KR100885794B1 - Dicing die bonding film composition using radical curing - Google Patents

Abstract

The present invention relates to an adhesive film composition for assembling a semiconductor, and more particularly, to a radical polymerization type elastomer resin which enables radical polymerization from a hydroxyl group, a carboxyl group or an epoxy group, a high glass transition temperature (Tg) in the range of 0 ° C to 200 ° C. Adhesion-promoting crystalline polyester film-forming resin, (meth) acrylate resin and monomer, (meth) acrylate resin curing agent, additives, silane coupling agent, filler, and an organic solvent It relates to an adhesive film composition. The adhesive film composition for semiconductor assembly of the present invention can provide an adhesive film for semiconductor assembly which can improve processability due to rapid curing during the semiconductor manufacturing process by curing is made by radical polymerization.

Adhesive film for semiconductor assembly, radical polymerization elastomer, peroxide, silane coupling agent, die share value, semiconductor process

Description

Adhesive film composition for radical curing type semiconductor assembly {DICING DIE BONDING FILM COMPOSITION USING RADICAL CURING}

1 is a schematic cross-sectional view of a sample for measuring a die share of a film according to the present invention.

The present invention relates to an adhesive film composition for assembling semiconductors, and more particularly, by curing using a radical polymerization method, radical curing type semiconductor assembling adhesives, which can shorten the curing time of a film when assembling electronic components and improve productivity. It is about a film.

Conventionally, silver paste has been mainly used for joining a semiconductor element and an element or support member, but according to the tendency of miniaturization and large capacity of semiconductor elements, support members used for such miniaturization and miniaturization are also required. However, conventionally used silver paste has disadvantages such as abnormality during wire bonding due to protrusion or inclination of semiconductor elements, bubble generation, and difficulty in controlling thickness. Therefore, in recent years, the adhesive film is mainly used in place of the silver paste.

The adhesive film used for semiconductor assembly is mainly used together with a dicing film, and the dicing film refers to a film used to fix a semiconductor wafer in a dicing process of a series of semiconductor chip manufacturing processes. The dicing process is a process of cutting individual chips from a semiconductor wafer, and an expand process, a pick-up process and a mounting process are performed successively to the dicing process. The dicing film is usually formed by coating an ultraviolet curable or general curable pressure-sensitive adhesive on a vinyl chloride or polyolefin base film and adhering a cover film of PET material thereon.

On the other hand, the general use of the adhesive film for assembling the semiconductor is attached to the adhesive film on the semiconductor wafer (wafer), and the dicing film having the above configuration is applied to the dicing film from which the cover film is removed, followed by the dicing process To fragment. In addition, the dicing film from which the PET cover film is removed and the adhesive film are laminated to each other to form a single film, and then a semiconductor wafer is attached thereon and fragmented according to the dicing process.

Most of the above adhesive films are epoxy type curing methods. However, the epoxy curing method has a high reliability but very long curing time.

That is, the semiconductor assembly process includes a wafer mounting process, a cutting process, a UV curing process, a chip bonding process, a wire bonding process, an epoxy molding process, and the like, from the chip bonding process to the epoxy molding process. The curing process in consideration of the curing characteristics of the proceeds. However, the epoxy curing method has a problem in that it must be heated for a long time to fix the chip and the chip.

The present invention is to overcome the problems of the prior art described above, one object of the present invention can shorten the semiconductor manufacturing time by a cure skip process by the radical polymerization method instead of the conventional epoxy cured adhesive film It is to provide an adhesive film composition for assembling a radically polymerized semiconductor.

Still another object of the present invention is to provide an adhesive film for semiconductor assembly manufactured using the adhesive film composition.

One aspect of the present invention for achieving the above object,

A radically polymerized elastomer resin, an adhesion promoting film-forming resin, a radically polymerized resin, a radically polymerized thermal initiator, an additive, a filler, and an organic solvent are related.

In the present invention, the radical polymerization elastomer resin may be a rubber containing a vinyl group, an acrylate group capable of radical polymerization from a hydroxyl group, a carboxyl group or an epoxy.

In the present invention, the radically polymerizable material may be selected from the group consisting of acrylate-based, methacrylate-based and maleimide-based.

One aspect of the present invention for achieving the above object relates to an adhesive film for semiconductor assembly comprising the composition.

Hereinafter, the present invention will be described in more detail.

The adhesive film composition for semiconductor assembly of the present invention is characterized in that it comprises a radically polymerizable composition capable of shortening the adhesive film production time by a cure skip process by the radical polymerization method. The radically polymerizable composition can be freely controlled and cured at low temperature according to the semiconductor assembly process because the curing time range is very diverse depending on the type and content of peroxide. warpage defects can be reduced.

The adhesive film composition for semiconductor assembly of the present invention includes a radical polymerized elastomer resin, an adhesion promoting film forming resin, a radical polymerized resin, a radical polymerized thermal initiator, an additive, and a filler.

The radically polymerizable elastomer resin is a rubber component necessary for film formation, and is a rubber containing a vinyl group and an acrylate group to enable radical polymerization from a hydroxyl group, a carboxyl group or an epoxy. It is preferable that the elastomer containing a hydroxyl group, carboxyl group, or epoxy which can be radically polymerized has a weight average molecular weight in the range of 500 to 5,000,000. The radically polymerizable elastomer resin that can be used in the present invention is produced by reacting an acrylate monomer capable of chemical bonding with an elastomer containing a hydroxyl group, a carboxyl group or an epoxy group.

As a specific example, an isocyanate-based (meth) acrylate monomer capable of chemically bonding to an elastomer containing a hydroxyl group is used. Examples of the isocyanate-based (meth) acrylate monomers include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and the like.

As the elastomer containing a carboxyl group, a glycidyl (meth) acrylate monomer capable of chemically bonding thereto is used. As glycidyl (meth) acrylate monomer, glycidyl methacrylate, glycidyl acrylate, methyl glycidyl methacrylate, methyl glycidyl acrylate, 2- (3,4-epoxycyclohexyl) Methacrylate, 2- (3,4-epoxycyclohexyl) acrylate, and the like.

As the elastomer containing an epoxy group, a carboxyl (meth) acrylate monomer capable of chemical bonding thereto is used. As the carboxyl (meth) acrylate monomer, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl hexa there is carboxy polycaprolactone monoacrylate, acrylic Acid dimer, etc. - dihydro phthalate, meta-acrylic Acid, ω.

These monomers are added to the elastomer and reacted by stirring for 1 to 3 days at 40 to 60 ° C.

Elastomers containing a hydroxyl group, a carboxyl group or an epoxy that can be radically polymerized may include, for example, acrylonitrile, butadiene, styrene, acryl, and isoprene. (Isoprene), ethylene (Ethylene), propylene (Propylene), polyurethane and silicone (silicone), and isocyanate, epoxy and carboxy clock which can chemically react with elastomers containing hydroxyl, carboxyl and epoxy groups One or more selected from the group consisting of acrylate or vinyl group-derived radical polymerized elastomers may be used, but is not limited thereto.

The content of the radically polymerizable elastomer resin is preferably 5 to 75 parts by weight based on the whole adhesive film composition for semiconductor assembly.

The adhesion promoting film-forming resin of the present invention has a high glass transition temperature (Tg) in the range of 0 ° C to 200 ° C as a resin which helps to form the adhesion film and promote interfacial adhesion. The adhesion promoting film-forming resin is a crystalline polyester resin, the weight average molecular weight is preferably in the range of 200 to 1,000,000. If the molecular weight is more than that, the crystallinity is inferior.

The crystalline polyester adhesion promoter resin used in the present invention is represented by the following formula (1).

[Formula 1]

In the above description, R1 is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, and an alkyl group is a glycol group, a cyclohexyl group, a seba group, an adipe group, a hexyl group, Butane group, oxalic group decay group, terephthal group, isophthal group and the aromatic is selected from the group consisting of naphthalene group, diphenyl group, oxybenzo group, trimellitic group, trimesic acid group, pyromellitic group, the substituent is a carboxyl group , A halogen group, a phenyl group, a siloxane group, an alkoxy group, a hydroxy group, and an alkyl group.

R2 is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, and the alkyl group may be an ethyl group, a propyl group, an isobutyl group, a neopentyl group, a cyclohexane group or a pentaeryrile. It is a troll group, an octahydro 4,7-methano-1H- indendimethyl group, and it is chosen from the group which consists of a hydroquinone group, a resorcinol group, a phenyl group, a bisphenol group, and a naphthalene group as aromatic, The said substituent is a carboxyl group, a halogen group, a phenyl group , At least one selected from the group consisting of a siloxane group, an alkoxy group, a hydroxy group, an alkyl group, a halogen, and a phenyl group, n is 1 to 300.

The crystalline polyester adhesion promoting resin of Chemical Formula 1 is polymerized from a diol having a carboxyl group having a bifunctional group or more and a hydroxyl group having a bifunctional group or more, and has fluidity and adhesiveness at a specific temperature of the crystalline polyester resin. It forms the structure to give. The crystalline polyester-based adhesion promoting resin has a special property that the viscosity drops rapidly with temperature. Examples of the compound containing a carboxyl group having a bifunctional or higher functional group before polymerization including R1 include oxalic acid, succinic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1 , 5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, diphenoxytene-4,4-dicarboxylic acid, diphenylsulfone Dicarboxylic acid, glycolic acid, para-oxybenzoic acid, para-oxyethoxybenzoic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, hexanedionic acid, butenedionic acid, trimellitic acid, trimesic acid Food acid, pyromellitic acid. Examples of diols containing hydroxyl groups of at least bifunctional groups before polymerization including R2 include ethylene glycol, propylene glycol, isobutylene glycol, 2,6-dihydroxynaphthalene, octahydro-4,7- as alcohols. Methano-1H-indene-dimethanol, butanediol, neopentylglycol, hydroquinone, lesosinol, dihydroxyphenyl, naphthalenediol, dihydroxyphenylester, cyclohexanediol, 2,2-bis (4-hydride And hydroxyphenyl) propane, diethoxybisphenol A, pentaerythritol and hydroxyl groups of at least bifunctional groups substituted with alkyl, alkoxy or halogen.

In embodiments of the present invention, the content of the crystalline polyester adhesion promoting resin is preferably 1 to 50 parts by weight based on the whole adhesive film composition for semiconductor assembly. If the content is 50 parts by weight or more, the tensile strength of the film may be significantly reduced, resulting in a coating defect of the film.

The radically polymerizable resin of the present invention may use one or more selected from the group consisting of acrylate, methacrylate and maleimide. The radically polymerizable material has one or more functional groups and is an oligomer or monomer having a weight average molecular weight in the range of 500 to 100,000.

Preferred examples of the radical polymerization type resin include urethane acrylate oligomers having a weight average molecular weight in the range of 300 to 100,000 or epoxy acrylate oligomers having a weight average molecular weight in the range of 300 to 30,000.

The urethane acrylate oligomer has a molecular structure of polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, ring-opening tetrahydrofuran Tetrahydrofurane-propyleneoxide ring opening copolymer, polybutadiene diol, polydimethylsiloxane diol, ethylene glycol, propylene glycol, 1,4-butanediol 1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol Methanol (1,4-cyclohexane dimethanol), bisphenol A, hydrogenated bisphenol A, 2,4-toluene diisocyanate, 1,3-xylene Diiso 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane diisocyanate It is synthesized from isocyanate (1,6-hexan diisocyanate), isophorone diisocyanate.

The epoxy acrylate oligomer is a bisphenol, such as 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, 4,4'-dihydroxy ratio It contains skeletons such as phenyl, bis (4-hydroxyphenyl) ether, phenol group, cresol group, cresol novolac, and prolene group, and includes alkyl group, aryl group, methylol group, allyl group, cyclic aliphatic group, halogen, nitro group It is selected from what introduced.

Moreover, although the (meth) acrylate type monomer can be used as said radical polymerization type resin, the (meth) acrylate type monomer containing an epoxy group or a carboxyl group can be used especially.

Preferred examples of the (meth) acrylate monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2- as hydroxyl groups. Hydroxy-3-acryloyl propyl (meth) atrylate 1-hydroxybutyl (meth) acrylate, polycaprolactone polyol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) Acrylate, 2-hydroxy 3-phenoxy propyl acrylate, 2-acryloyl hydroxyethyl 2-hydroxy ethyl phthalate, di (meth) acrylate based bisphenol A (e.g. EB-600 manufacturer: SK-UCB ) May be included.

Examples of the (meth) acrylate-based monomer containing an epoxy group include (meth) acrylate (eg, dicel) containing glycidyl (meth) acrylate and methylglycidyl (meth) acrylate alicyclic epoxy. M100 or A200) can be mentioned.

Examples of the (meth) acrylate-based monomer containing the carboxyl group include 2-methacryloyloxyethyl hexahydro phthalate, 2-methacryloyloxyethyl succinate, and the like. Pentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritolpenta (meth) acrylate (Dipentaerythritolpenta (meth) acrylate), glycerin Di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isodecyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (Meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate , Ethoxy addition type nonylphenol (meth) acrylate (ethoxylated nonylphenolacrylate), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethyleneglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butylene glycoldi (meth) acrylate, tripropylene glycol di (meth) acrylic Ethylene, ethoxy addition type bisphenol- idi (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, 2-methacryloyloxyethyl phosphate, 2-methacryl Royloxyethylphosphate, dimethylol tricyclo decaine di (meth) acrylate, dipentaerythritol hexaacrylate, trimethylpropanebenzoate acrylate And it may be selected from the group consisting of a mixture thereof.

It is preferable that the said radical polymerization type resin contains 5-50 weight part with respect to the whole composition for adhesive films of this invention.

The radical polymerization type thermal initiator of the present invention generates free radicals by heat, and preferred examples thereof may include peroxide initiators.

Examples of the peroxide initiator include methyl ethyl ketone peroxide, dipercumyl peroxide, t-butyl peroxylaurate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanone

, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-butylhydroperoxide, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocapcarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t- Hexylperoxybenzoate, t-butylperoxyacetate, α, α-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5, -dimethyl-2,5-di (t- Butyl peroxy) hexane, t-butyl cumylture oxide, t-exyl peroxy neodecanoate, t-hexyl peroxy-2-ethyl hexanonate, t-butylperoxy-2-2-ethylhexanoate , t-butylperoxy isobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexyl peroxyisopropyl monobarcarbonate, t-butylperoxy-3,5,5-trimethylhexa Nonate, t-butylperoxy pivalate, cumylperoxy neodecanoate, diisopropylbenzenehi Dropperoxide, diisopropylbenzenehydroperoxide, cumenehydroperoxide, isobutylperoxide, 2,4-dichlorobenzoylperoxide, 3,5,5-trimethylhexanoylperoxide, octanoylperoxide, lauro Yl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxy toluene, benzoyl peroxide, 1,1,3 , 3-tetramethylbutylperoxy neodecanoate, 1-cycloexyl-1-methylethylperoxynodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, Bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate , Di (3-methyl-3-methoxybutylperoxy) dicarbonate, 1,1-bis (t-exylperoxy) -3,3,5- Dimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t- Butyl peroxy) cyclododecane, 2,2-bis (t-butylperoxy) decane, t-butyltrimethylsilylperoxide, bis (t-butyl) dimethylsilylperoxide, t-butyltriallylsilyl peroxide, Bis (t- butyl) diallyl silyl peroxide, tris (t- butyl) yl silyl peroxide, etc. are mentioned, Preferably, the said radical polymerization type | mold thermal initiator consists of a peroxide resin, and the 10-hour half life temperature is The adhesive film composition for semiconductor assembly, characterized in that at least one member selected from the group of 60 ℃ or more.

In the present invention, the radical polymerization type thermal initiator preferably contains 0.001 to 10 parts by weight based on the whole composition for the adhesive film.

The silane coupling agent of the present invention is not particularly limited as an adhesion promoter for enhancing the adhesion between the surface of an inorganic material such as silica and the resins of the adhesive film when the composition is blended, and the (meth) acrylate group, isocyanate group, The silane coupling agent containing an amino group or a mercito group can be used.

Specific examples of the silane coupling agent include a (meth) acrylate group-containing silane coupling agent such as (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) triethoxysilane and methacrylamide. Propyl triethoxysilane), N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) bis (trimethylsiloxy) methyl silane, (methacryl Oxymethyl) dimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyl diethyl methoxysilane, methacryloxypropyl methyl diethoxysilane, methacryloxy 3-mercetopropylmethyldimethoxysilane containing 3-propyl methyldimethoxysilane, methacryloxypropyltriethoxysilane, and methacryloxypropyltrimethoxysilane mercury, 3-mercetopropyltri Methoxysilane, 3-isocyanatepropyltriethoxysilane containing isocyanate, N-2 (aminoethyl) 3-amitopropylmethyldimethoxysilane containing amine group, N-2 (aminoethyl) 3-aminopropyltrimeth Methoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysil-N- (1,3 -Dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and mixtures thereof can be used.

In the present invention, the content of the silane coupling agent is preferably 0.001 to 10 parts by weight based on the entire adhesive film composition for semiconductor assembly.

The filler of the present invention may be inorganic or organic filler, if necessary, as the inorganic filler, alumina, magnesium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, Aluminum oxide, aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide, ceramic, and the like can be used, and as the organic filler, carbon, rubber filler, polymer or the like can be used. The shape and size of the filler is not particularly limited, but in the inorganic filler, spherical silica and amorphous silica are mainly used, and the size thereof is preferably in the range of 5 μm to 10 μm in diameter.

The content of the filler in the present invention is preferably 0.1 to 60 parts by weight based on the entire adhesive film composition for semiconductor assembly.

The adhesive film composition for semiconductor assembly according to the present invention may further comprise additives such as polymerization inhibitors, antioxidants, thermal stabilizers, ion trapping agents.

The anti-polymerization agent is an additive that exhibits storage stability of the composition. It may be selected from the group consisting of.

The antioxidant may be a phenolic-based or hydroxy cinnamate-based material to prevent oxidation of the composition induced by heat. The material not only prevents oxidation but also has thermal stability. Examples of the antioxidant, tetrakis- (methylene- (3,5-di-tetrabutyl-4-hydrocinnamate) methane (tetrakis- (methylene- (3,5-di-terbutyl-4- hydrocinnamate) methane ), 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenenepropanoic acid thioldi-2,1-ethanediyl ester (3,5-bis (1,1-dimethylethyl)- 4-hydroxybenzenepropanoic acid thiodi-2,1-ethanediyl ester), octadecyl 3,5-di- (tertiary) -butyl-4-hydroxyhydrocinnamate (Octadecyl 3,5-Di- (tert) -butyl- 4-hydroxyhydrocinnamate) (above manufactured by Cibageigy), 2,6-di-tertary-para-methylphenol (2,6-di-tert-butyl-p-methylphenol), 4-tert-butylbutylcatechol (4- Tertiarylbutylcatechol) and mixtures thereof.

The thermal stabilizer is an additive that suppresses decomposition by high temperature heat. 2,6-di-tert-butyl-p-methyl phenol (4-tertary) Butylcatechol (4-Tertiarylbutylcatechol).

The ion trapping agent is for absorbing the ionic impurities and realizing insulation reliability during moisture absorption, and is not particularly limited. For example, triazine thiol compounds, zirconium compounds, and antimony bismuth compounds may be used. inorganic ion adsorbents such as bismuth) and magnesium aluminum compounds.

In the present invention, the content of the additive is preferably 0.001 to 5 parts by weight based on the entire adhesive film composition for semiconductor assembly.

The organic solvent of the present invention is to facilitate the film production by lowering the viscosity of the adhesive film composition for semiconductor assembly, but is not particularly limited, toluene, xylene, propylene glycol monomethyl ether acetate, benzene, acetone, methyl ethyl ketone , Tetrahydrofuran, dimethylformaldehyde, cyclohexanone and the like can be used.

In the present invention, the content of the organic solvent is a residual amount excluding the content of the remaining components in the entire composition for the adhesive film for semiconductor assembly, preferably 5 to 85 parts by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for illustrative purposes only and are not intended to limit the protection scope of the present invention.

[ Example  1-5]

To the 1L cylindrical flask containing a high-speed stirring rod, respectively, the ingredients corresponding to Examples 1 to 5 were added and dispersed at high speed at 4000 rpm for 20 minutes to prepare a composition. The composition was then ground completely using a 3 roll mill. The grinding operation was performed two or more times and filtered using a 50 μm capsule filter and then coated with an applicator to a thickness of 20 μm to prepare an adhesive film, and dried at 80 ° C. for 10 minutes and then stored at room temperature for 3 days.

Example  One

(a) Carboxylic and hydroxyl group-containing elastomer resin (WS-023, manufactured by Nagase Chemtex) 400 g, 2-isocyanatoethyl methacrylate (Karens MOI, manufactured by Sowa Denko) 2 g, diurethane reaction catalyst 2000 ppm of butyltin dilaurylate was added and stirred at 40 ° C for 1 day.

(b) 100 g of polyester adhesion promoter resin (AR-LTH, manufactured by Daegu) 100 g of solid epoxy film forming agent (YD-013K, manufactured by Kukdo Chemical)

(c) Bisphenol-based bifunctional acrylate 120g (VR-60, manufactured by bovine high molecular weight)

(d) 15 g by weight of tris (2-hydroxyethyl) isocyanurate triacrylate (SR-368, manufactured by Satomer), which is an isocyanurate trifunctional acrylate (unreacted 2-isocyanato) To remove ethyl methacrylate, 2 g of trishydrocyethyl isocyanurate diacrylate (M-215. Manufactured by Toagosei Chemical Industries, Ltd.) containing a dihydroxy group was added and stirred at 40 ° C. for 1 day.

(e) 2 g of benzoyl peroxide (Nyper BW, manufactured by NOF),

(f) 0.1 g of hydroquinone monomethylether,

(g) 0.5 g of mercury silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.),

  0.5g of acrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Co., Ltd.),

(h) 40 g of amorphous silica filler (Aerosil 200, manufactured by Daegu),

Example  2

(a) 600 g of epoxy-containing elastomer resin (Teisan P3-TEA, manufactured by Nagase Chemtex) and 10 g of acryloyloxyethylphthalic acid (M-5400, manufactured by Toagosei Chemical Industry Co., Ltd.) were added at 60 ° C. Stir for days.

(b) 100 g of polyester adhesion promoter resin (Elitel UE3600, manufactured by Unitika), 100 g of solid epoxy film forming agent (YD-013K, manufactured by Kukdo Chemical)

(c) Bisphenol-based bifunctional acrylate 120g (VR-90, manufactured by bovine high molecular weight)

(d) tris (2-hydroxyethyl) isocy which is isocyanurate trifunctional acrylate

15 g of anurate triacrylate (SR-368, manufactured by Satomer),

(e) tbutylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF) 2 g,

(f) 0.1 g of hydroquinone monomethylether,

(g) Merchito silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.) 0.5 g,

   Acrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

(h) amorphous silica filler (Aerosil 200, manufactured by Daegu) 40 g,

Example  3

(a) Carboxyl group and hydroxyl group-containing elastomer resin (KLS-1046, manufactured by Fujikura Chemical Co., Ltd.) 600 g, 1,1-bisacryloyloxymethylethyl isocyanate (Carens BEI, manufactured by Sowadenko) 2 g, glycidyl 2 g of methacrylate and 2000 ppm of dibutyl tin dilaurate as a urethane reaction catalyst were added and stirred at 60 ° C. for 3 days.

(b) 100 g of polyester adhesive promotion resin (AR-2325, manufactured by Daegu), 100 g of solid epoxy film forming agent (YD-013K, manufactured by Kukdo Chemical)

(c) Bisphenol-based bifunctional acrylate 120g (VR-60, manufactured by bovine high molecular weight)

(d) 15 g of tris (2-hydroxyethyl) isocyanurate triacrylates (SR-368, manufacturer: Satomer) which is isocyanurate trifunctional acrylate, unreacted 2-isocyanatoethyl meta To remove the acrylate, 2 g of trishydrocyethyl isocyanurate diacrylate (M-215. Manufactured by Toagosei Chemical Industries, Ltd.) containing a dihydroxy group was added and stirred at 40 ° C. for 1 day.

(e) 2 g of benzoyl peroxide (Nyper BW manufactured by NOF),

(f) 0.1 g of hydroquinone monomethylether,

(g) Merchito silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.) 0.5 g,

  Acrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

(h) amorphous silica filler (Aerosil 200, manufactured by Daegu) 40 g,

Example 4

(a) 800 g of epoxy-containing elastomer resin (Teisan SG-80H, manufactured by Nagase Chemtex) and 10 g of 2-acryloyloxy hexahydrophthalate (HOA-HH, manufactured by Co., Ltd.) were added thereto, and the result was 3 days at 60 ° C. Stirred.

(b) 100 g parts by weight of polyester adhesion promoting resin (Elitel UE3320, manufactured by Unitika), 100 g of a solid epoxy film-forming agent (YD-013K, manufactured by Kukdo Chemical)

(c) Bisphenol-based bifunctional acrylate 120g (VR-60, manufactured by bovine high molecular weight)

(d) 15 g of tris (2-hydroxyethyl) isocyanurate triacrylate which is an isocyanurate trifunctional acrylate (SR-368, a manufacturer: Satomer),

(e) tbutylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF) 2 g,

(f) 0.1 g of hydroquinone monomethylether,

(g) Merchito silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.) 0.5 g,

  Acrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

(h) amorphous silica filler (Aerosil 200, manufactured by Daegu) 40 g,

Example 5

(a) 600 g of epoxy-containing elastomer resin (KLS-1045DR, manufactured by Fujikura Corporation) and 10 g of 2-acryloyloxyethyl succinate (HOA-MS, manufactured by Kogyo Co., Ltd.) were added thereto, and the mixture was stirred at 60 ° C for 3 days. .

(b) 100 g of polyester adhesion promoter resin (AR-2440, manufactured by Daegu), 100 g of solid epoxy film forming agent (YD-013K, manufactured by Kukdo Chemical)

(c) Bisphenol-based bifunctional acrylate 20g (EB-600, manufactured by SK-UCB), Bisphenol-based bifunctional acrylate 100g (VR-60, manufactured by bovine high molecular weight)

(d) 15 g of tris (2-hydroxyethyl) isocyanurate triacrylate which is an isocyanurate trifunctional acrylate (SR-368, a manufacturer: Satomer),

(e) tbutylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF) 2 g,

(f) 0.1 g of hydroquinone monomethylether,

(g) Merchito silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.) 0.5 g,

  Acrylate silane coupling agent (KBM-503, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

(h) amorphous silica filler (Aerosil 200, manufactured by Daegu) 40 g,

[ Comparative example  ]

Since the adhesive film for a semiconductor assembly commonly used is a curing reaction of an epoxy resin and a phenol resin, a comparative film was prepared in the same manner as in the above example except that the composition was added as follows.

(a) carboxyl group and hydroxyl group-containing elastomer resin (KLS-1046, manufactured by Fujikura Corporation) 400g,

(b) 100 g of film-forming resin consisting of bisphenol A and bisphenol F (E4275, manufactured by JER, molecular weight 60,000), 100 g of polyester adhesion promoting resin (Elitel UE3320, manufactured by Unitica)

(c) 150g of epoxy resin (YDCN-500-90P, manufactured by Kukdo Chemical, molecular weight 10,000 or less) consisting of cresol novolac system

(d) Xylox curing agent (MEH-7800S, manufacturer: Meiwa Plastic Industries) 145g,

(e) imidazole-based curing catalyst (2P4MZ, manufactured by Shukuk Chemical) 0.6g,

(f) Merceto silane coupling agent (KBM-803, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

   Epoxy silane coupling agent (KBM-303, manufactured by Shin-Etsu Co., Ltd.) 0.5g,

(g) 40 g of amorphous silica filler (OX-50, manufactured by Daegu),

** Example  And In the comparative example  Evaluation of physical properties of the prepared adhesive film **

Physical properties of the adhesive film for semiconductor assembly prepared in Example 1-5 was evaluated as follows, and the results are shown in Table 1 below. In addition, in order to measure the curing rate, the residual curing rate at a constant temperature condition was measured, and the results are shown in Table 1 below.

TABLE 1

** Property Evaluation Method **

(1) Residual hardening rate: After leaving each film at 125 ° C for 10 minutes, 30 minutes, and 1 hour, DSC (Differential Scanning Calorimeter) was measured, followed by calorific value at room temperature and 10 minutes, 30 minutes, and 1 hour at 125 ° C. After standing, the calorific value was measured and the residual curing rate was measured. Calculation of the residual hardening rate is shown in [Equation 1].

△ H (specific temperature, time) / △ H (room temperature, time) X 100% = residual cure rate (%)

(2) Die Shear Strength: Cut a 720um wafer coated with a dioxide film into 5mm x 5mm size as shown in Figure 1, lamination at 60 degrees with adhesive film and leave only the adhesive part. Cut. Place a wafer with a thickness of 720 μm and a size of 10 mm x 10 mm on a hotplate with a temperature of 120 degrees, attach a piece of wafer with adhesive lamination on it, and compress it with a force of 1 kgf for 20 seconds, and then at 150 degrees for 1 hour [Comparative Example 175 4 hours] completely cured. Measuring method was a die share at 250um 100sec / sec as shown in the figure.

As shown in Table 1, in the case of the adhesive film prepared by using the radical polymer type elastomer and the resin (Example), the curing time is shorter than the case of the general epoxy curable adhesive film (Comparative Example), the die share value is different It can be applied to the epoxy resin and phenol resin curable adhesive film commonly used in the semiconductor assembly process, and can improve the processability due to the control of a wide curing time.

The adhesive film composition for assembling semiconductors according to the present invention includes a radical polymerization type (meth) acrylate, which improves the curing speed, so that curing can be skipped at an intermediate stage during the semiconductor manufacturing process, and adhesive strength is also used for curing an epoxy resin and a phenolic resin. It is possible to provide an adhesive film for semiconductor assembly that can secure the film level.

Claims (14)

Radically polymerized elastomer resins; Adhesion promoting crystalline polyester film forming resins; Radically polymerized resins; Radical polymerization thermal initiators; A silane coupling agent containing a (meth) acrylate group, an isocyanate group, an amino group or a mercito group; Fillers; additive; And organic solvents, The additives include polymerization inhibitors, antioxidants, heat stabilizers, ion trapping agents, The ion trapping agent comprises an inorganic ion adsorbent comprising a triazine thiol compound, zirconium-based, antimony bismuth-based, magnesium aluminum-based compound, the adhesive film composition for semiconductor assembly. The adhesive film composition for semiconductor assembly according to claim 1, wherein the radically polymerizable elastomer resin is formed by bonding a (meth) acrylate monomer to an elastomer containing a hydroxyl group or a carboxyl group or an epoxy group. The (meth) acrylate-containing monomer capable of chemically reacting with the functional group of the elastomer resin, wherein the hydroxyl group is an isocyanate-based (meth) acrylate, the carboxyl group is a glycidyl-based (meth) acrylate, and the epoxy group is a carboxyl clock. An adhesive film composition for semiconductor assembly comprising (meth) acrylate.   The adhesive film composition for semiconductor assembly according to claim 1, wherein the crystalline polyester-based adhesion promoting resin is represented by the following general formula (1). [Formula 1]

In the above description, R1 is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, and an alkyl group is a glycol group, a cyclohexyl group, a seba group, an adipe group, a hexyl group, Butane group, oxalic group decay group, terephthal group, isophthal group and the aromatic is selected from the group consisting of naphthalene group, diphenyl group, oxybenzo group, trimellitic group, trimesic acid group, pyromellitic group, the substituent is a carboxyl group At least one selected from the group consisting of a halogen group, a phenyl group, a siloxane group, an alkoxy group, a hydroxy group, and an alkyl group, R2 is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, and the alkyl group may be an ethyl group, a propyl group, an isobutyl group, a neopentyl group, a cyclohexane group or a pentaeryrile. It is a troll group, an octahydro 4,7-methano-1H- indendimethyl group, and it is chosen from the group which consists of a hydroquinone group, a resorcinol group, a phenyl group, a bisphenol group, and a naphthalene group as an aromatic, The said substituent is a carboxyl group, a halogen group, a phenyl group , At least one selected from the group consisting of a siloxane group, an alkoxy group, a hydroxy group, an alkyl group, a halogen, and a phenyl group, n is 1 to 300. The method of claim 4, wherein the adhesion promoting resin is a special polyester resin having a glass transition temperature (Tg) in a range of 0 ° C. to 200 ° C., and has a weight average molecular weight in the range of 200 to 1,000,000. Film composition. According to claim 1, 5 to 75 parts by weight of the radical polymer elastomer resin relative to the entire adhesive film composition for assembling semiconductor; 5 to 50 parts by weight of adhesion promoting crystalline polyester film forming resin; 10 to 50 parts by weight of the radical polymerization resin; 0.001 to 10 parts by weight of the radical polymerization type initiator; 0.001 to 10 parts by weight of the silane coupling agent; 0.1 to 60 parts by weight of a filler; Adhesive film composition for semiconductor assembly comprising an additive 0.001 to 5 parts by weight. The method of claim 1, wherein the radically polymerizable resin (meth) acrylate having at least one functional group, the weight average molecular weight of the adhesive film composition for semiconductor assembly, characterized in that the oligomer or polymer in the range of 500 to 100,000. According to claim 7, wherein the (meth) acrylate oligomer is a urethane (meth) acrylate oligomer having a weight average molecular weight of 300 to 100,000 or an epoxy (meth) acrylate oligomer having a weight average molecular weight of 300 to 30,000 Adhesive film composition for semiconductor assembly, characterized in that The adhesive film composition for a semiconductor assembly according to claim 1, wherein the radical polymerization type thermal initiator is made of a peroxide-based resin, and at least one selected from the group having a 10-hour half-life temperature of 60 ° C or more. delete The method of claim 1, wherein the filler is a non-metallic inorganic filler is spherical or amorphous, the size of the adhesive film composition for the semiconductor assembly is a diameter of 5μm to 10μm range. delete delete An adhesive film for semiconductor assembly manufactured using the adhesive film composition according to any one of claims 1 to 9 and 11.

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