WO2011071107A1 - Composition adhésive photosensible ayant une adhésivité même après réaction de photodurcissement et après formation de motif - Google Patents

Composition adhésive photosensible ayant une adhésivité même après réaction de photodurcissement et après formation de motif Download PDF

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WO2011071107A1
WO2011071107A1 PCT/JP2010/072117 JP2010072117W WO2011071107A1 WO 2011071107 A1 WO2011071107 A1 WO 2011071107A1 JP 2010072117 W JP2010072117 W JP 2010072117W WO 2011071107 A1 WO2011071107 A1 WO 2011071107A1
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Prior art keywords
acid
pattern formation
photosensitive adhesive
adhesive composition
alkali
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PCT/JP2010/072117
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English (en)
Japanese (ja)
Inventor
正臣 高野
滑川　崇平
健 青山
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新日鐵化学株式会社
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Priority to JP2011545239A priority Critical patent/JP5833928B2/ja
Publication of WO2011071107A1 publication Critical patent/WO2011071107A1/fr

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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2463/00—Presence of epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a photosensitive adhesive composition having adhesiveness even after photocuring reaction and after pattern formation. Specifically, a pattern of a portion that is photocured by alkali development and photocured by alkali development. After forming, by using the thermosetting function of the pattern, for example, bonding between silicon wafers required in the semiconductor device manufacturing process, bonding between glass substrates, bonding between a silicon wafer and a glass substrate, etc.
  • the present invention relates to a photosensitive adhesive composition capable of bonding an object with excellent adhesive strength and heat resistance.
  • the photosensitive adhesive part that is, the part where the substrate is bonded with the formed pattern, withstands heat resistance at high temperature and cure shrinkage at cooling, and adhesive strength Need to hold. That is, it is required that the reflow resistance is strong.
  • thermosetting resin when a photosensitive adhesive composition that can be patterned without containing a thermosetting resin is used, the heat resistance during assembly of the semiconductor package is low, peeling and cracking are likely to occur at the bonding interface, and reliability Therefore, it tends to cause insulation failure.
  • the photosensitive adhesive composition containing a thermosetting resin when it is set as the photosensitive adhesive composition containing a thermosetting resin, it exists in the tendency for the exposure sensitivity at the time of pattern formation to be low, and for alkali developability to become inadequate.
  • the photosensitive adhesive composition in which a polyimide resin and a thermosetting resin are combined a high adhesive force during heat is maintained by including a polyimide resin having a relatively low melting point, and 250 ° C. during mounting.
  • the inclusion of a thermosetting resin does not dissolve during alkali development, and a residue is likely to be generated.
  • the present invention has been made in view of such circumstances of the prior art, and after photocuring a portion to be imparted with an adhesive function and forming a pattern of the photocured portion by alkali development, the pattern is
  • the thermosetting function for example, bonding objects such as bonding of bonding objects such as bonding between silicon wafers, glass substrates, bonding between a silicon wafer and a glass substrate, which are necessary in a semiconductor device manufacturing process.
  • an adhesive layer having high adhesive strength, heat resistance including reflow resistance and high reliability to semiconductors can be formed, pattern formation is possible, and each step of the assembly process of the semiconductor package is possible.
  • An object of the present invention is to provide a photosensitive adhesive composition that does not cause problems such as tack that affect the photosensitive adhesive composition.
  • the gist of the present invention is as follows. That is, the present invention relates to a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid as a resin component in the resin composition.
  • An alkali-soluble resin obtained by reacting an acid or a tricarboxylic acid or an acid anhydride thereof and b) a tetracarboxylic acid or an acid dianhydride in a range where the molar ratio of a / b is 0.1 to 10.
  • the present invention also relates to (A) a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, and a) a dicarboxylic acid or tricarboxylic acid, or these And b) an alkali-soluble resin obtained by reacting a tetracarboxylic acid or its acid dianhydride in a range where the molar ratio of a / b is 0.1 to 10, (B) at least 1 A photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation, comprising a photopolymerizable monomer having one ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) an epoxy resin It is a thing.
  • the alkali-soluble resin (A) is preferably a compound represented by the following general formula (1).
  • W shows the bisphenol derivative represented by following General formula (2)
  • Y shows a tetravalent carboxylic acid residue.
  • G represents a substituent represented by the following general formula (3) or (4)
  • Z represents a hydrogen atom or a substituent represented by the general formula (5).
  • N represents a number from 1 to 20.
  • R 1 , R 2 , R 3 , and R 4 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a phenyl group, but R 1 , R 2 , R 3 and R 4 are preferably hydrogen atoms.
  • X represents —CO—, —SO 2 —, —C (CF 3 ) 2 —, —Si (CH 3 ) 2 —, —CH 2 —, —C (CH 3 ) 2 —, —O—, 9 , 9-fluorenediyl group or a direct bond
  • A is preferably a 9,9-fluorenediyl group.
  • m represents an integer of 0 to 10.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents a divalent alkylene or alkylarylene group having 2 to 22 carbon atoms
  • R 7 represents a divalent aliphatic or aromatic hydrocarbon having 2 to 20 carbon atoms.
  • a group, p is a number from 0 to 60, and q is 0 or 1.
  • L is a divalent or trivalent carboxylic acid residue, and r is 1 or 2.
  • the specific composition of the composition is as follows: an epoxy having two glycidyl ether groups derived from bisphenols For a reaction product of a compound and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and b) a tetracarboxylic acid or an acid dianhydride thereof.
  • examples of the saturated linear hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid.
  • succinic acid acetylsuccinic acid
  • adipic acid adipic acid
  • azelaic acid citralmalic acid
  • malonic acid glutaric acid
  • citric acid citric acid, tartaric acid, oxoglutaric acid.
  • There are compounds such as acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid (or their anhydrides), and further, straight-chain hydrocarbon dicarboxylic acids and tricarboxylic acids substituted with saturated hydrocarbons (or acids thereof) Anhydride).
  • alicyclic dicarboxylic acids and tricarboxylic acids include, for example, hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid (and their acids).
  • alicyclic dicarboxylic acids and tricarboxylic acids substituted with saturated hydrocarbons.
  • unsaturated dicarboxylic acid and tricarboxylic acid for example, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, trimellitic acid (or Their acid anhydrides).
  • succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferred, and succinic acid, itaconic acid and tetrahydrophthalic acid are more preferred. Two or more of these acids or acid monoanhydrides can be used in combination.
  • examples of the saturated linear hydrocarbon tetracarboxylic acid or acid dianhydride thereof include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or acid dianhydride thereof. Further, it may be a saturated cyclic tetracarboxylic acid substituted with a saturated cyclic hydrocarbon or an acid dianhydride thereof.
  • cycloaliphatic tetracarboxylic acid or its acid dianhydride cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid or its acid dianhydride
  • an alicyclic tetracarboxylic acid substituted with a saturated hydrocarbon or an acid dianhydride thereof may be used.
  • aromatic tetracarboxylic acid or acid dianhydride thereof examples include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid or acid dianhydride thereof. be able to.
  • the acid or acid dianhydride in the present invention is preferably biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid or acid dianhydride, more preferably biphenyl tetracarboxylic acid or biphenyl ether tetracarboxylic acid. Or its acid dianhydride. Two or more of these acids or acid dianhydrides can be used in combination.
  • the alkali-soluble resin (A) includes a diol compound obtained by reaction of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated monocarboxylic acid, a saturated or unsaturated polybasic acid anhydride, And having a weight average molecular weight of 3,000 to 40,000 and an acid value of 50 to 200 mgKOH / g are preferred.
  • the diol compound reacted with acid dianhydride has the same reactivity between the two hydroxyl groups in the molecule and acid dianhydride from the viewpoint of increasing the molecular weight during the polymerization reaction. Those having a symmetric molecular structure are preferred.
  • the photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation of the present invention is a photopolymerizable monomer having at least one ethylenically unsaturated bond ( It is preferable to further contain B), a photopolymerization initiator or sensitizer (C), and an epoxy compound (D) having at least one epoxy group.
  • Examples of the photopolymerizable monomer (B) include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipent
  • the content of the photopolymerizable monomer (B) is such that the mass ratio [(A) / (B)] of the alkali-soluble resin (A) and the photopolymerizable monomer (B) is 20/80 to 90. / 10 is preferable, more preferably 40/60 to 80/20, and particularly preferably 60/40 to 80/20. If the mass ratio is less than the above lower limit, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so the solubility in an alkali developer is lowered, and the pattern edge is jagged and sharp. There is a tendency for problems to occur.
  • the proportion of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is not sufficient, and the acid value in the resin component is too high, so that the exposed portion is dissolved in an alkaline developer. Since the property becomes high, there is a tendency that the formed pattern becomes thinner than the target line width and the pattern is easily lost.
  • Examples of the photopolymerization initiator or sensitizer (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- Acetophenones such as butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2 -(O-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fu Bi
  • the content of these photopolymerization initiators or sensitizers (C) is 2 to 30 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the photopolymerizable monomer (B).
  • the amount is preferably 5 to 20 parts by mass. If the content of the photopolymerization initiator or sensitizer (C) is less than the lower limit, the photopolymerization rate tends to be slow and the sensitivity tends to decrease. On the other hand, if the content exceeds the upper limit, the sensitivity is too strong and the pattern is low. The line width becomes thicker than the pattern mask, and the line width faithful to the mask tends to be difficult to reproduce.
  • Examples of the epoxy compound (D) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, and alicyclic epoxies.
  • epoxy resins such as resins
  • compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate and the like can be mentioned.
  • epoxy compounds (D) can be used individually by 1 type or in combination of 2 or more types. By blending these epoxy compounds (D), thermosetting or tackiness can be imparted to the photosensitive adhesive composition having adhesion even after the photocuring reaction and pattern formation used in the present invention. .
  • the content of the epoxy compound (D) is 10 to 30 parts by mass with respect to 100 parts by mass of the total amount of the alkali-soluble resin (A) and the photopolymerizable monomer (B). Preferably, the amount is 10 to 20 parts by mass. If the content of the epoxy compound (D) is less than the lower limit, the moisture resistance and heat resistance of the coating film and the adhesiveness to the substrate tend to be lowered. The preservability of the functional resin tends to decrease.
  • the photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation according to the present invention includes, for example, silica and alumina for the purpose of reducing the thermal expansion of the cured product and improving the elastic modulus and hygroscopicity.
  • one or more inorganic fillers such as titanium oxide and boron nitride may be blended.
  • other additives such as an epoxy resin curing accelerator, a polymerization inhibitor, a plasticizer, a leveling agent, and an antifoaming agent can be added to the composition of the present invention as necessary.
  • Examples of the epoxy resin curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds.
  • Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.
  • Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate.
  • Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.
  • a solvent can be blended as necessary to adjust the viscosity.
  • the solvent is preferably one that dissolves the resin composition and does not react with the resin and additives of the resin composition, and is not particularly limited as long as these conditions are satisfied.
  • the method for applying the photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation of the present invention described above is not particularly limited, and the adhesiveness is also maintained after the photocuring reaction and after the pattern formation.
  • a method of laminating a photosensitive adhesive composition having a film, a method of coating a photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation, a liquid coating method, after photocuring reaction and after pattern formation In addition, a known method such as a method of arranging a photosensitive adhesive composition having adhesiveness by printing can be appropriately selected and employed.
  • the coating thickness after drying of the photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation varies depending on the application, but for example, 1 to 10 ⁇ m for liquid crystal displays and 1 to 100 ⁇ m for circuit boards It is.
  • Vias and fine lines less than or equal to the coating thickness can be formed. For example, when the film thickness is 30 ⁇ m, a via diameter of 30 ⁇ m is obtained, and lines and spaces with a width of 20 ⁇ m can be formed. Further, when the film thickness is 5 ⁇ m, 2.5 ⁇ m isolated lines and isolated dots can be formed.
  • a part of the photosensitive adhesive composition having adhesiveness after the photocuring reaction and after the patterning is removed by photolithography. Any method can be used as long as it can irradiate a predetermined portion of the photosensitive adhesive composition having adhesiveness even after pattern formation, and then remove the portion not irradiated with light, and appropriately adopt a known photolithography technique. can do.
  • the light irradiation amount when the photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation is irradiated varies depending on the ambient temperature and the thickness of the photosensitive adhesive composition.
  • a range of 50 to 1000 mJ / cm 2 is preferable, and a range of 200 to 800 mJ / cm 2 is more preferable. If the light irradiation amount is less than the lower limit, the exposed portion irradiated with light tends to be soluble, whereas if the upper limit is exceeded, a part of the unexposed portion is photocured due to a dark reaction, resulting in resolution. Decreases.
  • a photosensitive adhesive composition having adhesiveness after the photocuring reaction and after the pattern formation is used to form the pattern portion, and the conditions for forming the pattern portion by photolithography are adjusted. As a result, it is possible to form a pattern portion having an adhesive property.
  • the thickness and width of the pattern portion to be formed are not particularly limited, and the thickness and width can be adjusted by appropriately changing the design according to the configuration of the member.
  • thermocompression bonding is not particularly limited, but it is preferable to perform pressure bonding at a temperature of 50 to 300 ° C., a time of 1 second to 60 minutes, and a pressure of 0.01 to 10 MPa, and particularly a temperature of 110 to 150 ° C. and a time of 30 seconds to 30 minutes.
  • the pressure bonding is preferably performed at a pressure of 0.05 to 1.0 MPa.
  • the adhesive strength can be further improved.
  • a desired structure can be obtained by performing a suitable assembly process using the bonded body obtained by thermosetting.
  • the silicon wafer and the silicon wafer, the glass substrate and the glass substrate, and the silicon wafer and the glass substrate are typically used as the objects to be bonded by the adhesive layer, but the silicon wafer and the organic substrate, the glass substrate and the organic substrate, and the like. It can also be used as an adhesive layer between various substrates including the above.
  • the photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation of the present invention high adhesive strength is obtained, and high reliability such as heat resistance and insulation properties is obtained. Excellent alkali developability is exhibited. As a result, high-density mounting of the semiconductor package becomes possible, and the assembly process can be greatly simplified and the cost can be reduced.
  • FIG. 1 is a diagram showing a planar shape of a mask used in the example.
  • FIG. 2 is an explanatory view schematically showing a cross-sectional configuration of a substrate with a photosensitive adhesive composition according to a preferred embodiment.
  • FIG. 3 is an explanatory diagram showing a mask pattern used in the reflow resistance test in the example.
  • FIG. 4 is an explanatory diagram showing a cross-sectional structure of the bonded body used in the reflow resistance test in the examples.
  • a synthesis example will be described as a method for producing an alkali-soluble resin.
  • the abbreviations used in the synthesis examples and the resin evaluation methods are as follows.
  • BPFE Bisphenol fluorene type epoxy resin (compound of general formula (2) wherein R 1 , R 2 , R 3 and R 4 are hydrogen atoms, X is a 9,9-fluorenediyl group, and m is 0)
  • HOA-HH (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate HOA-HH (in general formula (3), R 5 is a hydrogen atom, R 6 is ethylene, R 7 is 1,2-cyclohexylene, p is 1 and q)
  • TPP Triphenylphosphine
  • BPDA Biphenyltetracarboxylic acid dianhydride
  • Solid content 100 ⁇ (W 2 ⁇ W 0 ) / (W 1 ⁇ W 0 )
  • alkali-soluble resin had a solid content of 55.1%, an acid value (in terms of solid content) of 68.6 mgKOH / g, and a Mn of 1510 by GPC analysis.
  • Example 1 (Preparation of photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation) 60 parts by weight of A-1 obtained above as an alkali-soluble resin (A), 12 parts by weight of trimethylolpropane triacrylate (TMPT) as an unsaturated compound, and 2-methyl-1- [4- as a photopolymerization initiator 2 parts by weight of (methylthio) phenyl] -2-monoforinopropane-1, 26 parts by weight of epoxy resin (Epicoat 834 manufactured by Yuka Shell Co., Ltd.), 0.04 of sensitizer (EABF manufactured by Hodogaya Chemical Co., Ltd.) Part by weight, 0.8 part by weight of a silane coupling agent, 0.8 part by weight of a surfactant, and 100 parts by weight of ethyl acetate were mixed and stirred for 1 hour with a stirrer to dissolve or disperse the solution. . Thereafter, pressure sensitive filtration was performed using a filter having a hole
  • a photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation prepared as described above was applied to a BT (bismaleimide-triazine resin) substrate (10 mm ⁇ 300 mm ⁇ 200 ⁇ m thick) using a spin coater. ) And dried in an oven set in a temperature range of 80 to 120 ° C. to obtain an adhesive layer made of a photosensitive resin composition having adhesiveness after the photocuring reaction with a film thickness of 20 ⁇ m and after pattern formation. It was.
  • BT bismaleimide-triazine resin
  • An ultra-high pressure mercury lamp (HITECH) is provided through a negative mask (FIG. 1) provided with a predetermined mask pattern (here, a mask pattern for forming a 2 mm ⁇ 2 mm square) on the adhesive layer obtained by drying as described above.
  • a predetermined mask pattern here, a mask pattern for forming a 2 mm ⁇ 2 mm square
  • company Ltd. after exposure to ultraviolet irradiation under the condition of 250 mJ / cm 2 at an intensity 11 mJ / cm 2, I line reference), a 2.38% TMAH aqueous solution was used as a developing solution, while swinging at 23 ° C.
  • the unexposed portion is dissolved and developed for 1 minute until the surface of the BT substrate is exposed, and then rinsed with pure water at a pressure of 3.0 kg / cm 2 for 30 seconds, and an adhesive layer (2 mm ⁇ 2 mm square size) 20) remained.
  • a silicon wafer (30) of 2 mm ⁇ 2 mm ⁇ thickness 300 ⁇ m is placed on the 2 mm ⁇ 2 mm square adhesive layer, and thermocompression bonded at 110 ° C. for 10 seconds while applying a pressure of 0.3 MPa. Then, the silicon wafer (30) was adhered to the adhesive layer (20). Next, it was cured in an oven at 180 ° C. for 90 minutes to obtain a test bonded body according to Example 1.
  • Example 2 The test application according to Example 2 was performed in the same manner as in Example 1 except that the bonding temperature when the silicon wafer (30) was thermocompression bonded to the adhesive layer (20) on the BT substrate was 120 ° C. A combined body was obtained.
  • Example 3 The test attachment according to Example 3 was performed in the same manner as in Example 1 except that the bonding temperature at the time of thermocompression bonding of the silicon wafer (30) to the adhesive layer (20) on the BT substrate was set to 130 ° C. A combined body was obtained.
  • Example 4 A test bonded body according to Example 4 was obtained in the same manner as in Example 1 except that a glass substrate (40) having a size of 2 mm ⁇ 2 mm ⁇ thickness of 300 ⁇ m was used instead of the silicon wafer (30).
  • Example 5 Bonding for test according to Example 5 in the same manner as in Example 4 except that the bonding temperature at the time of thermocompression bonding of the glass substrate (40) to the adhesive layer (20) on the BT base material was set to 120 ° C. Got the body.
  • Example 6 Test bonding according to Example 6 except that the bonding temperature when the glass substrate (40) is thermocompression bonded to the adhesive layer (20) on the BT base material is 130 ° C. Got the body.
  • Example 7 A test bonded body according to Example 7 was obtained in the same manner as in Example 1 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • Example 8 A test bonded body according to Example 8 was obtained in the same manner as in Example 2 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • Example 9 A test bonded body according to Example 9 was obtained in the same manner as in Example 3 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • Example 10 A test bonded body according to Example 10 was obtained in the same manner as in Example 4 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • Example 11 A test bonded body according to Example 11 was obtained in the same manner as in Example 5 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • Example 12 A test bonded body according to Example 12 was obtained in the same manner as in Example 6 except that the alkali-soluble resin (A-2) was used instead of the alkali-soluble resin (A-1).
  • ⁇ Moisture resistance reliability test> After exposing the entire surface under the conditions of Example 1, it was cured in an oven at 180 ° C. for 90 minutes. Thereafter, the substrate with resin was placed in a PCT measuring instrument, taken out every 50 hours while being left under the conditions of a temperature of 121 ° C. and a humidity of 100%, and the change of the coating film was confirmed with a microscope. Those in which a change was observed compared with the original coating film immediately after curing were judged to be deteriorated, and the test was stopped for the sample.
  • Adhesive strength is 20 MPa or more and less than 30 MPa, and the fracture state is interfacial peeling.
  • ⁇ Adhesive strength is 1 MPa or more and less than 20 MPa.
  • X Adhesive strength cannot be measured.
  • a photosensitive adhesive composition having adhesiveness after photocuring reaction and pattern formation used in the above-mentioned Examples and Comparative Examples was spin coated on a separately prepared silicon wafer substrate (30) or glass substrate (40). Apply and dry in an oven set at a temperature range of 80 to 120 ° C to form a coating film with a film thickness of 20 ⁇ m, and then apply a predetermined mask pattern (mask pattern that forms 3mm x 3mm square, 1mm space) Except using the provided negative mask (part of the mask pattern shown in Fig. 3 as a model), exposure and development were performed under the same conditions as in Example 1, and a 3 mm ⁇ 3 mm square, 1 mm space grid adhesive layer (20) was formed.
  • a silicon wafer substrate (30) or a glass substrate (40) is bonded on the adhesive layer of the substrate with the photosensitive adhesive under the same conditions as in each example and each comparative example, cured and bonded (Fig. 4 shows a part of the cross-sectional structure as a model).
  • Each bonded body was placed on a 270 ° C. hot plate, allowed to cool for 3 minutes, and then visually checked for the presence or absence of peeling between the adhesive layer and the substrate interface, and evaluated according to the following criteria. The results are summarized in Table 1. ⁇ : No peeling even after repeated 10 times ⁇ : No peeling after 5 to 10 times ⁇ : Peeling from the first time

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Die Bonding (AREA)

Abstract

La présente invention concerne une composition adhésive photosensible ayant une adhésivité même après réaction de photodurcissement et après formation de motif, la composition présentant une résistance adhésive élevée, ayant une résistance à la chaleur, conférant une fiabilité élevée à des semi-conducteurs, et présentant une excellente aptitude au développement d'alcali. La composition adhésive photosensible ayant une adhésivité même après réaction de photodurcissement et après formation de motif comprend une composition de résine qui contient, en tant que composant principal de résine, une résine soluble dans un alcali obtenue à partir d'un produit de la réaction d'acide (méth)acrylique avec un composé époxy ayant deux groupes éther glycidylique et dérivé d'un composé bisphénol, par réaction du produit de réaction avec a) un acide dicarboxylique (ou un acide tricarboxylique) ou l'anhydride de celui-ci et b) un acide tétracarboxylique ou le dianhydride de celui-ci, le rapport molaire a/b étant dans la plage de 0,1 à 10.
PCT/JP2010/072117 2009-12-11 2010-12-09 Composition adhésive photosensible ayant une adhésivité même après réaction de photodurcissement et après formation de motif WO2011071107A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016530365A (ja) * 2013-09-30 2016-09-29 エルジー・ケム・リミテッド ラジカル硬化型接着剤組成物及びこれを含む偏光板

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339356A (ja) * 1992-02-04 1993-12-21 Nippon Steel Corp 光重合性不飽和化合物及びアルカリ現像型感光性樹脂組成物
JPH1022641A (ja) * 1996-07-03 1998-01-23 Toppan Printing Co Ltd 多層プリント配線板及びその製造方法
JPH10183088A (ja) * 1996-12-26 1998-07-07 Sumitomo Bakelite Co Ltd 感光性アディティブ接着剤組成物及び多層プリント配線板の製造方法
JP2003176343A (ja) * 2001-12-11 2003-06-24 Nagase Chemtex Corp 光重合性不飽和樹脂、その製造方法及びそれを用いたアルカリ可溶型感放射線性樹脂組成物
JP2006003860A (ja) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd 感光性樹脂組成物及びそれを用いたカラーフィルター
WO2006129669A1 (fr) * 2005-05-31 2006-12-07 Taiyo Ink Manufacturing Co., Ltd. Composition pour former un modele adhesif, structure multicouche obtenue en utilisant celle-ci, et procede pour produire une telle structure multicouche
JP2009185270A (ja) * 2007-05-30 2009-08-20 Nagase Chemtex Corp 縮環構造含有樹脂

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339356A (ja) * 1992-02-04 1993-12-21 Nippon Steel Corp 光重合性不飽和化合物及びアルカリ現像型感光性樹脂組成物
JPH1022641A (ja) * 1996-07-03 1998-01-23 Toppan Printing Co Ltd 多層プリント配線板及びその製造方法
JPH10183088A (ja) * 1996-12-26 1998-07-07 Sumitomo Bakelite Co Ltd 感光性アディティブ接着剤組成物及び多層プリント配線板の製造方法
JP2003176343A (ja) * 2001-12-11 2003-06-24 Nagase Chemtex Corp 光重合性不飽和樹脂、その製造方法及びそれを用いたアルカリ可溶型感放射線性樹脂組成物
JP2006003860A (ja) * 2003-11-26 2006-01-05 Nippon Steel Chem Co Ltd 感光性樹脂組成物及びそれを用いたカラーフィルター
WO2006129669A1 (fr) * 2005-05-31 2006-12-07 Taiyo Ink Manufacturing Co., Ltd. Composition pour former un modele adhesif, structure multicouche obtenue en utilisant celle-ci, et procede pour produire une telle structure multicouche
JP2009185270A (ja) * 2007-05-30 2009-08-20 Nagase Chemtex Corp 縮環構造含有樹脂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016530365A (ja) * 2013-09-30 2016-09-29 エルジー・ケム・リミテッド ラジカル硬化型接着剤組成物及びこれを含む偏光板

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