KR20120090984A - Adhesive resin composition for silicon wafers - Google Patents

Abstract

This invention is a silicone wafer adhesive resin composition which has favorable adhesiveness after hardening with respect to a silicon wafer, The characteristic is the compound which has a urea structure with respect to 100 weight part of epoxy resins, The urea structure part in the compound It exists in the point which contains so that it may become 0.1-50 weight part. It is preferable that the said epoxy resin is an epoxy resin which has a bisphenol A frame | skeleton or a bisphenol F frame | skeleton, and it is preferable that the compound which has the said urea structure is a reaction product of an amine compound and an isocyanate compound.

Description

Adhesive resin composition for silicon wafers {ADHESIVE RESIN COMPOSITION FOR SILICON WAFERS}

TECHNICAL FIELD The present invention relates to an adhesive resin composition, and more particularly, to an epoxy resin composition containing a predetermined amount or more of a compound having a urea structure, which is remarkably excellent in adhesion to a silicon wafer.

Recently, various mounting technologies have been developed with the development of IT technology. In particular, since the direct fixing of the semiconductor element, the insulating property, the adhesiveness to the substrate, and the like are indispensable for the process and the mounting reliability of various mounting technologies, an adhesive for bonding a semiconductor wafer to another substrate is important. The application method of an adhesive agent is limited by the mounting form of a semiconductor, The main application methods are methods, such as underfill, screen printing, inkjet, dry film lamination, and spin coat. The adhesive resin apply | coated by such a method requires low viscosity, a solvent-free, heat resistance after adhesion | attachment, etc. according to a use. Moreover, as a hardening mechanism, the thermosetting mechanism which can satisfy said request easily is preferable.

However, as a resin having good adhesion to a silicon wafer, only a few resins, such as a solubilized polyimide, exist in the past, and it is not yet known that a thermosetting resin has good adhesion to a silicon wafer.

Therefore, the objective of this invention is providing the thermosetting resin composition which exhibits favorable adhesiveness with respect to a silicon wafer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors discovered that the epoxy resin composition containing the fixed amount or more of a urea structure is extremely favorable, and reached this invention.

That is, this invention contains the compound which has a urea structure with respect to 100 weight part of epoxy resins so that the urea structure part in this compound may be 0.1-50 weight part, The silicone wafer adhesive resin composition characterized by the above-mentioned.

In the present invention, at least one member selected from the group consisting of a polyamide compound having a phenolic hydroxyl group at a position adjacent to an amino group and having a structure derived from an aromatic diamine having a phenolic hydroxyl group, and a phenol resin You may contain resin.

Moreover, it is preferable that the said epoxy resin is an epoxy resin which has a bisphenol A skeleton or a bisphenol F skeleton, and it is preferable that the compound which has the said urea structure is a reaction product of an amine compound and an isocyanate compound.

Since the silicone wafer adhesive resin composition of this invention turns into an epoxy resin hardened | cured material which has a suitable urea structure at the time of thermosetting, it adhere | attaches extremely favorable with respect to a silicon wafer.

As an epoxy resin used for this invention, For example, Polyglycidyl ether compound of mononuclear polyhydric phenol compounds, such as hydroquinone, a resorcinol, a pyrocatechol, a phloroglucinol; Dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolak Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as terpene phenol; Polyglycides of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodi glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Dilether compounds; Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azaline acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromelli Homopolymers or copolymers of glycidyl esters and glycidyl methacrylates of aliphatic, aromatic or cycloaliphatic polybasic acids such as triacid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid; Epoxy compounds having glycidylamino groups such as N, N-diglycidyl aniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, and diglycidyl ortho toluidine; Vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methyl Epoxides of cyclic olefin compounds such as cyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; And heterocyclic compounds such as epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers and triglycidyl isocyanurate.

Said epoxy resin may be internally crosslinked by the prepolymer of terminal isocyanate, or may be high molecular weight by polyhydric active hydrogen compound (polyhydric phenol, polyamine, carbonyl group containing compound, polyphosphate ester, etc.).

As a compound which has a urea structure used by this invention, the reaction product of an amine compound and an isocyanate compound is preferable. As said amine compound, Alkylene diamine, such as ethylenediamine, 1,2-diaminopropane, 1, 3- diamino propane, 1, 3- diamino butane, 1, 4- diamino butane; Polyalkyl polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; Alicyclic polyamines such as 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; Guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2 Imidazoles such as -phenyl-4-methyl-imidazole and 2-aminopropylimidazole; Oxalic acid hydrazide, maron acid hydrazide, succinic acid hydrazide, glutaric acid hydrazide, adipine acid hydrazide, submersan hydrazide, azeline hydrazide, sebacin hydrazide, phthalic hydrazide, etc. Dihydrazides; N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N-diisopropylaminoethylamine, N, N-diallylaminoethylamine, N, N-benzylmethylaminoethylamine, N, N-dibenzylaminoethylamine, N, N-cyclohexylmethylaminoethylamine, N, N-dicyclohexylaminoethylamine, N- (2-aminoethyl) pyrrolidine, N- (2-amino Ethyl) piperidine, N- (2-aminoethyl) morpholine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N'-methylpiperazine, N, N-dimethylamino Propylamine, N, N-diethylaminopropylamine, N, N-diisopropylaminopropylamine, N, N-diallylaminopropylamine, N, N-benzylmethylaminopropylamine, N, N-dibenzyl Aminopropylamine, N, N-cyclohexylmethylaminopropylamine, N, N-dicyclohexylaminopropylamine, N- (3-aminopropyl) pyrrolidine, N- (3-aminopropyl) piperidine, N- (3-aminopropyl) morpholine, N- (3-aminopropyl) pipera , N- (3-aminopropyl) -N'-methylpiperizine, 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N -Diisopropylamino) benzylamine, N, N-dimethylisophoronediamine, N, N-dimethylbisaminocyclohexane, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethyl Ethylenediamine, N, N, N'-trimethylethylenediamine, N'-ethyl-N, N-dimethylpropanediamine, N'-ethyl-N, N-dibenzylaminopropylamine; N, N- (bisaminopropyl) -N-methylamine, N, N-bisaminopropylethylamine, N, N-bisaminopropylpropylamine, N, N-bisaminopropylbutylamine, N, N-bis Aminopropylpentylamine, N, N-bisaminopropylhexylamine, N, N-bisaminopropyl-2-ethylhexylamine, N, N-bisaminopropylcyclohexylamine, N, N-bisaminopropylbenzylamine, N, N-bisaminopropylallylamine, bis [3- (N, N-dimethylaminopropyl)] amine, bis [3- (N, N-diethylaminopropyl)] amine, bis [3- (N, N-diisopropylaminopropyl)] amine, bis [3- (N, N-dibutylaminopropyl)] amine, etc. are mentioned.

As said isocyanate compound, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 4, 4- diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl, for example. Xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylene methane isocyanate, 3,3'-dimeth Methoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, etc. are mentioned.

As a commercial item of the compound which has a urea structure which can be used by this invention, For example, Adeka Hardner EH-4380S (Brand name of the amine-type hardening | curing agent which has a urea structure made by ADEKA Co., Ltd.) Weight% of NHCONH-): 22.8% by weight '', U-CAT 3502T (aromatic dimethyl urea compound manufactured by San Apro Co., Ltd.), U-CAT 3503N (trade name of aliphatic dimethyl urea compound manufactured by San Apro Co., Ltd.), Dyhard UR 500 (brand name of aromatic dimethyl urea compound made by Degussa Japan), Dyhard UR 300 (brand name of aromatic dimethyl urea compound made by Degussa Japan Co., Ltd.), Dyhard UR 200 (aromatic dimethyl made by Degussa Japan Co., Ltd.) Trade names of urea compounds).

In the silicone wafer adhesive resin composition of this invention, the compound which has a urea structure with respect to 100 weight part of epoxy resins so that the urea structure part in the compound may be 0.1-50 weight part, Preferably it is 0.2-30 weight part use. When the part (-NHCONH-) which has a urea structure exceeds 0.1 weight part or more than 50 weight part, since sufficient adhesiveness is not obtained, it is unpreferable.

In the silicone wafer adhesive resin composition of the present invention, another resin can be used in combination with the epoxy resin. As said other resin, a phenol resin, a polyamide resin, a polyimide resin, a cyanate ester compound, a phenoxy resin, a polybutadiene rubber, etc. are mentioned, for example.

It is preferable that the silicone wafer adhesive resin composition of this invention contains a phenol resin further. Thereby, high oil transition temperature, toughness, water resistance, chemical resistance, high adhesiveness, etc. are obtained.

As said phenol resin, there exists a phenol resin synthesize | combined from phenols and aldehydes. Examples of the phenols include phenol, cresol, ethyl phenol, n-propyl phenol, isopropyl phenol, butyl phenol, tertiary butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, cyclohexyl phenol, chloro phenol and bromine. Mophenol, resorcin, catechol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpene phenol, phenolylated dish Clopentadiene, etc. are mentioned, As said aldehyde, formaldehyde is mentioned.

Moreover, in this invention, what substituted a part of phenols with aromatic compounds, such as biphenyl, can also be used. Moreover, the phenol resin obtained by connecting the said phenols with dicyclopentadiene can also be used.

It is preferable that the silicone wafer adhesive resin composition of this invention contains the polyamide compound which has a phenolic hydroxyl group in the position adjacent to an amino group, and also has a structure derived from phenolic hydroxyl group containing aromatic diamine. This further improves the high oil transition temperature, toughness, high adhesion, and low thermal expansion.

In the silicon wafer adhesive resin composition of the present invention, glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, and carbon black, as necessary. Fillers or pigments such as graphite, iron oxide, bitumen, metal particles and resin particles coated with metal; Thickener; Thixotropic agents; Flame retardant; Antifoam; Waterproofing agent; Commercial additives, such as colloidal silica and colloidal alumina, may be included, and adhesive resins, such as xylene resin and a petroleum resin, can also be used together.

In particular, when the silica filler is used in combination, not only the control of the coefficient of thermal expansion of the composition becomes easy, but also the elastic modulus of the cured resin after the thermosetting of the silicon wafer adhesive resin composition of the present invention is improved, whereby the resin after thermosetting Is preferable since it becomes high strength.

EXAMPLES Hereinafter, the silicone wafer adhesive resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Examples 1-11 and Comparative Examples 1-5]

After mixing the resin composition of the formulation shown in the following Table 1 or 2, and propylene glycol monomethyl ether, apply | coating so that the film thickness after hardening may be set to 30-40 micrometers on a silicon wafer, and a solvent is removed at 100 degreeC for 10 minutes. It dried, and hardened resin over 1 hour at 180 degreeC after that. Using the obtained test piece, the peel test (crosscut test) by the cellophane adhesive tape based on the crosscut test method of JIS DO202 was performed, and the number of remainders was shown in the table | surface. Moreover, after the pressure cooker test was performed for 96 hours under 121 degreeC / 2.1 atmosphere / 100% RH conditions, the crosscut test was done and the number of remainders was shown in the table | surface.

Reference Example (Synthesis of Urea-containing Compound 1)

162.5 g of isobutanol, 162.5 g of xylene, 408 g of N, N-dimethylaminopropylamine, and 148 g of 1,2-propanediamine were added thereto, followed by mixing and stirring at 60 to 70 ° C for 30 minutes. Next, 190 g of adecarazine EP-4100E (trade name of bisphenol A type epoxy resin manufactured by ADEKA Corporation; brand name of epoxy equivalent 190) was slowly added dropwise so that the temperature in the reaction system did not increase, and the mixture was refluxed for 2 hours to mature.

Moreover, 666 g of xylene solution of 67 weight% of isophorone diisocyanate was slowly dripped so that the temperature in a reaction system might not rise. After completion | finish of dripping, it heated up and reflux aging at 140-150 degreeC for 2 hours, and after confirming that absorption of 2250cm <^-1> which is absorption of isocyanate disappeared by IR, it heated up to 200 degreeC and carried out desolvent treatment at normal pressure for 2 hours. Was carried out. Furthermore, it depressurized at 190-200 degreeC and 50-60 mmHg for 1 hour, and obtained the pale white solid.

[Table 1]

[Table 2]

The result of Table 1 and Table 2 demonstrates the effect of this invention containing the compound which has a urea structure with respect to 100 weight part of epoxy resins so that the urea structure part in this compound may be 0.1-50 weight part.

The silicon wafer adhesive resin composition of the present invention has a good adhesiveness after curing to a silicon wafer, and is useful not only when bonding other materials to metallic silicon or when directly mounting a semiconductor device on another substrate. Instead, the composition itself can be used as an interlayer insulating film or a protective film, which is extremely useful industrially.

Claims (9)

A silicone wafer adhesive resin composition comprising a compound having a urea structure in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the epoxy resin. The method of claim 1,
Moreover, the adhesive resin composition for silicone wafers which has a phenolic hydroxyl group in the position adjacent to an amino group, and contains the polyamide compound which has a structure derived from the aromatic diamine which has a phenolic hydroxyl group. The method of claim 1,
Furthermore, the silicone wafer adhesive resin composition which contains a phenol resin. The method of claim 2,
Furthermore, the silicone wafer adhesive resin composition which contains a phenol resin. The method of claim 1,
Adhesive resin composition for silicon wafers whose said epoxy resin is an epoxy resin which has a bisphenol A frame | skeleton or a bisphenol F frame | skeleton. The method of claim 2,
Adhesive resin composition for silicon wafers whose said epoxy resin is an epoxy resin which has a bisphenol A frame | skeleton or a bisphenol F frame | skeleton. The method of claim 3,
Adhesive resin composition for silicon wafers whose said epoxy resin is an epoxy resin which has a bisphenol A frame | skeleton or a bisphenol F frame | skeleton. The method of claim 4, wherein
Adhesive resin composition for silicon wafers whose said epoxy resin is an epoxy resin which has a bisphenol A frame | skeleton or a bisphenol F frame | skeleton. The method of claim 1,
The adhesive resin composition for silicon wafers whose said compound which has a urea structure is a reaction product of an amine compound and an isocyanate compound.