), as other compositions is the zinc octoate of 0.3 quality % relative to total solids composition, relative to ア デ カ ス タ Block 260 (ADEKA system: phosphorus antioxidants) as additive that total solids composition is 0.2 quality %, relative to two (1-undecane oxygen bases-2 that total solids composition is 0.2 quality %, 2,6,6-tetramethyl piperidine-4-base) carbonic ether, relative to 2,4-two [2-hydroxyl-4-butoxy phenyl]-6-(2,4-dibutoxy phenyl)-1,3-5-triazines that total solids composition is 0.2 quality %, count the methylethylketone as diluting solvent of the amount of 70 quality % using total solids composition, be heated to 70 DEG C and make it dissolve, obtain curable resin (A) diluted composition.
Table 3
Embodiment 2: prepreg
And then, the composition epoxy resin obtained in embodiment 1 is diluted to the solids component ratio recorded in table, be infiltrated up to and be cut in square E-woven fiber glass (b) of about 30cm (all quite IPC specification 1037, specific refractory power 1.561), then, by solvent in the baking oven of 90 DEG C dry 30 minutes, obtain the prepreg that thickness is about 40 μm.
The weight ratio of the resin in the glass of the prepreg obtained/resin ratio, i.e. total tablet weight is as follows.Solids component ratio by with by utilizing Thermgravimetric Analysis Apparatus (TGA) to heat at 550 DEG C 1 hour in atmosphere obtained prepreg, resinous principle being oxidized, volatilizing after the ratio of residual components calculate.
Table 4
| Embodiment | Resin (A) | Solids component ratio | Resin ratio | Whipability |
| 2-1 | Embodiment 1-1 | 60％ | 58％ | ○ |
| 2-2 | Embodiment 1-2 | 60％ | 63％ | ○ |
| 2-3 | Embodiment 1-3 | 60％ | 60％ | ○ |
| 2-4 | Embodiment 1-1 | 40％ | 46％ | ○ |
Foaminess: the dried state of visual judgement prepreg.
Zero: the generation not observing bubble.
×: there is air bubble-shaped thing at prepreg left on surfaces.
Embodiment 3: the preparation of substrate sheets
The prepreg obtained in embodiment 2 is formed as individual layer or two-layer, sandwich and implement the polyester chips (PET) after peeling off processing, further use vacuum pressed machine, makes curable resin solidify under pressure 2MPa, temperature 150 DEG C, the condition of 5 hours set times.Take out from vacuum pressed machine, after cooling, peel off PET, obtain substrate sheets.
The specific refractory power of cured sheets is measured with prism coupler formula index meter (633nm).In addition, by obtained sheet digital flexion, be confirmed whether that there is sufficient flexibility.
The characteristic of obtained substrate sheets is shown in following table.
Table 5
| Embodiment | Prepreg | Layer is formed | The specific refractory power of cured article | The transparency | Flexibility |
| 3-1 | Embodiment 2-1 | Two-layer | 1.561 | ○ | ○ |
| 3-2 | Embodiment 2-2 | Two-layer | 1.560 | ○ | △ |
| 3-3 | Embodiment 2-3 | Two-layer | 1.562 | ○ | ○ |
| 3-4 | Embodiment 2-4 | Two-layer | 1.561 | ○ | ○ |
| 3-5 | Embodiment 2-1 | Individual layer | 1.561 | ○ | ◎ |
The transparency: the visual confirmation transparency.
Zero: do not observe gonorrhoea or painted.
Flexibility: strip sheet being cut into width 3cm, the long side direction digital flexion sheet rectangular by this, observes and makes the state that diameter is about the sheet of the bowlder of 5cm.
◎: enough soft, does not have crackle or scar.
Zero: there is no crackle or scar.
△: pole produces scar slightly, but be unlikely to become problem.
Synthesis example 3: the synthesis of tackiness agent acrylic resin
Add 65g butyl acrylate, 25g vinylformic acid 2-hydroxyl ethyl ester, 10g vinylformic acid, 200g as MEK (making solids component be 33 quality %), the 0.3g of solvent as the Diisopropyl azodicarboxylate of initiator, in stream of nitrogen gas, be warming up to while 80 DEG C successively from 50 DEG C, carrying out copolyreaction in 5 hours.
After copolymerization terminates, add 10g2-isocyanatomethyl ethyl propenoate, 0.5g butylated hydroxytoluene, 20g as the MEK (making solids component be 33 quality %) of solvent, reaction atmosphere is changed to air from nitrogen, at 80 DEG C, carry out reaction in 10 hours further, and then make amino-formate bond and unsaturated link(age) grafting and obtain acrylic copolymer.
Embodiment 4: the preparation of tackiness agent
Add prepare in synthesis example tackiness agent acrylic resin MEK solution 300g (being converted into solids component is 100g), dipentaerythritol acrylate 80g, as コ ロ ネ mono-ト L (the Japanese polyurethane industry system) 5g of linking agent, Le シ リ Application TPO (BASF system) 2g as light trigger, dissolve, preparation adhesive coated liquid.
Use applicator, by this coating solution on the polyester film implementing stripping processing, to make dried film reach 100 μm, in the baking oven of 80 DEG C, make solvent evaporates further, prepare tackiness agent.
Embodiment 5 and comparative example 1: the preparation of semiconductor machining jointing material and evaluating characteristics (imitating the evaluation of grinding back surface adhesive tape)
Carry out Corona discharge Treatment to the base material of preparation in embodiment 3, after making surface active, use vacuum laminator, the jointing material of preparation in laminating embodiment 4, obtains jointing material of the present invention.
In addition, as comparative example, base material is changed to each base material recorded in table by embodiment 2, fit similarly to Example 2, obtain the jointing material of comparative example.
Polyester film is peeled off, the silicon wafer (naked wafer, thickness 0.73mm) of laminating 8 inches thereon from obtained jointing material.
Then, while utilizing milling drum to the back side spraying cooling water of wafer, thickness 0.1mm is ground to.After grinding terminates, make moisture drying, evaluate the warpage situation (warpage evaluates 1) under room temperature under with the state of jointing material, further by wafer mounting 3 minutes on the hot plate of 100 DEG C and 200 DEG C, evaluate the warpage situation (warpage evaluates 100 DEG C and 200 DEG C) when imitating heating process.
Then, on the adsorption plate being heated to 60 DEG C, chip join that grinding surface is fitted sheet (Hitachi changes into system).500mJ/cm is irradiated from grinding back surface adhesive tape side
2ultraviolet, carry out the stripping of jointing material of the present invention.The evaluation result of its separability is as shown in table 6.
Table 6
Note) table in write a Chinese character in simplified form
PI: aromatic series quasi-polyimide (カ プ ト Application 200H, Dong Li Du Pont system)
PEN: PEN (テ オ ネ ッ Network ス Q51, Di Ren Du Pont system)
PET: polyethylene terephthalate (テ ト ロ Application G2, Di Ren Du Pont system)
OPP: biaxial stretch-formed polypropylene (ト レ Off ァ Application 2500H, eastern beautiful system)
The evaluation of warpage: about warpage, to when placing in the plane, due to generation warpage, the height of the highest part confirms.
Slightly: warpage is below 1mm
Little: 1mm ~ 5mm
In: 5mm ~ 10mm
Large: more than 10mm
Separability: observe the state in peeling off, after stripping.
Good especially: successfully to peel off especially, also do not observe generation of adhesive deposit.
Good: successfully to peel off, also do not observe generation of adhesive deposit.
Slightly difficult: successfully not peel off, but there is no generation of adhesive deposit.
Bad: to observe generation of adhesive deposit, or wafer breakage and cannot peeling off.
As can be known from the above results, use of the present invention has high dimensional stability by the sheet that makes curable resin (A) be infiltrated up to obtain in glass fibre (B) as the jointing material of base material.In wide temperature range, the warpage of the silicon wafer after processing film is little, therefore known, and jointing material of the present invention has excellent characteristic as semiconductor technology purposes.
Utilizability in industry
Semiconductor technology jointing material of the present invention plays high dimensional stability in wide temperature range, further, there is the good transparency simultaneously, therefore, be not limited to semiconductor technology jointing material, also can be applied to the jointing material of other objects requiring such characteristic.
Claims (5)
1. a semiconductor technology jointing material, obtain by making curable resin (A) be infiltrated up in glass fibre (B), it possesses the layer with fusible material, and the curable resin (A) after solidification is less than 0.005 with the difference of the light refractive index of glass fibre (B).
2. semiconductor technology jointing material as claimed in claim 1, wherein, curable resin (A) comprises the solidifying agent (a-2) containing more than one carboxyl or acid anhydride in the epoxy resin (a-1) and molecule containing more than one epoxy group(ing) in molecule.
3. semiconductor technology jointing material as claimed in claim 1, wherein, solidifying agent (a-2) is the compound represented by general formula (1),
In formula (1), multiple R of existence
1, R
2respective independence, R
1represent alkyl or the carboxyl of hydrogen atom, carbonatoms 1 ~ 6, R
2represent hydrogen atom or methyl, more than one for being selected from the group shown in described general formula (1) of P, at * place and methylene radical bonding.
4. semiconductor technology jointing material as claimed in claim 1, wherein, carboxylic-acid solidifying agent (a-2) is the compound represented by general formula (2),
In formula (2), multiple R of existence
3, R
4respective independence, R
3represent alkyl or the carboxyl of hydrogen atom, carbonatoms 1 ~ 6, R
4represent the alkyl of hydrogen atom, carbonatoms 1 ~ 15, P as described in as shown in general formula (2), at * place and methylene radical bonding.
5. semiconductor technology jointing material as claimed in claim 1, wherein, glass fibre (B) is woven fiber glass (b).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-118863 | 2013-06-05 | ||
| JP2013118863A JP2014234500A (en) | 2013-06-05 | 2013-06-05 | Adhesive material for semiconductor manufacturing process |
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| CN104231958A true CN104231958A (en) | 2014-12-24 |
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| JP (1) | JP2014234500A (en) |
| KR (1) | KR20140143084A (en) |
| CN (1) | CN104231958A (en) |
| TW (1) | TW201510157A (en) |
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| TWI724179B (en) * | 2016-06-10 | 2021-04-11 | 日商昭和電工材料股份有限公司 | Adhesive film and die-cut die-bonded integrated film |
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| WO2020137934A1 (en) * | 2018-12-28 | 2020-07-02 | リンテック株式会社 | Film-like adhesive agent, layered sheet, composite sheet, and method for producing layered body |
| KR102428497B1 (en) * | 2019-12-11 | 2022-08-02 | 미츠비시 가스 가가쿠 가부시키가이샤 | Compound and its manufacturing method, resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
| KR20240021144A (en) * | 2021-06-15 | 2024-02-16 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin compositions, resin sheets, multilayer printed wiring boards, and semiconductor devices |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606597A (en) * | 2002-01-25 | 2005-04-13 | 住友电木株式会社 | Transparent composite composition |
| CN1656156A (en) * | 2002-05-27 | 2005-08-17 | 日东电工株式会社 | Resin sheet and liquid-crystal cell substrate comprising the same |
| WO2010150524A1 (en) * | 2009-06-22 | 2010-12-29 | 日本化薬株式会社 | Polyvalent carboxylic acid, composition thereof, curable resin composition, cured product, and method for manufacturing a polyvalent carboxylic acid |
-
2013
- 2013-06-05 JP JP2013118863A patent/JP2014234500A/en active Pending
-
2014
- 2014-05-08 KR KR1020140054746A patent/KR20140143084A/en not_active Application Discontinuation
- 2014-05-30 TW TW103118956A patent/TW201510157A/en unknown
- 2014-06-05 CN CN201410246886.8A patent/CN104231958A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606597A (en) * | 2002-01-25 | 2005-04-13 | 住友电木株式会社 | Transparent composite composition |
| CN1656156A (en) * | 2002-05-27 | 2005-08-17 | 日东电工株式会社 | Resin sheet and liquid-crystal cell substrate comprising the same |
| WO2010150524A1 (en) * | 2009-06-22 | 2010-12-29 | 日本化薬株式会社 | Polyvalent carboxylic acid, composition thereof, curable resin composition, cured product, and method for manufacturing a polyvalent carboxylic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI724179B (en) * | 2016-06-10 | 2021-04-11 | 日商昭和電工材料股份有限公司 | Adhesive film and die-cut die-bonded integrated film |
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| TW201510157A (en) | 2015-03-16 |
| JP2014234500A (en) | 2014-12-15 |
| KR20140143084A (en) | 2014-12-15 |
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