TWI500724B - And a photosensitive adhesive composition having an adhesive property after the photohardening reaction and pattern formation - Google Patents

Description

Photosensitive adhesive composition having adhesion after photohardening reaction and pattern formation

The present invention relates to a photosensitive adhesive composition which has adhesiveness after photohardening reaction and after formation of a pattern, and more specifically, is a part of the photohardening after the adhesion function is given, and the photohardening portion is made by alkali imaging. Forming a pattern, and by using the heat-hardening function having the pattern, for example, the germanium wafers necessary for the steps of manufacturing the semiconductor device, the glass substrates, the germanium wafer and the glass substrate, etc. A photosensitive adhesive composition which adheres to a bonded object in a manner of excellent adhesion strength and heat resistance.

As a result of the increase in the size of the wafer due to the high integration of the IC and the LSI, for example, the adhesive composition using the polyimide resin is substituted for the silver paste as an adhesive material for mounting or assembling a semiconductor unit. (Refer to Patent Documents 1 and 2).

In recent years, in order to mount a semiconductor unit at a higher density, to simplify the assembly process and to reduce the cost, it is necessary to selectively attach the necessary portion to the adhesive function. Therefore, the demand can form a pattern and the adhesive function can be imparted to the material of the pattern portion. In particular, when the semiconductor unit is assembled, it has sufficient adhesion, and it is important to ensure heat resistance and adhesion reliability after adhesion. For example, in the step of assembling the semiconductor unit, the step of placing the converter into the furnace is required for the welding of the electrical connection. At this time, it is exposed to a temperature of 270 ° C, so it is necessary to ensure a part of the photosensitive adhesive, that is, a portion of the formed pattern-adhering substrate, heat resistance at a high temperature and endurance of hardening shrinkage at the time of cooling. That is, it is required to have strong resistance to melt conversion.

In addition, when a liquid acrylic resin or the like which adheres to such an adhesive function is used as a material which has heat resistance and adhesion reliability after adhesion, the dry coating film before light patterning also has a sticky feeling (viscosity), so The rationality of the exposure step is deteriorated, and the pattern cannot be formed automatically. For example, the portion of the coating film that contacts the conveying member during processing may leave marks and produce a stain-like portion, which may contaminate the mask when exposed to exposure, and is difficult to form a pattern. That is, generally, the adhesive function is mostly viscous, and therefore it is required to satisfy the opposite performance required to ensure sufficient adhesion even if the viscosity is lowered. However, it is difficult to obtain a pattern with a good alkali developability, and it is easy to adhere after forming a pattern, and has sufficient adhesion strength and heat resistance. The step of assembling a semiconductor unit does not cause viscous photosensitive adhesion. Agent.

For example, a photosensitive adhesive composition which can form a pattern without a thermosetting resin reduces heat resistance when assembling a semiconductor unit, easily peels off or cracks an adhesive interface, and tends to cause poor insulation due to low reliability. . Further, the photosensitive adhesive composition containing a thermosetting resin has a low exposure sensitivity when forming a pattern, and tends to have insufficient alkali developability. In particular, when a photosensitive adhesive composition comprising a combination of a polyimide resin and a thermosetting resin is used, the polyimide resin having a low melting point can maintain a high adhesion during heating and is resistant to mounting. Solder heat treatment at a temperature of about 250 ° C is heat-resistant, but it does not dissolve when the alkali is developed due to the inclusion of a thermosetting resin, and residue is liable to occur.

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Publication No. 6-145,639

Patent Document 2: Japanese Patent Publication No. 7-228,697

In view of the prior art problems of the present invention, the present invention is to form a pattern of a photohardenable portion by alkali imaging after photohardening of the adhesive function, and then by the heat hardening function of the pattern, for example, It is possible to adhere the bonded object by holding the bonded object, such as adhesion between the tantalum wafers and the glass substrates, and between the wafer and the glass substrate. Things. Therefore, it is an object of the present invention to provide an adhesive layer which can form a heat-resistant adhesive having high adhesive strength, includes melt resistance, and has high reliability with respect to a semiconductor, and can form a pattern, and is not formed in each step of the assembly process of the semiconductor unit. A photosensitive adhesive composition that produces problems such as influential viscosity.

In order to achieve the above object, the gist of the present invention is as follows.

That is, the main component of the resin component contained in the resin composition of the present invention is a reactant derived from an epoxy compound having two glycidyl ether groups and a monocarboxylic acid containing an unsaturated group derived from a bisphenol. Photosensitive adhesion of an alkali-soluble resin obtained by reacting a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and b) a tetracarboxylic acid or an acid dianhydride thereof in a molar ratio of a/b of from 0.1 to 10 In the composition of the agent, the characteristics are adhesive after the photohardening reaction and after the formation of the pattern.

Further, the present invention is a reaction product containing (A) an epoxy compound having two glycidyl ether groups derived from a bisphenol and an unsaturated group-containing monocarboxylic acid, and a molar ratio of a/b is An alkali-soluble resin obtained by reacting a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and b) a tetracarboxylic acid or an acid dianhydride thereof, and (B) having at least one ethylenically unsaturated bond; The photopolymerizable monomer, (C) photopolymerization initiator, and (D) a photosensitive adhesive composition having an adhesive property after photohardening reaction and pattern formation.

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

【化1】

In the formula, W is a bisphenol derivative represented by the following general formula (2), Y is a tetravalent carboxylic acid residue, and G is a substituent represented by the following general formula (3) or (4), Z The hydrogen atom or the substituent represented by the general formula (5), n is a number from 1 to 20.

[Chemical 2]

In the above general formula (2), R ₁ , R ₂ , R ₃ and R ₄ each 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 and R ₃ and R _{4 is} preferably a hydrogen atom. Further, X is -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9 , 9-fluorenyl or a straight bond, but X is preferably a 9,9-fluorenyl group. m is an integer from 0 to 10.

[化3]

Wherein R ₅ is a hydrogen atom or a methyl group, R ₆ is a divalent alkylene group having 2 to 22 carbon atoms or an alkylaryl group, and R ₇ is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. p is a number from 0 to 60, and q is 0 or 1.

【化4】

Wherein L is a 2 or 3 valent carboxylic acid residue and r is 1 or 2.

The specific composition of the photosensitive adhesive composition which is adhesive after the photohardening reaction and the pattern formation is composed of the main component of the resin component, and has two shrinkages derived from the bisphenol derivative. A reaction product of a glycerol ether group-containing epoxy compound and an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, wherein the molar ratio of a/b is from 0.1 to 10, preferably from 0.2 to 1, such that a) An alkali-soluble resin (A) obtained by reacting a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and b) a tetracarboxylic acid or an acid dianhydride thereof. In other words, by using such a photosensitive adhesive composition, only a specific portion having an adhesive function can be selectively subjected to a photocuring reaction, whereby a photosensitive adhesive layer 20 having adhesiveness can be formed. Therefore, in the later-described steps, only These adhesive portions which are inherently adhesive with selective formation of the necessary portions.

Wherein, a) a saturated linear hydrocarbon dicarboxylic acid or a tricarboxylic acid such as succinic acid, acetyl succinic acid, adipic acid, sebacic acid, cis malic acid, malonic acid, glutaric acid, citric acid, a compound such as tartaric acid, carbonyl glutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid (or an anhydride thereof), or a linear hydrocarbon dicarboxylic acid substituted with a saturated hydrocarbon and a tricarboxylic acid Acids (or their anhydrides). Further, alicyclic dicarboxylic acids and tricarboxylic acids (or anhydrides thereof) such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrobenzonitrile The compound such as an acid (or an acid anhydride) may be an alicyclic dicarboxylic acid or a tricarboxylic acid (or an anhydride thereof) substituted with a saturated hydrocarbon. Further, unsaturated dicarboxylic acids and tricarboxylic acids (or such anhydrides) such as maleic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, methylmethicin tetrahydrofurfuric acid, chloric acid, partial Triphenylcarboxylate (or such anhydride). Among these, succinic acid, itaconic acid, tetrahydrofurfuric acid, hexahydrotrimellitic acid, citric acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrofurfuric acid are more preferred. These acids or their acid anhydrides may be used in combination of two or more kinds.

Further, b) a saturated linear hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, such as butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid or its acid dianhydride, or a saturated cyclic hydrocarbon Substituted saturated cyclic tetracarboxylic acid or its acid dianhydride. Further, an alicyclic tetracarboxylic acid or an acid dianhydride thereof such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid or The acid dianhydride or the like may be an alicyclic tetracarboxylic acid or an acid dianhydride substituted with a saturated hydrocarbon. Further, the aromatic tetracarboxylic acid or its acid dianhydride such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylphosphonium tetracarboxylic acid or its acid Diacid anhydride, etc. In the present invention, the acid or its acid dianhydride is preferably biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid or acid dianhydride thereof, more preferably biphenyltetracarboxylic acid or biphenyl. Ether tetracarboxylic acid or its acid dianhydride. These acids or their acid dianhydrides may be used in combination of two or more kinds.

The alkali-soluble resin (A) is preferably a diol compound obtained by reacting an epoxy compound having two glycidyl ether groups with an unsaturated monocarboxylic acid derived from a bisphenol, and reacting with a saturated or unsaturated polyvalent acid anhydride. The acid having a weight average molecular weight of 3,000 to 40,000 is 50 to 200 mgKOH/g. The diol compound which reacts with the acid dianhydride in order to obtain an alkali-soluble resin is preferably one in which the molecular weight is increased in the polymerization reaction, and the reactivity of the two hydroxyl groups in the molecule with the acid dianhydride is uniform, for example, having a symmetrical molecular structure. Things.

The photosensitive adhesive composition which is adhesive after the photohardening reaction and the pattern formation of the present invention is preferably a photopolymerizable product having at least one ethylenically unsaturated bond in addition to the alkali-soluble resin (A). A monomer (B), a photopolymerization initiator or a sensitizer (C), and an epoxy compound (D) having at least one epoxy group.

The photopolymerizable monomer (B) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or the like has a hydroxyl group. Monomer, and ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate , tetramethyl glycol di(meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. (methyl ) acrylates. These photopolymerizable monomers (B) may be used alone or in combination of two or more.

Further, the content of the photopolymerizable monomer (B) is preferably such that the mass ratio [(A)/(B)] of the alkali-soluble resin (A) to the photopolymerizable monomer (B) is 20/ 80 to 90/10, more preferably 40/60 to 80/20, and particularly preferably 60/40 to 80/20. When the mass ratio is less than the above lower limit value, the cured product after photohardening is embrittled, and the acidity of the coating film in the unexposed portion is lowered, so that the solubility with respect to the alkali developing solution is lowered, and the tendency tends to occur. The pattern edge is jagged and cannot be sharply formed. Further, when the content exceeds the above upper limit, the ratio of the photoreactive functional group in the resin is too small to sufficiently form a crosslinked structure, and the acid content in the resin component is too high to increase the exposure portion for alkali imaging. The solubility of the liquid tends to make the formed pattern thinner than the target line width, which tends to cause pattern defects.

The photopolymerization initiator or sensitizer (C), for example, acetophenone, 2,2-diethoxyethyl benzene, p-dimethyl acetophenone, p-dimethylamino propyl benzene, Ethylene benzene such as chlorinated benzene, trichloroacetonitrile, p-tert-butyl acetophenone; benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamine Benzophenones such as benzophenone; benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; -(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-( O-fluorophenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryl Diimidazole-based compounds such as diimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl) a halomethyldiazole compound such as -1,3,4-oxadiazole or 2-trichloromethyl-5-(p-methoxystyryl)-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-chlorophenyl)-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-methyl Oxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-double (trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. Halomethyl-S-triazine compounds; 1,2-octanedione, 1-(4-phenylthio)phenyl]-2-(O-benzoquinone), 1-[4-( Phenylthio phenyl)butane-1,2-dione-2-indole-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione- O-thiol-repellent compounds such as 2-肟-O-acetate and 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate; benzyl dimethyl Sulfur compounds such as ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethylhydrazine Anthraquinones such as hydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylfluorene; azo-isobutyronitrile, benzoquinone peroxide, cumene peroxide, etc. Peroxide; 2-mercaptobenzoimine , 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, benzothiazole mercaptan compounds; triethanolamine, triethylamine grade 3 amine. These photopolymerization initiators or sensitizers (C) may be used singly or in combination of two or more kinds.

In addition, the content of the photopolymerization initiator or the sensitizer (C) is preferably from 2 to 30 based on 100 parts by mass of the total of the alkali-soluble resin (A) and the photopolymerizable monomer (B). The amount of the mass fraction is more preferably 5 to 20 parts by mass. When the content of the photopolymerization initiator or the sensitizer (C) is less than the above lower limit, the photopolymerization rate tends to be lowered to lower the sensitivity, and when the above upper limit is exceeded, the sensitivity is excessively increased to cause the pattern. The line width is too thick relative to the pattern cover, and it tends to be difficult to reproduce the faithful line width with respect to the picture cover.

The epoxy compound (D) is, for example, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, Epoxy resin such as biphenyl type epoxy resin or alicyclic epoxy resin, and phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl trimer isocyanate, diglycidyl isocyanurate, A compound having at least one epoxy group such as allyl glycidyl ether or glycidyl methacrylate. These epoxy compounds (D) may be used alone or in combination of two or more. By adding such an epoxy compound (D), the thermosetting property or the adhesiveness can be imparted to the photosensitive adhesive composition which is adhesive after the photohardening reaction used in the present invention and after the pattern formation.

In addition, the content of the epoxy compound (D) is preferably from 10 to 30 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin (A) and the photopolymerizable monomer (B). Preferably, it is 10 to 20 parts by mass. When the content of the epoxy compound (D) is less than the above lower limit, the coating film tends to lower the moisture resistance, heat resistance, and adhesion to the substrate, and when it exceeds the above upper limit, the tendency is lowered. Graphic properties and preservability of photosensitive resins.

Further, the photosensitive adhesive composition having adhesiveness after the photo-curing reaction of the present invention and after forming the pattern, for example, in order to improve the low thermal expansion, the elastic modulus, the hygroscopicity, and the like of the cured product, for example, cerium oxide may be added. One or two or more kinds of inorganic fillers such as alumina, titania, and boron nitride. Further, if necessary, other additives such as an epoxy resin hardening accelerator, a polymerization inhibiting agent, a plasticizer, a coating agent, and an antifoaming agent may be added to the composition of the present invention.

The epoxy resin hardening accelerator is, for example, an amine compound, an imidazole compound, a carboxylic acid, a phenol, a 4-grade ammonium salt or a compound containing a methylol group. Thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like. Plasticizers such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Defoaming agents and coating agents such as lanthanoid, fluorine-based, and acrylic-based compounds.

The photosensitive adhesive composition which is adhesive after the photo-hardening reaction and the pattern formation may be added with a solvent to adjust the viscosity. The solvent is preferably such that the resin composition is soluble and does not react with the resin and the additive of the resin composition. There are no special restrictions on the things that meet these conditions.

The coating method of the photosensitive adhesive composition which has adhesiveness after the photohardening reaction of the present invention described above and after the pattern formation is not particularly limited, and may be appropriately selected and used, after photohardening reaction and pattern formation. A method of laminating a photosensitive adhesive composition having an adhesive property into a film form, a method of applying a photosensitive adhesive composition which is adhesive after liquid photo-curing reaction, and forming a pattern, by printing configuration A known method such as a method of forming a photosensitive photosensitive adhesive composition after photohardening reaction and forming a pattern.

The coating thickness of the photosensitive adhesive composition which is adhesive after the photohardening reaction and after the pattern formation may vary depending on the application, for example, 1 to 10 μm when facing the liquid crystal display and 1 to 100 μm when the circuit substrate is used. . When the coating thickness of the photosensitive adhesive composition which is adhesive after the photohardening reaction and the pattern formation is thinned, the resolution can be improved, and the photosensitive adhesive which is adhesive after the photohardening reaction and the pattern formation is formed. The coating composition has a coating thickness equal to or less than the fine passage. For example, when the film thickness is 30 μm, a pass path of 30 μm can be obtained, and a line and space having a width of 20 μm can be formed. Further, when the film thickness is 5 μm, an independent line of 2.5 μm and an independent spot can be formed.

In order to form a pattern on a substrate to be bonded, a method of removing a part of the photohardening reaction by the photolithography method and forming a photosensitive adhesive composition having an adhesive pattern after the pattern formation may be irradiated with light. After the photohardening reaction and the formation of the pattern, the specific location of the photosensitive adhesive composition having adhesiveness is removed, and the method of removing the unexposed light is removed. In this case, the known photolithography method can be suitably employed. Further, in the photolithography method, the amount of light irradiation when the light is irradiated to the photosensitive adhesive composition which is adhesive after the photo-curing reaction and after the pattern formation is caused by the ambient temperature and the photosensitive adhesive composition The thickness varies depending on the thickness, and is preferably from 50 to 1000 mJ/cm ² , more preferably from 200 to 800 mJ/cm ² . When the amount of light irradiation does not reach the above lower limit value, the exposure portion after the light irradiation tends to be soluble, and when it exceeds the above upper limit value, the partially unexposed portion is photohardened by the dark reaction, so that the resolution is lowered. . In order to form a pattern portion, the present invention can adjust a photosensitive adhesive composition which is adhesive after use of a photo-curing reaction and after forming a pattern, and forms a pattern portion by the above-described photolithography method to form a pattern portion. These are inherently adhesive patterns. Further, the thickness and width of the pattern portion after formation are not particularly limited, and the thickness and width can be adjusted in accordance with the change in the composition of the member.

Secondly, the heat curing function of the photosensitive adhesive composition is photohardened, and a pattern having a certain shape can be formed on the substrate by thermocompression bonding, and the photosensitive property is adhered after the photohardening reaction and the pattern formation. The layer formed of the adhesive composition is adhered to the second substrate. The conditions of the thermocompression bonding are not particularly limited, and it is preferably a temperature of 50 to 300 ° C, a time of 1 second to 60 minutes, and a pressure of 0.01 to 10 MPa, particularly a temperature of 110 to 150 ° C, a time of 30 seconds to 30 minutes, a pressure of 0.05. Pressed to a condition of 1.0 MPa. This can further improve the adhesion strength. Thereafter, using a laminate obtained by thermal hardening, a desired structure can be obtained by an appropriate assembly step. The representative objects bonded by the adhesive layer at this time may be a germanium wafer and a germanium wafer, a glass substrate and a glass substrate, a germanium wafer and a glass substrate, and may also be used as a germanium wafer and an organic substrate, a glass substrate and an organic substrate. It is used for an adhesive layer between various substrates such as a substrate.

By using the photosensitive adhesive composition which is adhesive after the photohardening reaction of the present invention and after forming a pattern, high adhesion strength, high reliability such as heat resistance and insulation, and excellent alkali imaging can be found. Sex. Therefore, the semiconductor unit can be mounted at a high density, and a substantially simple assembly step and a low cost can be achieved.

Form of implementing the invention

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

First, a method for producing an alkali-soluble resin will be described by way of a synthesis example, and the code used for the synthesis example and the resin evaluation method are as follows.

[code]

BPFE: bisphenol fluorene type epoxy resin (in the general formula (2), R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, X is a 9,9-fluorenyl group, and m is a compound of 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-cyclohexene, p is 1 And q is a compound of 1)

PGMEA: propylene glycol monomethyl ether acetate

TPP: triphenylphosphine

BPDA: biphenyltetracarboxylic dianhydride

[solid content concentration]

The glass filter [weight: W ₀ (g)] was impregnated with ₁ g of the resin solution (including the reaction product and the alkali-soluble resin) obtained in the synthesis example (including the comparative example), and weighed [W ₁ (g)], The weight [W ₂ (g)] after heating for 2 hours from 160 ° C was obtained by the following formula.

Solid content (%) = 100 × (W _{2 -} W ₀ ) / (W _{1 -} W ₀ )

[acid price]

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

[molecular weight]

The number average molecular weight (Mn) of the standard polystyrene conversion value was determined by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

[Synthesis Example 1] (synthetic alkali soluble resin (A-1)

BPFE 240.00g (0.52mol), acrylic acid 74.78g (1.04mol), PGMEA 362.00g and TPP 1.36g were placed in a 1000ml four-necked flask equipped with a reflux cooler, and heated and stirred at 90 to 100 ° C for 12 hours to obtain a reaction. (diol compound).

Next, BPDA 76.31 g (0.26 mol) and THPA 39.46 g (0.26 mol) were added to the reaction product (diol compound), and the reaction was stirred at 100 to 120 ° C for 4 hours to synthesize an alkali-soluble resin (A-1). 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 an Mn of 1400 by GPC analysis.

[Synthesis Example 2] (synthetic alkali soluble resin (A-2)

BPFE 160.00g (0.35mol), HOA-HH 186.99g (0.69mol), PGMEA 346.98g and TPP 0.91g were placed in a 1000ml four-necked flask equipped with a reflux cooler, and heated and stirred at 90 to 100 ° C for 16 hours. Reaction product (diol compound).

Next, 50.89 g (0.17 mol) of BPDA and 26.32 g (0.17 mol) of THPA were added to the reaction product (diol compound), and the reaction was stirred at 100 to 120 ° C for 6 hours to synthesize an alkali-soluble resin (A-2). 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 an Mn of 1510 by GPC analysis.

[Example 1] (Photosensitive adhesive composition which has adhesion after photohardening reaction and pattern formation)

A-160 parts by weight of the above-mentioned alkali-soluble resin (A), 12 parts by weight of trimethylolpropane triacrylate (TMPT) for unsaturated compounds, and 2-methyl-1 for photopolymerization initiator. -12 parts by weight of [4-(methylthio)phenyl]-2-morpholinylpropane, 26 parts by weight of epoxy resin (Yupik 834, manufactured by Oiled Oyster Co., Ltd.), sensitizer (guarantee 0.04 parts by weight of EABF), 0.8 parts by weight of a decane coupling agent, 0.8 parts by weight of a surfactant, and 100 parts by weight of ethyl acetate, and then stirred or dispersed by a stirrer for 1 hour to prepare a solution. Next, a photosensitive adhesive composition having adhesiveness after photohardening reaction and pattern formation was prepared by pressure filtration using a filter having a pore size of 1 μm.

(Substrate for producing a photosensitive adhesive composition which is adhesive after photohardening reaction and after pattern formation)

A photosensitive adhesive composition having an adhesive property after the above-mentioned modulated light hardening reaction and forming a pattern is applied to a BT (double maleimide-triazine resin) of 150 mm × 300 mm × 200 μm by using a spin coater. After the substrate (10), it is dried in an oven set to a temperature range of 80 to 120 ° C to obtain a photosensitive resin composition having a film thickness of 20 μm and having adhesion after forming a pattern. Adhesive layer.

(development, pattern formation)

On the above-mentioned dry adhesive layer, a negative-type mask (Fig. 1) with a certain mask pattern (which is a pattern of 2 mm × 2 mm square) is used, and an ultra-high pressure mercury lamp (Haiti) is used. The company manufactured by the company, illuminance 11 mJ/cm ² , I line standard) was exposed to ultraviolet light under the conditions of 250 mJ/cm ² , and then irradiated with a 2.38% TMAH aqueous solution as a developing solution, and dissolved at 23 ° C for 1 minute. The exposed portion was exposed to a developing step on the surface of the BT substrate, and then washed with pure water for 30 seconds at a pressure of 3.0 kg/cm ² . As a result, the adhesive layer (20) remained in a square shape of 2 mm × 2 mm.

(making a laminate)

Next, a 2 mm × 2 mm × 300 μm thick tantalum wafer (30) was placed on an adhesive layer forming a square of 2 mm × 2 mm, and a pressure of 0.3 MPa was applied while heat-pressing at 110 ° C for 10 seconds to bond the adhesive layer (20). ) with wafers (30). Next, it was placed in an oven and hardened at 180 ° C for 90 minutes to obtain a test composition of Example 1.

[Embodiment 2]

The test laminate of Example 2 was obtained in the same manner as in Example 1 except that the adhesion temperature at 120 ° C when the wafer (30) was thermocompression bonded to the adhesive layer (20) on the BT substrate.

[Example 3]

The test laminate of Example 3 was obtained in the same manner as in Example 1 except that the adhesion temperature at 130 ° C when the wafer (30) was thermocompression bonded to the adhesive layer (20) on the BT substrate.

[Example 4]

The test laminate of Example 4 was obtained in the same manner as in Example 1 except that the tantalum wafer (30) was replaced with a glass substrate (40) of 2 mm × 2 mm × 300 μm.

[Example 5]

The test laminate of Example 5 was obtained in the same manner as in Example 4 except that the adhesion temperature was 120 ° C when the glass substrate (40) was thermocompression bonded to the adhesive layer (20) on the BT substrate.

[Embodiment 6]

The test laminate of Example 6 was obtained in the same manner as in Example 4 except that the adhesion temperature was 130 ° C when the glass substrate (40) was thermocompression bonded to the adhesive layer (20) on the BT substrate.

[Embodiment 7]

The test laminate of Example 7 was obtained in the same manner as in Example 1 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Embodiment 8]

The test laminate of Example 8 was obtained in the same manner as in Example 2 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Embodiment 9]

The test laminate of Example 9 was obtained in the same manner as in Example 3 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Embodiment 10]

The test laminate of Example 10 was obtained in the same manner as in Example 4 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Example 11]

The test laminate of Example 11 was obtained in the same manner as in Example 5 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Embodiment 12]

The test laminate of Example 12 was obtained in the same manner as in Example 6 except that the alkali-soluble resin (A-1) was changed to the alkali-soluble resin (A-2).

[Comparative Example 1]

In addition to the use of a cresol novolak (resin solid content concentration = 50% by weight, manufactured by Nippon Chemical Co., Ltd. CCR-1172H) 60 parts by weight of the alkali-soluble resin (A) after the photohardening reaction and the formation of the pattern are adhesive The test laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except for the photosensitive adhesive composition.

[Comparative Example 2]

In addition to the use of a cresol novolak (resin solid content concentration = 50% by weight, manufactured by Nippon Chemical Co., Ltd. CCR-1172H) 60 parts by weight of the alkali-soluble resin (A) after the photohardening reaction and the formation of the pattern are adhesive The test laminate of Comparative Example 2 was obtained in the same manner as in Example 4 except for the photosensitive adhesive composition.

The substrate and the test laminate of the photosensitive adhesive compositions having the adhesiveness after the photo-curing reaction of the examples 1 to 12 and the comparative examples 1 and 2 and the pattern formation were evaluated by the following methods.

<stickiness test>

After the photo-curing reaction used in the above examples and comparative examples and the photosensitive adhesive composition having adhesiveness after pattern formation were spin-coated on a substrate, the dry coating film after oven drying was evaluated by finger touch. . A substance that is completely viscous is regarded as "○", a substance that is slightly viscous is regarded as "△", and a substance that is obviously viscous is regarded as a "stage" evaluation of "X". The results are shown in Table 1.

<Resolving test>

The photosensitive adhesive composition having the adhesiveness after the photohardening reaction and the pattern formed in the above-described examples and comparative examples prepared was applied onto a tantalum wafer to have a film thickness of 20 μm, and then set. The negative pattern mask of the via pattern of 10 to 100 μm was exposed, and the development was carried out by a horizontal automatic developing machine by the same development conditions as those of the above-described respective examples and comparative examples, and the minimum pass path was measured. Thereafter, the object which can form a path is regarded as "○", and the thing which does not form a path is regarded as "x", and the thing which remains a path, but the residue remains is regarded as "△" three-stage evaluation. The results are shown in Table 1.

<Humidity resistance test>

After comprehensive exposure under the conditions of Example 1, it was hardened at 180 ° C for 90 minutes using an oven. Next, the substrate with the resin was placed in a PCT measuring device, and placed under the conditions of a temperature of 121 ° C and a humidity of 100%, and the change of the coating film was observed under a microscope every 50 hours. Further, after it was judged that the change in the original coating film after hardening was judged to be deteriorated, the sample was stopped.

<Welding heat resistance test>

Prepare the resin-attached substrate with the moisture-resistance test, and immerse it in a solder bath at 260 °C for 30 seconds according to JIS C-6481 test method, and then use a tape to perform the peeling test and treat it as 1 cycle, repeating cycle 1 After 3 times, the state of the coating film was visually observed and evaluated by the following criteria. The results are shown in Table 1.

◎: The film was still not abnormal after repeated cycles of 3 times.

○: The coating film slightly changed after repeating the cycle three times.

△: The coating film changed after repeated cycles of 2 times.

×: The coating film changed after repeating the cycle once.

<Shear strength (adhesion strength) test>

The adhesion strength (adhesive layer) of each of the laminates obtained in Examples 1 to 12 and Comparative Examples 1 to 2 was subjected to a shear strength test using a slitting tester, and the adhesion was measured after the photohardening reaction and the formation of the pattern. The adhesion strength of the adhesive layer formed by the photosensitive adhesive composition to the wafer or the glass substrate. The evaluation is based on the following criteria, and the results are shown in Table 1.

◎: The adhesive strength was 30 MPa or more, and the state of destruction was equal to or higher than the strength of the wafer or the glass substrate (the adhesive layer could not be peeled off even if the wafer or the glass was broken).

○: The adhesive strength was 20 MPa or more and less than 30 MPa, and the fracture state was interfacial peeling.

△: The adhesive strength was 1 MPa or more and less than 20 MPa.

×: The adhesive strength was not measured.

<Turn resistance test>

The photosensitive adhesive composition having the adhesiveness after the photohardening reaction and the pattern formation used in the above examples and comparative examples was applied to a separately prepared tantalum wafer substrate (30) or a glass substrate (using a spin coater). 40), after drying in an oven set to a temperature range of 80 to 120 ° C to form a coating film having a film thickness of 20 μm, in addition to using a pattern of a mask (forming a 3 mm × 3 mm square, 1 mm space) The negative mask of the mask pattern (Fig. 3 is a pattern diagram of a partial mask pattern), and exposed and developed under the same conditions as in the first embodiment to form a grid-like adhesion of 3 mm × 3 mm square and 1 mm space. Layer (20). The wafer substrate (30) or the glass substrate (40) was bonded to the adhesive layer of the substrate with the photosensitive adhesive in the same manner as in each of the examples and the comparative examples, and cured to obtain a laminate (Fig. 4 is Schematic diagram of partial section structure). Next, each of the laminates was placed on a hot plate at 270 ° C, left for 3 minutes, cooled, and visually confirmed whether or not the interface between the adhesive layer and the substrate was peeled off, and then evaluated on the following basis. The results are shown in Table 1.

○: Even if it is repeated 10 times, it is not peeled at all.

△: 5 to 10 times or less

×: peeled off the first time

As shown in Table 1, the results of the self-shearing strength test were obtained from the results of the examples 1 to 6 when the photosensitive adhesive composition and the wafer or glass were adhered after the photohardening reaction and after the pattern formation. When the adhesion temperature is 110 ° C or 120 ° C, the adhesive strength is 20 MPa or more, and at 130 ° C, the strength of the substrate is more than or equal. Therefore, comparative examples 1 and 2 can obtain better adhesion strength. Further, when the alkali-soluble resin (A) of Examples 1 to 6 was used, good developability was obtained, and when the cresol novolacs of Comparative Examples 1 and 2 were used, the developability was low. Therefore, it is judged that the photosensitive adhesive composition which is adhesive after the photohardening reaction of the present invention and after the formation of the pattern can have high adhesive strength and good alkali developability.

10. . . BT substrate

20. . . Adhesive layer

30. . . Wafer

40. . . glass substrate

Fig. 1 is a plan view showing the shape of a mask used in the embodiment.

Fig. 2 is a schematic cross-sectional structural view showing a substrate of a photosensitive adhesive composition according to a preferred embodiment.

Fig. 3 is an explanatory view of a mask pattern used in the resistance to melt resistance test in the examples.

Fig. 4 is a cross-sectional structural explanatory view of a laminate used in the melt resistance test in the examples.

Claims (4)

A method for adhering a substrate, which is a method for adhering a substrate to each other by using a photosensitive adhesive composition having an adhesive property after photohardening reaction and pattern formation, wherein the photosensitive adhesive composition contains and is relatively a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and a monocarboxylic acid having an unsaturated group, wherein a) a dicarboxyl group has a molar ratio of a/b of from 0.1 to 10. An acid or a tricarboxylic acid or an acid anhydride thereof, and b) a tetracarboxylic acid or an acid dianhydride thereof, and an alkali-soluble resin represented by the following general formula (1) is used as a resin component. (wherein, W is a bisphenol derivative represented by the following general formula (2), Y is a tetravalent carboxylic acid residue, and G is a substituent represented by the following general formula (3) or (4), Z is a hydrogen atom or a substituent represented by the general formula (5), and n is a number from 1 to 20), (wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a phenyl group, and X is -CO-, -SO ₂ -, -C ( CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a straight bond, m is 0 to 10 Integer), (wherein R ₅ is a hydrogen atom or a methyl group, R ₆ is a divalent alkyl group having 2 to 22 carbon atoms or an alkylaryl group, and R ₇ is a divalent aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms. , p is the number from 0 to 60, q is 0 or 1), (wherein, L is a 2 or a trivalent carboxylic acid residue, and r is 1 or 2), and the photosensitive adhesive composition is applied onto one of the substrates and photohardened by the reaction. Like the pattern formed, it is thermocompression bonded to another substrate 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 to adhere the substrates to each other. The method of adhering a substrate according to the first aspect of the invention, wherein the photosensitive adhesive composition having an adhesive property after the photo-curing reaction and the pattern formation contains the (A) alkali-soluble resin, and further contains (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) an epoxy resin. The method of adhering a substrate according to claim 1 or 2, wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 40,000 and an acid value of 50 to 200 mgKOH/g. The method of adhering a substrate according to claim 1 or 2, wherein the bisphenol which forms an alkali-soluble resin is a bisphenol having an anthracene skeleton.