WO2011071107A1

WO2011071107A1 - Photosensitive adhesive composition having adhesiveness even after photocuring reaction and after pattern formation

Info

Publication number: WO2011071107A1
Application number: PCT/JP2010/072117
Authority: WO
Inventors: 正臣高野; 滑川　崇平; 健青山
Original assignee: 新日鐵化学株式会社
Priority date: 2009-12-11
Filing date: 2010-12-09
Publication date: 2011-06-16
Also published as: JPWO2011071107A1; JP5833928B2; TW201137070A; TWI500724B

Abstract

Provided is a photosensitive adhesive composition having adhesiveness even after photocuring reaction and after pattern formation, the composition attaining high adhesive strength, having heat resistance, imparting high reliability to semiconductors, and showing excellent alkali developability. The photosensitive adhesive composition having adhesiveness even after photocuring reaction and after pattern formation includes a resin composition which contains, as a main resin component, an alkali-soluble resin obtained from a product of the reaction of (meth)acrylic acid with an epoxy compound having two glycidyl ether groups and derived from a bisphenol compound, by reacting the reaction product with a) a dicarboxylic acid (or tricarboxylic acid) or the anhydride thereof and b) a tetracarboxylic acid or the dianhydride thereof, the a/b molar ratio being in the range of 0.1-10.

Description

Photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation

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.

As ICs and LSIs become more highly integrated, the size of the chip increases. For example, instead of conventional silver paste, an adhesive composition using polyimide resin is used for bonding in the mounting and assembly of semiconductor packages. It is used as a material (see Patent Documents 1 and 2).

In recent years, there is a case where it is necessary to selectively provide a bonding function only to a necessary portion for high-density mounting of a semiconductor package, simplification of an assembly process, and cost reduction. Therefore, there is a demand for a material capable of forming a pattern and having an adhesion function applied to the pattern portion. In particular, it is very important to have sufficient adhesion when assembling a semiconductor package and to ensure heat resistance and adhesion reliability after bonding. For example, in an assembly process of a semiconductor package, there is a process of entering a reflow furnace for the purpose of soldering for electrical connection. At that time, since it is exposed to a high temperature of 270 ° C., 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.

In addition, even with materials that have heat resistance and adhesion reliability after bonding, if a liquid acrylic resin or the like is used with emphasis on these bonding functions, the dried coating film before photopatterning will become sticky (tack), and the exposure process The front / rear handling becomes worse, and the pattern formation itself may fail. For example, marks may be left on the coating film part that the conveying member contacts during handling, or a spot-like part may be formed, and in the case of contact exposure, mask contamination may occur or pattern formation may not be successful. . That is, since those having an adhesion function generally have tackiness in general, it is also necessary to satisfy the contradictory performance requirement that sufficient adhesion can be secured even if the tackiness is reduced. However, it has good alkali developability and can be patterned, and can be easily bonded after pattern formation. Furthermore, it has sufficient adhesion strength and reliability such as heat resistance, and is tacky in the assembly process of semiconductor packages. It is difficult to simply obtain a photosensitive adhesive that does not cause this problem.

For example, 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. On the other hand, 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. In particular, according to 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. Although it is possible to have heat resistance that can withstand front and rear soldering heat treatments, the inclusion of a thermosetting resin does not dissolve during alkali development, and a residue is likely to be generated.

JP-A-6-145,639 JP-A-7-228,697

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 By using 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. Can be bonded with excellent adhesive strength and heat resistance. As a result, 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.

In order to achieve the above object, 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. Is a photosensitive adhesive composition containing as a main component, and has adhesiveness after photocuring reaction and after pattern formation.

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.

In the present invention, the alkali-soluble resin (A) is preferably a compound represented by the following general formula (1).

However, 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), and Z represents a hydrogen atom or a substituent represented by the general formula (5). N represents a number from 1 to 20.

In the general formula (2), 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. Further, 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, and 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.

However, L is a divalent or trivalent carboxylic acid residue, and r is 1 or 2.

Regarding the photosensitive adhesive composition having adhesiveness after such photocuring reaction and after pattern formation, 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. The alkali-soluble resin (A) obtained by reacting in the range where the molar ratio of a / b is 0.1 to 10, preferably 0.2 to 1, is contained as a main component of the resin component. That is, by using such a photosensitive adhesive composition, it is possible to selectively form a photosensitive adhesive layer 20 having adhesiveness even after a photocuring reaction only on a specific portion having an adhesive function. Therefore, it becomes possible to selectively form an adhesive layer portion having adhesiveness only in a necessary portion in a process described later.

Here, with regard to a), 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. 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). Examples of the alicyclic dicarboxylic acids and tricarboxylic acids (or acid anhydrides thereof) include, for example, hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid (and their acids). And alicyclic dicarboxylic acids and tricarboxylic acids (or acid anhydrides thereof) substituted with saturated hydrocarbons. Moreover, as unsaturated dicarboxylic acid and tricarboxylic acid (or those acid anhydrides), for example, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, trimellitic acid (or Their acid anhydrides). Of these, 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.

As for b), 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. Moreover, as cycloaliphatic tetracarboxylic acid or its acid dianhydride, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid or its acid dianhydride In addition, an alicyclic tetracarboxylic acid substituted with a saturated hydrocarbon or an acid dianhydride thereof may be used. Examples of the aromatic tetracarboxylic acid or acid dianhydride thereof 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. In order to obtain an alkali-soluble resin, 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.

In addition to the alkali-soluble resin (A), 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, dipentaerythritol hexa (meth) acrylate, glycerol (meth) (meth) acrylic acid esters such as acrylate. These photopolymerizable monomers (B) can be used singly or in combination of two or more.

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. On the other hand, if the upper limit is exceeded, 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 Biimidazole compounds such as orophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Halomethyldiazole compounds such as styryl) -1,3,4-oxadiazole; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (Trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chloro Enyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloro Halomethyl-S-triazine compounds such as methyl) -1,3,5-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1- (4- Phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4 O-acyloxime compounds such as -methylsulfanylphenyl) butan-1-one oxime-O-acetate; benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone Sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; azobisisobutylnitrile, benzoyl peroxide, cumene pero Organic peroxides such as oxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators or sensitizers (C) can be used alone or in combination of two or more.

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. In addition to 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. These 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.

In addition, 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. In addition, one or more inorganic fillers such as titanium oxide and boron nitride may be blended. Furthermore, 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.

In the photosensitive adhesive composition having adhesiveness after the photocuring reaction and after the pattern formation, 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 μm for liquid crystal displays and 1 to 100 μm for circuit boards It is. The thinner the coating thickness of the photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation, the higher the resolution, and the photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation. Vias and fine lines less than or equal to the coating thickness can be formed. For example, when the film thickness is 30 μm, a via diameter of 30 μm is obtained, and lines and spaces with a width of 20 μm can be formed. Further, when the film thickness is 5 μm, 2.5 μm isolated lines and isolated dots can be formed.

In order to form a pattern on the substrates to be bonded, 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. In the photolithography, 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. Although not particularly limited, 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. In the present invention, 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. In addition, 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.

Thereafter, a layer formed of a photosensitive adhesive composition having a pattern formed in a predetermined shape on the substrate and having an adhesive property after the photocuring reaction and after the pattern formation, and the second substrate are combined with the photosensitive adhesive composition. These are bonded and bonded together by thermocompression using the thermosetting function after photocuring. Conditions for thermocompression bonding are 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. Thereby, the adhesive strength can be further improved. And a desired structure can be obtained by performing a suitable assembly process using the bonded body obtained by thermosetting. In this case, 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.

According to 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.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

First, 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.

[Abbreviation]
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) Is a compound in which 1 is
PGMEA: Propylene glycol monomethyl ether acetate TPP: Triphenylphosphine BPDA: Biphenyltetracarboxylic acid dianhydride

[Solid content]
1 g of a resin solution (including the case of a reaction product or an alkali-soluble resin) obtained in the synthesis examples (including comparative examples) is impregnated into a glass filter [weight: W ₀ (g)] and weighed [ W ₁ (g)], and the weight [W ₂ (g)] after heating at 160 ° C. for 2 hours was obtained from the following formula.
Solid content (%) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using phenolphthalein as an indicator.

[Molecular weight]
It is the value which calculated | required the number average molecular weight (Mn) as a standard polystyrene conversion value by the gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

[Synthesis Example 1]
(Synthesis of alkali-soluble resin (A-1))
A 1000 ml four-necked flask equipped with a reflux condenser was charged with 240.00 g (0.52 mol) of BPFE, 74.78 g (1.04 mol) of acrylic acid, 362.00 g of PGMEA, and 1.36 g of TPP, and heated at 90 to 100 ° C. Under stirring for 12 hours, a reaction product (diol compound) was obtained.

Next, 76.31 g (0.26 mol) of BPDA and 39.46 g (0.26 mol) of BPDA were charged into this reaction product (diol compound), and the mixture was stirred at 100 to 120 ° C. for 4 hours to react with an alkali-soluble resin ( A-1) was synthesized. The obtained alkali-soluble resin had a solid content of 54.8%, an acid value (in terms of solid content) of 106.8 mgKOH / g, and Mn of 1400 by GPC analysis.

[Synthesis Example 2]
(Synthesis of alkali-soluble resin (A-2))
In a 1000 ml four-necked flask equipped with a reflux condenser, 160.00 g (0.35 mol) of BPFE, 186.99 g (0.69 mol) of HOA-HH, 346.98 g of PGMEA, and 0.91 g of TPP were charged and heated at 90 to 100 ° C. Under stirring for 16 hours, a reaction product (diol compound) was obtained.

Next, 50.89 g (0.17 mol) of BPDA and 26.32 g (0.17 mol) of THPA 仕 were charged into this reaction product (diol compound) and stirred at 100 to 120 ° C. for 6 hours to cause an alkali-soluble resin ( A-2) was synthesized. The obtained 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 diameter of 1 μm to prepare a photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation.

(Preparation of a substrate with a photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation)
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 μm 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 μm and after pattern formation. It was.

(Development, pattern formation)
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. 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.

(Production of bonded body)
Next, a silicon wafer (30) of 2 mm × 2 mm × thickness 300 μm 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 μm 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).

[Comparative Example 1]
Photosensitivity having adhesiveness after photocuring reaction and pattern formation using 60 parts by weight of cresol novolak (resin solid content concentration = 50 wt%, Nippon Kayaku CCR-1172H) instead of alkali-soluble resin (A) A test bonded body according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the adhesive composition was used.

[Comparative Example 2]
Photosensitivity having adhesiveness after photocuring reaction and pattern formation using 60 parts by weight of cresol novolak (resin solid content concentration = 50 wt%, Nippon Kayaku CCR-1172H) instead of alkali-soluble resin (A) A test bonded body according to Comparative Example 2 was obtained in the same manner as in Example 4 except that the adhesive composition was used.

The following evaluations were performed on the substrates with the photosensitive adhesive composition and the test laminates having adhesiveness after the photocuring reaction and after pattern formation in Examples 1 to 12 and Comparative Examples 1 and 2. It was.

<Tack test>
After the photocuring reaction and the pattern formation used in the above examples and comparative examples, the photosensitive adhesive composition having adhesiveness was spin-coated on the substrate, and the dried coating film at the time of oven drying was evaluated by touch. . Here, the case where no tack was recognized was evaluated as “◯”, the case where slight tack was recognized was “Δ”, and the case where marked tack was recognized was evaluated as “x” in three stages. The results are summarized in Table 1.

<Resolution test>
After the photocuring reaction and the pattern formation used in the above examples and comparative examples, a photosensitive adhesive composition having adhesiveness was applied to a separately prepared silicon wafer so as to have a film thickness of 20 μm. Exposure was performed with a negative mask provided with a via hole pattern of ˜100 μm, and development was performed with a horizontal automatic developing machine under the same development conditions as in the above Examples and Comparative Examples, and the minimum via diameter was measured. Here, “○” indicates that the via could be formed, “×” indicates that the via could not be formed, and “Δ” indicates that the via could be formed, but some residue remained as “Δ”. Rated by stage. The results are summarized in Table 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.

<Solder heat resistance test>
Substrate with resin prepared in the same way as the moisture resistance reliability test is immersed in a solder bath at 260 ° C for 30 seconds according to the test method of JIS C-6481, and the peeling test with cellophane tape is set as one cycle, which is 1 to 3 times. The state of the coating film after the repetition was visually observed and evaluated according to the following criteria. The results are summarized in Table 1.
(Double-circle): Even if it repeats 3 cycles, there is no abnormality in a coating film.
A: After repeating 3 cycles, a slight change is observed in the coating film.
(Triangle | delta): After repeating 2 cycles, a change is recognized by the coating film.
X: After repeating 1 cycle, a change is recognized by the coating film.

<Shear strength (adhesive strength) test>
The bonded portion (adhesive layer) of each bonded body obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was subjected to a shear strength test with a die shear tester, and had adhesiveness after photocuring reaction and after pattern formation. The adhesive strength between the adhesive layer made of the photosensitive adhesive composition and the wafer or glass substrate was measured. And it evaluated on the following references | standards and the result was put together in Table 1.
A: Adhesive strength is 30 MPa or more, and the fracture state is higher than the strength of the wafer or glass substrate (the adhesive layer does not peel off even if the wafer or glass is damaged).
○: Adhesive strength is 20 MPa or more and less than 30 MPa, and the fracture state is interfacial peeling.
Δ: Adhesive strength is 1 MPa or more and less than 20 MPa.
X: Adhesive strength cannot be measured.

<Reflow resistance test>
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 20μm, 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

As shown in Table 1, when the photosensitive adhesive composition having adhesiveness after the photocuring reaction and after the pattern formation was bonded to the wafer or glass under the conditions of Examples 1 to 6, the shear strength test result was obtained. As can be seen from the graph, when the bonding temperature is 110 ° C. or 120 ° C., the bonding strength is 20 MPa or more, and when it is 130 ° C., the bonding strength is higher than that of the base material, which is superior to those of Comparative Examples 1 and 2. It was found that Further, when the alkali-soluble resins (A) of Examples 1 to 6 were used, the developability was good, whereas when the cresol novolak was used as in Comparative Examples 1 and 2, the developability was low. The result was obtained. From these results, it was found that the photosensitive adhesive composition having adhesiveness after the photocuring reaction and pattern formation of the present invention can provide high adhesive strength and good alkali developability. did.

10: BT base material 20: adhesive layer 30: wafer 40: glass substrate

Claims

As a resin component in the resin composition, a) a dicarboxylic acid or a tricarboxylic acid, or a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid. And b) a photocuring containing an alkali-soluble resin obtained by reacting a tetracarboxylic acid or an acid dianhydride thereof in a range where the molar ratio of a / b is 0.1 to 10. A photosensitive adhesive composition having adhesiveness after reaction and pattern formation.
(A) For a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and an unsaturated group-containing monocarboxylic acid, a) a dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, and b) an alkali-soluble resin obtained by reacting tetracarboxylic acid or its acid dianhydride in a range where the molar ratio of a / b is 0.1 to 10, and (B) at least one ethylenically unsaturated group. The photosensitive adhesive composition which has adhesiveness after photocuring reaction and after pattern formation of Claim 1 containing the photopolymerizable monomer which has a coupling | bonding, (C) photoinitiator, and (D) epoxy resin .
3. The photosensitive adhesive having adhesiveness after photocuring reaction and after pattern formation, wherein the alkali-soluble resin has a weight average molecular weight of 3000 to 40000 and an acid value of 50 to 200 mgKOH / g. Composition.
The photosensitive adhesive composition having adhesiveness after photocuring reaction and after pattern formation according to any one of claims 1 to 3, wherein the bisphenol forming the alkali-soluble resin is a bisphenol having a fluorene skeleton.
A photosensitive adhesive composition is applied onto the substrate and photocured to form a pattern formed by alkali development on another substrate under conditions of temperature 50 to 300 ° C, time 1 second to 60 minutes, and pressure 0.01 to 10 MPa. The photosensitive adhesive having adhesiveness after photocuring reaction and after pattern formation according to any one of claims 1 to 4, wherein the substrate can be bonded by thermocompression bonding Composition.