JP5353064B2 - Photosensitive adhesive composition, adhesive film obtained using the same, adhesive sheet, adhesive pattern, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photo-sensitive adhesive composition superior in a pattern forming property by an alkaline developer and having sufficient re-adhesion after exposed, and to provide an adhesive film also superior in pattern forming property by an alkaline developer, having a sufficient re-adhesion after exposure and capable of adhering it to an adherend at a low temperature. <P>SOLUTION: The photo-sensitive adhesive composition comprises (A) an alkali-soluble resin, (B) an epoxy resin, (C) a radiation-polymerizable compound and (D) a photo-initiator, in which (A) the alkali-soluble resin has a glass transition temperature of 150&deg;C or lower, (B) the epoxy resin has (B1) a component with three or more functions and (B2) a liquid component of which a part or all may be also (B1) a component with three or more functions. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive adhesive composition. Furthermore, the present invention relates to an adhesive film, an adhesive sheet, an adhesive pattern, and a semiconductor device.

  2. Description of the Related Art In recent years, semiconductor packages having various forms have been proposed as electronic components have been improved in performance and functionality. In the semiconductor package, the adhesive for bonding the semiconductor element and the support substrate for mounting the semiconductor element includes, in addition to low stress, low temperature adhesion, moisture resistance reliability, solder reflow resistance, functions of the semiconductor package, Depending on the form and the method of simplifying the assembly process, it may be required to have a photosensitive function capable of forming a pattern. Photosensitivity is a function in which a portion irradiated with light is chemically changed and insolubilized or solubilized in an aqueous solution or an organic solvent. When this photosensitive photosensitive adhesive is used, a high-definition adhesive pattern can be formed by exposing through a photomask and forming a pattern with a developer.

  As a material having a photosensitive function, a material containing a polyimide resin precursor (polyamic acid) or a polyimide resin as a main component in addition to a photoresist has been used so far (see Patent Documents 1 to 3). However, these materials have not been designed assuming the function as an adhesive. In addition, when these materials are used as adhesives for the above applications, it is difficult to ensure heat resistance with materials such as photoresists, while in the case of polyimide resin precursors and polyimide resins, in terms of heat resistance Although excellent, the former requires high temperature of 300 ° C. or higher during thermal ring-closing imidization, and the latter requires high temperature of 300 ° C. or more, respectively, so that thermal damage to the surrounding materials is large and thermal stress is likely to occur. There was a problem such as.

On the other hand, attempts have also been made to improve low-temperature workability and solder heat resistance by blending and crosslinking a thermosetting resin in an adhesive using a polyimide resin or the like.
JP 2000-290501 A JP 2001-329233 A Japanese Patent Laid-Open No. 11-24257

  However, in the conventional design using a polyimide resin or the like, it has been difficult to simultaneously achieve a high level of both the pattern formability with an alkali developer and the adhesion property to an adherend at a low temperature. In addition, it has been difficult to impart re-adhesiveness capable of expressing a sufficiently high adhesive force when thermocompression bonded after exposure.

  This invention is made | formed in view of such a situation, It aims at providing the photosensitive adhesive composition which is excellent in the pattern formation property by an alkali developing solution, and has sufficient re-adhesiveness after exposure. . Another object of the present invention is to provide an adhesive film that has excellent pattern formability with an alkaline developer, has sufficient re-adhesion after exposure, and can be attached to an adherend at a low temperature. To do. It is another object of the present invention to provide a highly reliable semiconductor device having excellent adhesion between a semiconductor element and a semiconductor element mounting support substrate.

  The photosensitive adhesive composition according to the present invention comprises (A) an alkali-soluble resin, (B) an epoxy resin, (C) a radiation polymerizable compound, and (D) a photopolymerization initiator. A photosensitive adhesive composition, wherein (A) the glass transition temperature of the alkali-soluble resin is 150 ° C. or lower, (B) the epoxy resin is (B1) a trifunctional or higher component, and (B2) a liquid component. In addition, (B2) a part or all of the liquid component may also serve as a (B1) trifunctional or higher functional component.

  By setting the photosensitive adhesive composition to the above composition, a photosensitive adhesive composition having both a pattern forming function with an alkaline developer and a function as a die bonding material can be obtained. In particular, good re-adhesiveness under relatively low-temperature pressure bonding conditions after exposure, stable adhesiveness that can suppress peeling of the adherend when assembling a semiconductor device, and sufficient heat resistance after exposure and heat-curing And the reliability of the semiconductor device or electronic component can be improved.

  The ratio of (B1) trifunctional or higher component to the whole epoxy resin is 10 to 90% by mass, and (B2) the ratio of the liquid component to the whole epoxy resin is preferably 10 to 90% by mass. Thereby, the photosensitive adhesive composition which has favorable developability, the re-adhesion property after exposure (thermocompression bonding property), and sufficient adhesive force at the time of high temperature is obtained.

  It is preferable that the photosensitive adhesive composition according to the present invention further contains (E) an epoxy resin curing agent.

  (A) The alkali-soluble resin is preferably a thermoplastic resin having a carboxyl group and / or a phenolic hydroxyl group. Thereby, the photosensitive adhesive composition which can ensure the pattern formation property by an alkali developing solution is obtained.

  (A) It is preferable that the weight average molecular weight of alkali-soluble resin is 5000-150,000. By using such a thermoplastic resin, a photosensitive adhesive composition that can be attached to an adherend such as a semiconductor wafer at a lower temperature after exposure is obtained.

(A) The alkali-soluble resin is preferably a polyimide obtained by reacting tetracarboxylic dianhydride and diamine. The diamine preferably contains an aromatic diamine represented by the following general formula (I) or (II). Thereby, the photosensitive adhesive composition excellent in the developability with respect to an alkali developing solution is obtained.

（式中、Ｑ_１、Ｑ_２及びＱ_３は各々独立に炭素数１〜１０のアルキレンを示し、ｎ_１は１〜８０の整数を示す。） The diamine further contains an aliphatic ether diamine represented by the following general formula (III), and the ratio of the aliphatic ether diamine to the whole diamine is preferably 10 to 90 mol%. Thereby, the photosensitive adhesive composition which makes it possible to affix on adherends, such as a semiconductor wafer, at lower temperature is obtained.

(In the formula, Q ₁ , Q ₂ and Q ₃ each independently represent an alkylene having 1 to 10 carbon atoms, and n ₁ represents an integer of ₁ to 80.)

（式中、Ｒ_１及びＲ_２は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｎ_２は１〜５の整数を示す。） The diamine further contains a siloxane diamine represented by the following general formula (IV), and the ratio of the siloxane diamine to the entire diamine is preferably 1 to 20 mol%. Thereby, the photosensitive adhesive composition which can further improve the adhesiveness after exposure is obtained.

(Wherein R ₁ and R ₂ each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ₃ , R ₄ , R ₅ and R ₆ are each independently alkyl group having 1 to 5 carbon atoms, phenyl or a phenoxy group, _{n 2} is an integer of 1-5.)

The tetracarboxylic dianhydride preferably contains 40 mol% or more of the compound represented by the following general formula (V) with respect to the total tetracarboxylic dianhydride. Thereby, the photosensitive adhesive composition which can provide the favorable solubility to a solvent, the outstanding moisture-proof reliability, and a favorable photosensitive characteristic is obtained.

(B1) The trifunctional or higher functional component is preferably a trisphenolmethane type epoxy resin represented by the following general formula (VI). As a result, there is little outgassing at the time of heating, the softening temperature is relatively low, the flowability at the time of thermocompression bonding is not impaired, the crosslink density of the cured product is high, and a high adhesive strength at the time of heating the film can be expressed Adhesive composition is obtained.

(B2) The liquid component is preferably bisphenol A bis (triethylene glycol glycidyl ether) ether represented by the following general formula (VII). Thereby, the photosensitive adhesive composition which can give the fluidity | liquidity at the time of thermocompression bonding with few outgases at the time of a heating, and can provide the favorable developability with respect to an alkaline developing solution is obtained.

  (E) The epoxy resin curing agent is preferably a compound having two or more phenolic hydroxyl groups. Thereby, the favorable solubility to the alkaline developing solution of (E) epoxy resin hardening | curing agent can be provided.

The compound having a phenolic hydroxyl group is preferably trisphenol represented by the following general formula (VIII). Thereby, the photosensitive adhesive composition which can provide a favorable photosensitive characteristic is obtained.

  The adhesive film according to the present invention is composed of the photosensitive adhesive composition according to the present invention. Moreover, the adhesive sheet which concerns on this invention is equipped with a base material and the adhesive bond layer which consists of the photosensitive adhesive composition which concerns on the said this invention provided on the one surface of this base material.

  In the adhesive pattern according to the present invention, an adhesive layer made of the photosensitive adhesive composition according to the present invention is formed on an adherend, the adhesive layer is exposed through a photomask, and the post-exposure layer is exposed. It is formed by developing the adhesive layer with an alkaline aqueous solution. Since this photosensitive adhesive composition according to the present invention is excellent in pattern formability, this adhesive layer can have a high-definition pattern and is excellent in re-adhesion after exposure.

  The semiconductor device according to the present invention uses the photosensitive adhesive composition according to the present invention.

  The photosensitive adhesive composition according to the present invention has a high dissolution rate in an alkali developer, is excellent in pattern formation with an alkali developer, and exhibits high adhesion after exposure. When the photosensitive adhesive composition according to the present invention is applied to an adherend, it has better alignment accuracy than the case of using a liquid resin composition, and can improve the patterning resolution by exposure. it can. Further, the adhesive film according to the present invention can be attached to an adherend at a relatively low temperature, and thermal damage to peripheral materials is suppressed, so that a highly reliable semiconductor device and electronic component can be obtained. . Furthermore, since it has excellent heat resistance after thermosetting, it can be suitably used for protection applications such as semiconductor elements, optical elements, or solid-state imaging elements, or adhesive applications that require a fine adhesion region. The reliability of the device can be improved.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The photosensitive adhesive composition according to this embodiment contains (A) an alkali-soluble resin, (B) an epoxy resin, (C) a radiation polymerizable compound, and (D) a photopolymerization initiator. It is a photosensitive adhesive composition.

  (A) The alkali-soluble resin is a resin having an alkali-soluble group in the molecule. Examples of the alkali-soluble group include a carboxyl group and a hydroxyl group. Among them, a carboxyl group or a phenolic hydroxyl group is preferable in terms of obtaining good developability, and a thermoplastic having these functional groups at the terminal or side chain. It is preferable to use a resin.

  (A) The alkali-soluble resin has a glass transition temperature (hereinafter referred to as “Tg”) of 150 ° C. or lower, and preferably 100 ° C. or lower. Although there is no particular lower limit, it is preferably 20 ° C. or higher. When Tg exceeds 150 ° C., when the photosensitive adhesive composition according to the present invention is formed into a film, the bonding temperature to an adherend such as a silicon wafer and the pressure bonding temperature after exposure are increased. When the photosensitive adhesive composition according to the present invention is formed into a film shape, it tends to easily damage peripheral members such as warpage due to stress, and Tg is less than 20 ° C. There is a tendency to become stronger, and the handleability tends to be worsened. In addition, said Tg is the peak temperature (main dispersion temperature) of tan-delta when measured as a film using a viscoelasticity measuring apparatus (made by a rheometric company).

  (A) The alkali-soluble resin preferably has a weight average molecular weight (hereinafter referred to as “Mw”) of 5,000 to 150,000, more preferably 10,000 to 100,000, and particularly preferably 10,000 to 50,000. By setting Mw within the above range, it is possible to obtain the effect of ensuring fluidity at the time of heat melting when the semiconductor element is bonded and fixed to the semiconductor element mounting support base. When Mw is smaller than 5000, the film formability tends to be lowered, and when it exceeds 150,000, the solubility in an alkaline developer is lowered and the developing time tends to be longer. In addition, said Mw is a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (For example, "C-R4A" (brand name) by Shimadzu Corporation).

  The thermoplastic resin is not particularly limited, and for example, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyurethaneimide resin, polyurethaneamideimide resin, siloxane polyimide resin, polyesterimide resin, or those In addition to these copolymers, at least one resin selected from the group consisting of phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyester resins, polyether ketone resins, (meth) acrylic copolymers, etc. Among them, a polyimide resin is preferably used because it has heat resistance. In addition, these thermoplastic resins preferably contain or introduce an alkali-soluble group such as a carboxyl group and / or a hydroxyl group at the side chain or terminal at the time of synthesis from the viewpoint of imparting developability.

  (A) It is preferable that alkali-soluble resin is a polyimide obtained by making tetracarboxylic dianhydride and diamine react (condensation reaction). In this case, Tg can be 150 degrees C or less and Mw can be 5000-150,000 by adjusting suitably the kind of diamine, its preparation ratio, reaction conditions, etc. The obtained polyimide may be used alone or as a mixture (blend) of two or more if necessary.

  The reaction of tetracarboxylic dianhydride and diamine can be carried out by a known method as understood by those skilled in the art. For example, in this reaction, first, tetracarboxylic dianhydride and diamine are added in an organic solvent in an equimolar or almost equimolar ratio at a reaction temperature of 80 ° C. or less, preferably 0 to 60 ° C. Let The order of adding each component is arbitrary. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The molecular weight can be adjusted by heating the produced polyamic acid to a temperature of 50 to 80 ° C. for depolymerization. A polyimide is produced by dehydrating and ring-closing the produced polyamic acid. The dehydration ring closure can be performed by a thermal ring closure method by heating or a chemical ring closure method using a dehydrating agent.

  More specifically, regarding the charging ratio of tetracarboxylic dianhydride and diamine, more specifically, the total amount of diamine is preferably 0.5 to 2.0 mol with respect to 1.0 mol of the total amount of tetracarboxylic dianhydride. More preferably, it is in the range of 0.8 to 1.0 mol. When the ratio of diamine exceeds 2.0 mol, a large amount of polyimide oligomers having an amino group at the end is produced, and when it is less than 0.5 mol, many polyimide oligomers having an acid anhydride at the end tend to be produced. When the amount of the polyimide oligomer increases, the weight average molecular weight of the polyimide decreases, and various characteristics including the heat resistance and the like of the photosensitive adhesive composition are liable to occur. By adjusting the charging ratio, the weight average molecular weight of polyimide can be adjusted to be in the range of 5000 to 150,000.

  Examples of the diamine used for the synthesis of polyimide include aromatic diamines having a phenolic hydroxyl group represented by the following general formula (9) or (10) in addition to the above general formula (I) or (II). The general formula (I) or (II) is preferably used in that good solubility in an alkali developer can be imparted. In addition, these diamine can be used individually or in combination of 2 or more types.

  The diamine preferably contains an aliphatic ether diamine represented by the general formula (III) in order to reduce the Tg of the polyimide and reduce the thermal stress. More specific examples of the aliphatic ether diamine of the general formula (III) include those represented by the following general formula (IIIa), (IIIb) or (IIIc). Among these, the aliphatic ether diamine of the general formula (IIIa) is preferable in that it can secure a low temperature sticking property and good adhesion to an adherend.

（ｎ_１は１〜８０の整数を示す。）

(N ₁ represents an integer of ₁ to 80.)

  As a commercial item of aliphatic ether diamine, for example, “Jefamine D-230”, “D-400”, “D-2000”, “D-4000”, “ED-600” manufactured by Sun Techno Chemical Co., Ltd. , “ED-900”, “ED-2001”, “EDR-148” (trade name), “Polyetheramine D-230”, “D-400”, “D-2000” (manufactured by BASF) As mentioned above, there are trade names).

It is preferable that the diamine further contains a siloxane diamine represented by the general formula (IV) in that good adhesion after exposure can be imparted. As the siloxane diamine represented by the general formula (IV), for example, when n _{2 in} the formula is 1, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminobutyl) disiloxane 1,3-dimethyl-1,3-dimethoxy- 1,3-bis (4-aminobutyl) disiloxane and the like, and when n ₂ is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) Trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy -1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1, 5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis ( 4-aminobutyl) trisiloxane, 1,1 , 5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3- Aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1 , 5-bis (3-aminopropyl) trisiloxane.

  These diamines can be used alone or in combination of two or more. In this case, the aromatic diamine represented by the general formula (I) or (II) is 10 to 50 mol% of the total diamine, and the aliphatic ether diamine represented by the general formula (III) is 10 to 90 mol of the total diamine. %, The siloxane diamine represented by the general formula (IV) is preferably 1 to 20 mol% (more preferably 5 to 10 mol%) of the total diamine.

  When the aliphatic ether diamine represented by the general formula (III) is less than 10 mol% of the total diamine, the Tg of the polyimide is increased, and the low-temperature workability (sticking property at a low temperature) tends to be reduced. If it exceeds mol%, the Tg of the polyimide becomes low, the adhesiveness of the film surface becomes strong, and voids tend to occur during thermocompression bonding. If the siloxane diamine represented by the general formula (IV) is less than 1 mol% of the total diamine, the adhesive strength after development tends to be reduced, and if it exceeds 20 mol%, the solubility in an alkaline developer is reduced. Tend to.

  The diamine may further contain a diamine other than those described above. For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3 , 4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethermethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3 ′ -Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diamino Diphenyls Phon, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 4,4 '-Diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2'-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2, 2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4 Aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) Phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) Sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl ) Sulfone, 1,3-bis (aminomethyl) cyclohexane and 2,2-bis (4-aminophenoxyphenyl) propane.

  Tetracarboxylic dianhydride used as a raw material for the synthesis of polyimide is preferably purified by recrystallization from acetic anhydride in order to suppress deterioration of various properties of the adhesive. Alternatively, the tetracarboxylic dianhydride may be dried by heating at a temperature lower by 10 to 20 ° C. than its melting point for 12 hours or more. The purity of tetracarboxylic dianhydride can be evaluated by the difference between the endothermic onset temperature and the endothermic peak temperature measured by a differential scanning calorimeter (DSC). It is preferable to use a tetracarboxylic dianhydride purified so as to have a temperature within 10 ° C., more preferably within 10 ° C., for the synthesis of the polyimide. The endothermic start temperature and endothermic peak temperature are measured using DSC (“DSC-7 type” manufactured by Perkin Elmer Co., Ltd.) under the conditions of sample amount: 5 mg, heating rate: 5 ° C./min, measurement atmosphere: nitrogen. The

  The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3 ′. -Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3 4-Zika Boxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3 '-Benzophenonetetracarboxylic dianhydride, 3,3,3', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1 , 4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1, 4,5 8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5 , 6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3, 2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3 , 4-Dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphe Nyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Anhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3 4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene- 2,3,5,6-teto Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 4, 4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2- Hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Xene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4 ′,-oxydiphthalic dianhydride represented by the above general formula (V) And tetracarboxylic dianhydride represented by the following general formula (11), tetracarboxylic dianhydride represented by the following general formula (12), and the like. Among the tetracarboxylic dianhydrides, 4,4 ′, − represented by the general formula (V) in that good solubility in a solvent, excellent moisture-reliability, and good photosensitive properties can be imparted. Oxydiphthalic dianhydride is preferred.

（式中、ｎは２〜２０の整数を示す）

(In the formula, n represents an integer of 2 to 20)

  The tetracarboxylic dianhydride represented by the general formula (11) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis (trimellitate). Anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1, 6- (Hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) Bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) Bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

  The content of tetracarboxylic dianhydride is preferably 40 mol% or more with respect to 100 mol% of all tetracarboxylic dianhydrides. If this ratio is less than 40 mol%, the effect of improving solubility and obtaining good photosensitive characteristics tends to be reduced.

  These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  (B) The epoxy resin contains (B1) a trifunctional or higher component and (B2) a liquid component. Part or all of the (B2) liquid component may also serve as a (B1) trifunctional or higher component. The ratio of the (B1) trifunctional or higher component to the total epoxy resin is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 10 to 70% by mass. The ratio of the (B2) liquid component to the total epoxy resin is preferably 10 to 90% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass.

  (B1) If the ratio of the trifunctional or higher functional component is less than 10% by mass, the cross-linking density of the cured product is not sufficient, and good adhesive strength at high temperatures tends not to be ensured. Moreover, when it exceeds 90 mass%, it exists in the tendency for the storage stability of a film to be impaired due to high reactivity. Further, when a solid epoxy resin is selected, if the ratio exceeds 90% by mass, the thermocompression bonding temperature tends to increase and the developability with respect to an alkaline developer tends to be impaired.

  (B2) If the ratio of the liquid component is less than 10% by mass, the fluidity during thermocompression tends to be insufficient, and if it exceeds 90% by mass, the reactivity of the system increases and the storage stability is impaired. In addition, when combined with the (B1) trifunctional or higher component, there is a tendency that it is impossible to suppress a decrease in adhesive strength at a high temperature accompanying a decrease in crosslinking density after thermosetting. In addition, ionic impurities due to the raw material of the epoxy resin tend to increase.

  (B) As the epoxy resin, (a) a bifunctional liquid epoxy resin, (b) a bifunctional solid epoxy resin, (c) a trifunctional or higher liquid epoxy resin, and (d) a trifunctional or higher solid epoxy resin. It is possible to use together. (C) The trifunctional or higher functional liquid epoxy resin corresponds to both (B1) a trifunctional or higher functional component and (B2) a liquid component. In such a case, the content of the (B1) trifunctional or higher component is represented by the sum of (c) and (d), and may be adjusted to 10 to 90% by mass with respect to the total epoxy resin. preferable. (B2) Content of a liquid component is represented by the sum total of (a) and (c), and it is preferable to adjust so that it may become 10-90 mass% with respect to all the epoxy resins. By adjusting (B1) trifunctional or higher functional component and (B2) liquid component as described above, the effect of the present invention can be further enhanced.

  (B1) The trifunctional or higher functional component is not particularly limited as long as it is an epoxy resin containing at least three epoxy groups in the molecule. Examples of such an epoxy resin include those represented by the general formula (VI). Trisphenolmethane type epoxy resin (2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)) ] Ethyl] phenyl] propane) and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- represented by the following general formula (13): [1- [4-([2,3-epoxypropoxy] phenyl) -1-] methylethyl] phenyl] ethyl] phenoxy] -2-propanol, phenol glycidyl ether type epoxy resin and the like It is. Examples of phenol glycidyl ether type epoxy resins include trifunctional or tetrafunctional glycidyl ethers, trifunctional or tetrafunctional glycidyl amines, glycidyl ethers of cresol novolac resins, glycidyl ethers of phenol novolac resins, and the like. Among them, the outgassing during heating is small, the softening temperature is relatively low, the flowability during thermocompression bonding is not impaired, the crosslink density of the cured product is high, and high adhesive strength during heating of the film can be expressed. The trisphenol methane type epoxy resin represented by the general formula (VI) is preferable. In addition, these (B1) trifunctional or higher functional components can be used alone or in combination of two or more.

  (B2) The liquid component is generally an epoxy resin that is liquid at 10 to 30 ° C., and the liquid state includes a viscous liquid state. As such an epoxy resin, for example, glycidyl ether of bisphenol A type (or AD type, S type, F type), glycidyl ether of water-added bisphenol A type, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin Glycidyl ether of bisphenol A novolac resin, glycidyl ether of naphthalene resin, trifunctional (or tetrafunctional) glycidyl ether, glycidyl ether of dicyclopentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) Type) glycidylamine, naphthalene resin glycidylamine, and the like, as well as an ethylene oxide 6-mol adduct bisphenol A type liquid epoxy resin represented by the above general formula (VII) (ie, bisphenol) A bis (triethylene glycol glycidyl ether) ether) and the like, to select one of the liquid at 10 to 30 ° C. from these. Among them, bisphenol A bis (triethylene glycol glycidyl ether) ether represented by the general formula (VII) has less outgassing during heating, can impart fluidity during thermocompression bonding, and has good developability for an alkaline developer. It is preferable at the point which can provide. In addition, these (B2) liquid components can be used individually or in combination of 2 or more types.

  (B) The content of the epoxy resin is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin, and 5 to 50 parts by mass. Is particularly preferred. (B) When the content of the epoxy resin is less than 5 parts by mass, the crosslinking density after thermosetting is not sufficient, and there is a tendency that high adhesive strength at high temperatures cannot be secured. In addition to the loss of formability, the solubility in an alkaline developer is lowered and the developability tends to be lowered.

  (B1) The content of the trifunctional or higher component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of (A) the alkali-soluble resin, and (B2) the content of the liquid component is ( A) It is preferable to contain 1-80 mass parts with respect to 100 mass parts of alkali-soluble resin. This is preferable in that good reliability of the package such as low outgassing, reflow resistance, and moisture resistance reliability can be secured at the same time when the lamination temperature is from room temperature to 100 ° C. or during assembly heating.

The (C) radiation polymerizable compound is not particularly limited as long as it is a compound that is polymerized and / or cured by irradiation with radiation such as ultraviolet rays and electron beams. Specific examples of radiation polymerizable compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, tetrahydro Furfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane Triacrylate, trimethylolpropane dimethacrylate, tri Tyrolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methan Acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, a compound represented by the following general formula (14), Examples include urethane acrylate or urethane methacrylate, and urea acrylate. In General Formula (14), R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, and q and r each independently represent an integer of 1 or more.

  The urethane acrylate and urethane methacrylate are produced, for example, by a reaction of a diol, an isocyanate compound represented by the following general formula (15), and a compound represented by the following general formula (16).

In the general formula (15), s represents 0 or 1, and R ₅ represents a divalent or trivalent organic group having 1 to 30 carbon atoms. In General Formula (16), R ₆ represents a hydrogen atom or a methyl group, and R ₇ represents an ethylene group or a propylene group.

  The urea methacrylate is produced, for example, by a reaction between a diamine represented by the following general formula (17) and a compound represented by the following general formula (18).

In General Formula (17), R ₈ represents a divalent organic group having 2 to 30 carbon atoms. In general formula (18), t represents 0 or 1.

  (C) As a radiation-polymerizable compound, in addition to the above compounds, a vinyl copolymer containing a functional group, at least one ethylenically unsaturated group, an oxirane ring, an isocyanate group, a hydroxyl group, or a carboxyl group The radiation-polymerizable copolymer etc. which have an ethylenically unsaturated group in the side chain obtained by addition-reacting the compound which has functional groups, such as these, can be used.

  (C) A radiation polymerizable compound can be used individually or in combination of 2 or more types. Among these, the radiation-polymerized compound represented by the general formula (14) is preferable in that it can impart solvent resistance after curing, and urethane acrylate and urethane methacrylate are preferable in terms of imparting flexibility after curing.

  (C) The molecular weight of the radiation polymerizable compound is preferably 2000 or less. When the molecular weight exceeds 2000, the solubility of the photosensitive adhesive composition in an alkaline aqueous solution tends to decrease, and the tackiness of the adhesive film decreases, so that it is attached to an adherend such as a semiconductor wafer at a low temperature. Tend to be difficult.

  (C) The content of the radiation-polymerizable compound is preferably 10 to 250 parts by mass, more preferably 20 to 200 parts by mass, and 40 to 150 parts per 100 parts by mass of the (A) alkali-soluble resin. Part by mass is more preferable. When the amount of the radiation-polymerizable compound exceeds 250 parts by mass, the fluidity at the time of thermocompression decreases due to photopolymerization, and the handleability of the film tends to be impaired. If the amount is less than 10 parts by mass, insolubilization in an alkaline developer after exposure tends to be difficult to be achieved, and it becomes difficult to form a pattern after development.

  (D) As a photoinitiator, what has an absorption band in 400 nm is preferable in order to improve the sensitivity at the time of pattern formation. (D) Specific examples of the photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, Aromatics such as 2-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone Ketone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl Benzoin ethers such as ether, benzoins such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer, -Acridine derivatives such as phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2, And bisacylphosphine oxides such as 4,6, -trimethylbenzoyl) -phenylphosphine oxide. These can be used alone or in combination of two or more.

  (D) Although there is no restriction | limiting in particular in content of a photoinitiator, Usually, it is 0.01-30 mass parts with respect to 100 mass parts of (A) alkali-soluble resin.

  The photosensitive adhesive composition according to this embodiment preferably further comprises (E) an epoxy resin curing agent.

  (E) There is no restriction | limiting in particular as an epoxy resin hardening | curing agent, For example, a phenolic compound, an aliphatic amine, an alicyclic amine, an aromatic polyamine, polyamide, an aliphatic acid anhydride, an alicyclic acid anhydride, aromatic Aliphatic acid anhydrides, dicyandiamides, organic acid dihydrazides, boron trifluoride amine complexes, imidazoles, tertiary amines, and the like. Among them, phenolic compounds are preferred because they can provide solubility in an alkaline developer. More preferred are phenolic compounds having at least two phenolic hydroxyl groups in the molecule.

  Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentagen cresol novolak resin, dicyclopentagen phenol novolak resin. And xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-vinylphenol resin, phenol aralkyl resin and the like. Among these, a trisphenol compound is preferable in that it can effectively reduce the outgas that causes contamination of the chip surface or device or the odor during package assembly heating.

  The trisphenol compound is a trisphenol novolak resin having three hydroxyphenyl groups in the molecule, and specific examples of such a trisphenol compound include, for example, 4,4 ′, 4 ″. -Methylidenetrisphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidenetris [ 2-methylphenol], 4,4 ′, 4 ″ -ethylidinetrisphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′-[(4- Hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'-[(3-hydroxyphenyl) methylene] bis [2,3-dimethylphenol] ], 2,2 '-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2'-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 '-[(2-hydroxyphenyl) methylene] bis [2,3,5-trimethylphenol], 4,4'-[(2-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol ], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bi [2,3,6-trimethylphenol], 4,4 '-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(3-hydroxyphenyl) methylene ] Bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(3,4- Dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(3,4- Dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylpheny) L) methyl] -1,2-benzenediol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4', 4 "-(3-methyl-1-propanyl) -3-ylidene) trisphenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4,4'-[(3-hydroxyphenyl) methylene] bis [2-methyl Ethylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylethylphenol], 2,2'-[(3-hydroxyphenyl) methylene] bis [3,5,6-trimethyl Phenol], 2,2 '-[(4-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4'-[(2-hydroxyphenyl) Tylene] bis [2-cyclohexylphenol], 4,4 '-[(3-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4'-[1- [4- [1- (4-hydroxy) -3,5-dimethylphenyl) -1-methylethyl] phenyl] ethylidene] bis [2,6-dimethylphenol], 4,4 ', 4 "-methylidynetris [2-cyclohexyl-5-methylphenol], 4,4 '-[1- [4- [1- (3-cyclohexyl-4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bis [2-cyclohexylphenol], 2,2'-[(3 , 4-Dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [ -(Methylethyl) phenol], 2,2 '-[(3,4-dihydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4'-[(3,4-dihydroxyphenyl) Methylene] bis [2-cyclohexylphenol], α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and the like. Among them, good photosensitive characteristics can be imparted. Therefore, trisphenol represented by the above general formula (VIII) is preferably used.

  (B1) The epoxy equivalent of the trifunctional or higher component is preferably 0.95 to 1.05 with respect to the OH equivalent of the phenolic compound (E) as the epoxy resin curing agent. (B2) It is preferable that the equivalent ratio of the epoxy equivalent of the liquid component is 0.95 to 1.05 with respect to the OH equivalent of the phenolic compound as the (E) epoxy resin curing agent. If it is outside the above range, unreacted monomers may remain or the crosslink density of the cured product may not increase.

  Moreover, a hardening accelerator can also be added to the photosensitive adhesive composition which concerns on this embodiment. There are no particular limitations on the curing accelerator, and imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, 1,8-diazabicyclo ( 5,4,0) undecene-7-tetraphenylborate and the like can be used. These can be used alone or in combination of two or more.

  0.01-20 mass parts is preferable with respect to 100 mass parts of epoxy resins, and, as for the addition amount of a hardening accelerator, 0.1-10 mass parts is more preferable. When the addition amount is less than 0.01 parts by mass, the curability tends to be inferior, and when it exceeds 20 parts by mass, the storage stability tends to decrease.

  The photosensitive adhesive composition according to this embodiment can further contain a filler. Examples of the filler include non-metallic inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, aluminum borate, and ceramics, and organic fillers such as rubber fillers.

  The filler can be used properly according to the desired function. For example, the nonmetallic inorganic filler is added for the purpose of imparting low thermal expansion and low hygroscopicity to the adhesive film, and the organic filler is added for the purpose of imparting toughness to the adhesive film. These nonmetallic inorganic fillers or organic fillers can be used alone or in combination of two or more. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

  When using a filler, the compounding quantity is preferably 100 parts by mass or less and more preferably 50 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. The lower limit is not particularly limited, but is generally 5 parts by mass. When the amount of the filler exceeds 100 parts by mass, the UV transmittance tends to deteriorate, and the adhesiveness tends to decrease.

  The photosensitive adhesive composition according to the present embodiment may contain a coupling agent as appropriate for the purpose of increasing the adhesive strength. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and the like, and among them, the silane coupling agent is preferable because it can provide high adhesive force.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, polyoxyethylenepropyltrialkoxysilane And polyethoxydimethylsiloxane. These can be used alone or in combination of two or more.

  When using a coupling agent, the usage-amount is preferable 0.1-50 mass parts with respect to 100 mass parts of alkali-soluble resin, and 0.1-20 mass parts is more preferable. When it exceeds 50 parts by mass, the storage stability of the photosensitive adhesive composition tends to be lowered.

  As described above, (A) an alkali-soluble resin (thermoplastic resin), (B) a thermosetting resin (epoxy resin), (C) a radiation polymerizable compound, and (D) a photopolymerization initiator, and further necessary Accordingly, the above-mentioned various characteristics can be achieved by blending fillers and the like and adjusting their kind and blending ratio.

Thereby, the photosensitive adhesive composition which has both the pattern formation function by an alkali developing solution, and the adhesion function as a die-bonding material is obtained. The pattern forming function is a method of laminating a photosensitive adhesive composition in the form of a film on an adherend such as a silicon wafer by pressing at a temperature of preferably 20 to 150 ° C. A mask is placed on the substrate, and exposure is performed using a high-precision parallel exposure machine under the condition of exposure amount: 100 to 1000 mJ / cm ² (after irradiation with ultraviolet rays), and then 1 to 5% by mass of tetramethylammonium hydride (TMAH). More preferably, it is a function of forming a pattern by spraying using a 2 to 4% by mass solution. The line width after pattern formation is preferably in the range of 0.01 mm to 20 mm.

In addition, about said pattern formation property, it evaluates as follows. A photosensitive adhesive composition in the form of a film is laminated on a silicon wafer by pressing with a roll, a mask is placed on the composition, and a high-precision parallel exposure machine (manufactured by Oak Manufacturing) is used to expose an exposure amount: After exposure under conditions of 100 to 1000 mJ / cm ² (after irradiating with ultraviolet rays), when spraying with a 2.38 mass% solution of tetramethylammonium hydride (TMAH), a pattern with a line width of about 1 mm is formed. Confirm that it is formed.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an adhesive film according to the present invention. An adhesive film 1 shown in FIG. 1 is obtained by forming the photosensitive adhesive composition into a film shape. FIG. 2 is a schematic cross-sectional view showing an embodiment of an adhesive sheet according to the present invention. The adhesive sheet 4 shown in FIG. 2 is comprised from the base material 3 and the adhesive bond layer which consists of the adhesive film 1 provided on this one surface.

  The adhesive film 1 (adhesive layer) is composed of, for example, a thermoplastic resin having an alkali-soluble group, a thermosetting resin (epoxy resin), a radiation polymerizable compound, a photopolymerization initiator, and other components as necessary. It can be obtained by mixing in a solvent, kneading the mixed solution to prepare a varnish, forming a layer of this varnish on the substrate 3, drying the varnish layer by heating, and then removing the substrate 3. . At this time, the base material 3 can be stored and used in the state of the adhesive sheet 4 without being removed.

  The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. In the case of using a thermosetting resin (epoxy resin), drying is performed at a temperature at which the thermosetting resin contained during the drying does not sufficiently react and under a condition that the solvent is sufficiently volatilized. Specifically, the varnish layer is dried by heating at 50 to 200 ° C. for 0.1 to 90 minutes.

  The temperature at which the thermosetting resin does not sufficiently react is specifically a DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.), and the sample amount: 10 mg , Temperature rising rate: 5 ° C./min, measurement atmosphere: air, the temperature is equal to or lower than the peak temperature of the reaction heat.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as the material can be uniformly dissolved or dispersed. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone.

  The thickness of the varnish layer is preferably 1 to 100 μm. If this thickness is less than 1 μm, the adhesive fixing function tends to be impaired, and if it exceeds 100 μm, the residual volatile matter described later tends to increase.

  The preferred residual volatile content of the obtained varnish layer is 10% by mass or less. When this residual volatile content exceeds 10% by mass, voids are likely to remain inside the adhesive layer due to foaming due to the volatilization of the solvent during heating for assembly, and the moisture resistance reliability tends to be impaired. . Moreover, there is a tendency that the possibility of contamination of surrounding materials or members due to volatile components generated during heating tends to increase. In addition, the measurement conditions of said residual volatile component are as follows. That is, for an adhesive film cut to a size of 50 mm × 50 mm, the initial mass is M1, and the mass after heating this adhesive film in an oven at 160 ° C. for 3 hours is M2, [(M2-M1) / M1] X100 = value when residual volatile content (%) is assumed.

  The substrate 3 is not particularly limited as long as it can withstand the above drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, or a methylpentene film can be used as the substrate 3. The film as the substrate 3 may be a multilayer film in which two or more kinds are combined, or the surface may be treated with a release agent such as a silicone or silica.

  FIG. 3 is a top view showing an embodiment of a substrate with an adhesive layer, and FIG. 4 is an end view taken along line IV-IV in FIG. A substrate 20 with an adhesive layer shown in FIGS. 3 and 4 includes a substrate 5 and an adhesive layer 1 made of the photosensitive adhesive composition provided on one surface of the substrate 5.

  The substrate (adherent) 5 is not particularly limited. For example, an organic substrate, a semiconductor wafer, a semiconductor element (semiconductor chip), a flexible substrate such as an interposer or a mother board, a rigid substrate, a lead frame, and an organic substance. Alternatively, an insulating substrate made of an inorganic material, an acrylic resin, the above-described base material, a transparent substrate such as glass, and the like can be given.

  The substrate 20 with an adhesive layer is obtained by laminating the adhesive film 1 on the substrate 5 while heating. Since the adhesive film 1 is a film made of the photosensitive adhesive composition, it can be attached to the substrate 5 at a low temperature of about room temperature (25 ° C.) to 150 ° C., for example.

  FIG. 5 is a top view showing an embodiment of the adhesive pattern according to the present invention, and FIG. 6 is an end view taken along the line VI-VI of FIG. The adhesive pattern 1a shown in FIGS. 5 and 6 is formed on the substrate 5 as the adherend so as to have a pattern along a substantially square side.

  The shape of the adhesive pattern 1a is not particularly limited, and examples thereof include a square or circular pattern provided with a through hole, a frame-like pattern, a rod-like shape, a square shape, and a round shape. Thereby, it can be used conveniently also as a spacer.

  In the adhesive pattern 1a, an adhesive layer 1 made of a photosensitive adhesive composition is formed on a substrate 5 as an adherend to obtain a substrate 20 with an adhesive layer, and the adhesive layer 1 is passed through a photomask. It is formed by exposing and developing the exposed adhesive layer 1 with an alkaline developer. Thereby, the board | substrate 20a with an adhesive layer in which the adhesive pattern 1a was formed is obtained.

  As an application of the adhesive film according to the present invention, a semiconductor device including the adhesive film will be specifically described with reference to the drawings. In recent years, semiconductor devices having various structures have been proposed, and the use of the adhesive film according to the present invention is not limited to the semiconductor device having the structure described below. For example, a semiconductor element or the like can be packaged. The semiconductor package, the camera module or camera sensor using a solid-state image sensor, the semiconductor device provided with the through hole, etc. are mentioned.

  FIG. 7 is a schematic cross-sectional view showing an embodiment of a semiconductor device according to the present invention. In the semiconductor device 200 shown in FIG. 7, the semiconductor element (semiconductor chip) 12 is bonded to the semiconductor element mounting support member 13 via the adhesive film 1 according to the present invention, and the connection terminals (not shown) of the semiconductor element 12 are It is electrically connected to an external connection terminal (not shown) via a wire 14 and sealed with a sealing material 15.

  In the semiconductor device (semiconductor package) shown in FIG. 7, for example, the semiconductor wafer 20b shown in FIG. 5 is diced along the broken line D, and the semiconductor element with a film adhesive after dicing is heated to the semiconductor element mounting support member 13. It can be obtained by crimping and bonding the two, followed by steps such as a wire bonding step and, if necessary, a sealing step with a sealing material. The heating temperature in the thermocompression bonding is usually 20 to 250 ° C., the load is usually 0.01 to 20 kgf, and the heating time is usually 0.1 to 300 seconds.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(Synthesis of polyimide PI-1)
2.28 g of 3,5-diaminobenzoic acid (hereinafter abbreviated as “DABA”), aliphatic ether diamine (“ED400” manufactured by BASF (trade name), (Molecular weight 433) 15.16 g and NMP were charged. Next, a solution in which 16 g of 4,4′-oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”) was dissolved in NMP was dropped into the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. After completion of dropping, the mixture was further stirred at room temperature for 5 hours. Next, a reflux condenser with a moisture receiver was attached to the flask, xylene was added, the temperature was raised to 180 ° C., and the temperature was maintained for 5 hours. The solution thus obtained was cooled to room temperature and then poured into distilled water for reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polyimide (hereinafter referred to as “polyimide PI-1”).

  When GPC was measured using N, N-dimethylformamide (DMF) as a mobile phase, the weight average molecular weight (polystyrene conversion) of polyimide PI-1 was 47,000.

  A varnish obtained by mixing polyimide PI-1 with a solvent was applied onto a PET film surface-treated with a release silicone and dried to prepare a polyimide film having a thickness of 40 μm. About the test piece cut out to the size of 35 mm x 10 mm from this film, using a viscoelasticity analyzer ("RSA-2" (trade name) manufactured by Rheometrics), the rate of temperature increase: 5 ° C / min, frequency: 1 Hz, measurement Temperature: The temperature at which tan δ exhibited a maximum value measured under the conditions of −150 ° C. to 300 ° C. was defined as Tg of polyimide PI-1. In the case where tan δ showed a maximum value at a plurality of temperatures, the temperature showing the maximum maximum value among them was defined as Tg. The Tg of polyimide PI-1 was 50 ° C.

(Synthesis of polyimide PI-2)
2.15 g of 5,5′-methylene-bis (anthranic acid) (hereinafter abbreviated as “MBAA”, molecular weight 286.28) and aliphatic ether in a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device Diamine (BASF “ED400” (trade name), molecular weight 433) 15.59 g and 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane (Shin-Etsu Chemical “LP” -7100 "(trade name), molecular weight 348.4) 2.26 g and NMP were charged. Subsequently, a solution in which 17 g of ODPA was dissolved in NMP was dropped into the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. All subsequent operations were performed in the same manner as the synthesis of polyimide PI-1, and polyimide (hereinafter referred to as “polyimide PI-2”) was obtained.

  When the weight average molecular weight and Tg of polyimide PI-2 were measured under the same conditions as for polyimide PI-1, the weight average molecular weight was 28000 and Tg was 30 ° C.

(Synthesis of polyimide PI-3)
7.6 g DABA and NMP were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device. Next, a solution obtained by dissolving 15.5 g of ODPA in NMP was dropped into the flask while adjusting the temperature of the reaction system so that it did not exceed 50 ° C. All subsequent operations were performed in the same manner as the synthesis of polyimide PI-1, and polyimide (hereinafter referred to as “polyimide PI-3”) was obtained.

  When the weight average molecular weight and Tg of polyimide PI-3 were measured under the same conditions as for polyimide PI-1, the weight average molecular weight was 72,000 and Tg was 200 ° C.

(Synthesis of polyimide PI-4)
6.83 g of 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as “BAPP”), 4,9-dioxadecane-1,12- in a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device. 3.40 g of diamine (hereinafter abbreviated as “B-12”) and NMP were charged. Subsequently, a solution obtained by dissolving 17.40 g of decamethylene bistrimellitate dianhydride (hereinafter abbreviated as “DBTA”) in NMP was dropped into the flask while adjusting the temperature of the reaction system so as not to exceed 50 ° C. All subsequent operations were performed in the same manner as the synthesis of polyimide PI-1, and polyimide (hereinafter referred to as “polyimide PI-4”) was obtained.

  When the weight average molecular weight and Tg of polyimide PI-4 were measured under the same conditions as for polyimide PI-1, the weight average molecular weight was 89000 and Tg was 73 ° C. In addition, polyimide PI-4 did not have a carboxyl group and was not alkali-soluble.

  Table 1 summarizes the preparation ratio (molar ratio) during polyimide synthesis and the evaluation results of the obtained polyimide. The numerical value of the charging ratio in Table 1 is a numerical value (mol%) based on the whole tetracarboxylic dianhydride and the whole diamine, respectively.

Example 1
Polyimide PI-1, ethoxylated bisphenol A dimethacrylate (“BPE-100” (trade name), manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radiation polymerizable compound, and urethane acrylate (“U-2PPA” (trade name), Shin Nakamura Chemical Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("I-819" (trade name), Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, thermosetting Bisphenol F type liquid epoxy resin (“YDF-8170” (trade name), manufactured by Tohto Kasei Co., Ltd.), cresol novolac type solid epoxy resin (“ESCN-195” (trade name), manufactured by Sumitomo Chemical Co., Ltd.) And α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-iso as a curing agent for the epoxy resin Propylbenzene (“TrisP-PA” (trade name), manufactured by Honshu Chemical Co., Ltd.) is uniformly mixed in NMP so as to have the composition (parts by mass) shown in Table 2, and a varnish for forming an adhesive film is obtained. Prepared. This varnish was applied onto a PET film surface-treated with a release silicone and dried in an oven under conditions of 80 ° C. for 30 minutes and 120 ° C. for 30 minutes to form an adhesive film having a thickness of 40 μm.

(Examples 2-5, Comparative Examples 1-8)
The raw materials and compositions shown in the following Tables 2 to 4 were used (the blending was by weight). About Examples 2-5 and Comparative Examples 1-8, it carried out similarly to Example 1, and produced the adhesive film.

In addition, the content of the raw material shown to the following Tables 2-4 means the following.
BPE-100: Shin-Nakamura Chemical, ethoxylated bisphenol A dimethacrylate U-2PPA: Shin-Nakamura Chemical, urethane acrylate I-819: Ciba Specialty Chemicals, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide YDF-8170: Tohto Kasei, bisphenol F type liquid epoxy resin (epoxy equivalent: 160, molecular weight: 320)
VG-3101L: Mitsui Chemicals, trifunctional solid epoxy resin (2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3 -Epoxypropoxy] phenyl)] ethyl] phenyl] propane) (epoxy equivalent: 210, molecular weight: 520)
ESCN-195: Sumitomo Chemical, cresol novolac type solid epoxy resin (epoxy equivalent: 200, molecular weight: 778)
BEO-60E: Shin Nippon Rika, bisphenol A bis (triethylene glycol glycidyl ether) ether (epoxy equivalent: 373, molecular weight: 746)
N-730: Dainippon Ink Chemical, phenol novolac type liquid epoxy resin (epoxy equivalent: 175, molecular weight: 600-800)
Epicoat 1001: Japan epoxy resin, bisphenol A type solid epoxy resin (epoxy equivalent: 450, molecular weight: 900)
TrisP-PA: Honshu Chemical, trisphenol compound (α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene) (OH equivalent: 141, molecular weight: 424)
H-1: Meiwa Kasei, phenol novolak resin (OH equivalent: 106, molecular weight: 653)
TPPK: Tokyo Kasei, tetraphenylphosphonium tetraphenylborate R972: Nippon Aerosil, hydrophobic fumed silica (average particle size: about 16 nm)

  About the produced adhesive film, pattern formation property, low temperature sticking property, and adhesive force (shearing adhesive force) were evaluated by the method shown below. The evaluation results are summarized in Tables 2 to 4 below. In addition, B1 and B2 in the table mean that they correspond to (B1) a trifunctional or higher functional component and (B2) liquid component, respectively.

(1) Pattern Formability The adhesive sheet was pressed on a silicon wafer (6 inch diameter, 400 μm thickness) at 80 ° C. with a roll with the adhesive layer facing the silicon wafer (linear pressure 4 kgf / cm, feed rate 0. 5 m / min). Next, a negative pattern mask (manufactured by Hitachi Chemical Co., Ltd., “No. G-2” (trade name)) is placed on the substrate (PET film), and a high-precision parallel exposure machine (manufactured by Oak Seisakusho, “EXM”). −1172-B-∞ ”(trade name)) at 500 mJ / cm ² and left on an 80 ° C. hot plate for about 30 seconds. Thereafter, the base material (PET film) is removed, and using a conveyor developing machine (manufactured by Yako Co., Ltd.), a 2.38 mass% solution of tetramethylammonium hydride (TMAH) is used as a developer, temperature is 28 ° C., spray pressure is 0.18 MPa. After spray development under the conditions, the film was washed with pure water at a temperature of 23 ° C. under a spray pressure of 0.02 MPa. After development, it is visually confirmed whether a pattern of line width / space width = 400 μm / 400 μm is formed, and when the pattern is formed without development residue, A, the pattern is formed, but the development residue is recognized The case was B, and the case where no pattern was formed was C.

(2) Low temperature sticking property An adhesive film is rolled (temperature 80 ° C., linear pressure 4 kgf / cm) on the back surface (surface opposite to the support table) of a silicon wafer (6 inch diameter, thickness 400 μm) placed on a support table. , And laminating by pressurizing at a feed rate of 0.5 m / min). The PET film was peeled off, and a polyimide film “Upilex” (trade name) having a thickness of 80 μm, a width of 10 mm, and a length of 40 mm was pressed and laminated on the adhesive film with a roll under the same conditions as described above. The sample prepared in this manner was subjected to a 90 ° peel test at room temperature (25 ° C.) using a rheometer “Strograph ES” (trade name), and the peel strength between the adhesive film and the upilex was measured. . A sample having a peel strength of 2 N / cm or more was designated as A, and a sample having a peel strength of less than 2 N / cm was designated as C.

(3) Shear adhesive force Using a device having a roll and a support on a silicon wafer (6 inch diameter, 400 μm thickness), conditions of 80 ° C., linear pressure: 4 kgf / cm, feed rate: 0.5 m / min The adhesive film was laminated with. Next, it exposed at 500 mJ / cm < ² > with the high precision parallel exposure machine (Oak Seisakusho make, "EXM-1172-B-infinity" (brand name)), and was left to stand for about 30 seconds on an 80 degreeC hotplate. The PET film was peeled off, and a pressure-sensitive dicing tape was laminated on the adhesive film. Thereafter, the silicon wafer was cut into a 3 mm × 3 mm size together with the adhesive film using a dicer to obtain a silicon chip on which the adhesive film was laminated. This silicon chip was placed on a glass substrate having a thickness of 10 mm × 10 mm × 0.55 mm so that the adhesive film was sandwiched between them, and thermocompression bonded on a 120 ° C. hot plate under the conditions of 2 kgf and 10 seconds. Then, it heated in 160 degreeC oven for 3 hours, and the adhesive film was heat-hardened. About the obtained sample, using a bond strength tester (manufactured by Dage, “Dage-4000” (trade name)) on a heating plate at 25 ° C. or 260 ° C., measurement speed: 50 μm / second, measurement height : The maximum stress when an external force in the shearing direction was applied to the silicon chip under the condition of 50 μm was defined as the shear adhesive strength at 25 ° C. or 260 ° C.

  As shown in Table 2, the adhesive films of the examples were excellent in all of pattern forming property, low temperature sticking property, re-adhesion property after exposure, and adhesive force at high temperature. On the other hand, as shown in Table 3 and Table 4, the adhesive film of the comparative example is not sufficient in any of pattern forming property, low temperature sticking property, re-adhesion property after exposure, and adhesive force at high temperature. It was.

It is sectional drawing which shows one Embodiment of the adhesive film which concerns on this invention. It is sectional drawing which shows one Embodiment of the adhesive sheet which concerns on this invention. It is a top view which shows one Embodiment of a board | substrate with an adhesive bond layer. FIG. 4 is an end view taken along line IV-IV in FIG. 3. It is a top view which shows one Embodiment of the adhesive agent pattern which concerns on this invention. FIG. 6 is an end view taken along line VI-VI in FIG. 5. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Adhesive film (adhesive layer), 1a ... Adhesive pattern, 3 ... Base material, 4 ... Adhesive sheet, 5 ... Board | substrate (adherence body), 12 ... Semiconductor element, 13 ... Support member for semiconductor element mounting, 14 DESCRIPTION OF SYMBOLS ... Wire, 15 ... Sealing material 20, 20a ... Substrate with adhesive layer, 200 ... Semiconductor device, D ... Broken line.

Claims (17)

(A) an alkali-soluble resin;
(B) an epoxy resin;
(C) a radiation polymerizable compound;
(D) a photopolymerization initiator, a photosensitive adhesive composition comprising:
Wherein (A) is an alkali-soluble resin Gapo Riimi de,
The glass transition temperature of the (A) alkali-soluble resin is 150 ° C. or lower,
The (B) epoxy resin contains (B1) a trifunctional or higher component, and (B2) a liquid component,
The (B1) trifunctional or higher functional component is a trisphenolmethane type epoxy resin represented by the following general formula (VI):
Wherein (B2) rather good also serve as a part or all of the (B1) 3 or more functional components of the liquid component,
The photosensitive adhesive composition whose said (C) radiation polymerizable compound is at least 1 type chosen from the group which consists of a compound represented by the following general formula (14), urethane acrylate, and urethane methacrylate .

(In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, and q and r each independently represent an integer of 1 or more.) The ratio of the (B1) trifunctional or higher functional component to the whole epoxy resin is 10 to 90% by mass,
The photosensitive adhesive composition of Claim 1 whose ratio with respect to the whole epoxy resin of the said (B2) liquid component is 10-90 mass%.   (E) The photosensitive adhesive composition of Claim 1 or 2 which further contains an epoxy resin hardening | curing agent. The photosensitive adhesive composition of Claim 3 whose said (E) epoxy resin hardening | curing agent is a compound which has a 2 or more phenolic hydroxyl group. The photosensitive adhesive composition of Claim 4 whose compound which has the said phenolic hydroxyl group is a trisphenol represented by the following general formula (VIII).

(A) the alkali-soluble resin is a thermoplastic resin having a carboxyl group and / or phenolic hydroxyl group, a photosensitive adhesive composition according to any one of claims 1-5. (A) the weight average molecular weight of the alkali-soluble resin is from 5,000 to 150,000, the photosensitive adhesive composition of any one of claims 1-6. (A) the alkali-soluble resin is a polyimide obtained by reacting a tetracarboxylic dianhydride and a diamine, the photosensitive adhesive composition of any one of claims 1-7. The photosensitive adhesive composition of Claim 8 in which the said diamine contains the aromatic diamine represented by the following general formula (I) or (II).

The diamine further contains an aliphatic ether diamine represented by the following general formula (III):
The photosensitive adhesive composition of Claim 8 or 9 whose ratio with respect to the whole diamine of the said aliphatic ether diamine is 10-90 mol%.

(In the formula, Q ₁ , Q ₂ and Q ₃ each independently represent an alkylene having 1 to 10 carbon atoms, and n ₁ represents an integer of ₁ to 80.) The diamine further contains a siloxane diamine represented by the following general formula (IV):
The ratio of total diamine siloxane diamine is 1 to 20 mol%, the photosensitive adhesive composition of any one of claims 8-10.

(Wherein R ₁ and R ₂ each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ₃ , R ₄ , R ₅ and R ₆ are each independently alkyl group having 1 to 5 carbon atoms, phenyl or a phenoxy group, _{n 2} is an integer of 1-5.) The tetracarboxylic acid dianhydride, a compound represented by the following general formula (V) including with respect to the total tetracarboxylic dianhydride 40 mole% or more, sensitization of any of claims 8-11 Adhesive composition.

Wherein (B2) the liquid component is bisphenol A bis (triethylene glycol glycidyl ether) ether represented by the following general formula (VII), a photosensitive adhesive composition of any one of claims 1 to 12.

  The adhesive film which consists of a photosensitive adhesive composition as described in any one of Claims 1-13.   An adhesive sheet comprising a base material and an adhesive layer made of the photosensitive adhesive composition according to any one of claims 1 to 13 provided on one surface of the base material.   An adhesive layer made of the photosensitive adhesive composition according to claim 1 is formed on an adherend, the adhesive layer is exposed through a photomask, and the exposed adhesive An adhesive pattern formed by developing a layer with an aqueous alkaline solution.   The semiconductor device using the photosensitive adhesive composition as described in any one of Claims 1-13.

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