JP2015034986A - Film-like positive type photosensitive adhesive composition, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-like positive type photosensitive adhesive composition that can exhibit adequate flowability in the connection of semiconductor chips with each other or the connection of a semiconductor chip with a supporting member for mounting a semiconductor chip and is excellent in pattern formability, reflow resistance and connectivity.SOLUTION: The film-like positive type photosensitive adhesive composition comprises (A) an alkali-soluble resin and (B) a compound generating an acid by light and is used as an underfill material in a semiconductor device in which a connection part in each of connection of semiconductor chips with each other or connection of a semiconductor chip with a support member for mounting a semiconductor chip is electrically connected. The alkali-soluble resin (A) includes a polyimide resin having a phenolic hydroxyl group or a polyamide resin having a phenolic hydroxyl group.

Description

  The present invention relates to a film-like positive photosensitive adhesive composition, an adhesive sheet, an adhesive pattern, a semiconductor wafer with an adhesive layer, 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 manufacturing the semiconductor package, an adhesive is used to bond the semiconductor chip and the semiconductor chip mounting support member.

In recent years, in the field of semiconductor mounting, a flip chip mounting method in which semiconductor chips are connected to each other or a semiconductor chip and a support member for mounting a semiconductor chip are connected via a plurality of conductive bumps has attracted attention. In the flip chip mounting method, abnormal connection between the substrate and the semiconductor chip via the conductive bumps may occur due to stress based on the difference in thermal expansion coefficient between the respective connection members. For this reason, a method of sealing conductive bumps by filling a resin (underfill material) between connecting members for the purpose of alleviating the stress is known (for example, Patent Document 1).
Furthermore, it has been studied to use a negative photosensitive adhesive composition as a connection material between semiconductor chips or a connection material between a semiconductor chip and a semiconductor chip mounting support member (for example, Patent Document 2).

Japanese Patent No. 3999840 International Publication No. 2011/049011

  However, in the case of Patent Document 1, the connection is made by heating and / or pressurization, but the resin at the connection portion cannot be sufficiently removed, and there are cases where the connection is difficult to take. In the case of Patent Document 2, since the photocrosslinking reaction is used in the exposure process, the fluidity may be insufficient in the connection between the semiconductor chip and the semiconductor chip mounting support member.

  The present invention has been made in view of the above circumstances, and can exhibit appropriate fluidity in connection between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member. An object of the present invention is to provide a film-like positive photosensitive adhesive composition having excellent properties and connectivity. It is another object of the present invention to provide an adhesive sheet, a semiconductor wafer with an adhesive layer, an adhesive pattern, and a semiconductor device using the film-like positive photosensitive adhesive composition.

  In order to solve the above problems, the present invention includes (A) an alkali-soluble resin, and (B) a compound that generates an acid by light, and includes semiconductor chips or semiconductor chips and a semiconductor chip mounting support member. Provided is a film-like positive photosensitive adhesive composition used as an underfill material for bonding. Here, the (A) alkali-soluble resin includes a polyimide resin having a phenolic hydroxyl group or a polyamide resin having a phenolic hydroxyl group.

By having the said structure, the film-form positive photosensitive adhesive composition which concerns on this invention expresses appropriate fluidity | liquidity in the connection between semiconductor chips or a semiconductor chip and the support member for semiconductor chip mounting. Good step embedding property can be expressed. That is, it leads to the reduction of voids at the interface, and further contributes to improving the reliability of the semiconductor device of the present invention. The inventors of the present invention are widely used for negative photosensitive materials in patterning processes such as exposure and development because the film-like positive photosensitive adhesive composition according to the present invention is excellent in fluidity. This is thought to be due to not using a high molecular weight reaction such as a photocrosslinking reaction.
In the present invention, the “underfill material” means a material that protects the connection parts by covering the connection parts between the semiconductor chips or between the semiconductor chip and the semiconductor chip mounting support member.

  In addition, the film-like positive photosensitive adhesive composition according to the present invention can obtain good electrical connectivity when connecting semiconductor chips or between semiconductor chips and a semiconductor chip mounting support member. it can. Furthermore, the film-form positive photosensitive adhesive composition according to the present invention is excellent in reflow resistance and patternability.

  Further, from the viewpoint of pattern forming properties, particularly sensitivity and resolution, it is preferable that the compound (B) that generates an acid by light is a quinonediazide compound.

  Moreover, it is preferable that the said alkali-soluble resin has a phenolic hydroxyl group in a terminal group from a viewpoint of high temperature adhesiveness and pattern formation.

  In addition, the film-like positive photosensitive adhesive composition containing the component (A) and the component (B) is either (C) itself or by heat from the viewpoint of thermocompression bonding, high-temperature adhesion, and moisture resistance reliability. It is preferable to further contain a compound that crosslinks with the resin.

  The compound (C) that crosslinks itself or the resin by heat is preferably a compound having an epoxy group from the viewpoints of high-temperature adhesiveness, pattern formation, and moisture resistance reliability.

  The present invention also provides an adhesive sheet comprising a base material and an adhesive layer formed on the base material, wherein the adhesive layer is made of the film-form positive photosensitive adhesive composition. By setting it as such a structure, it becomes easy to wind up and store in roll shape. By applying pressure from the base material side at the time of pasting, it becomes possible to use the film-like positive photosensitive adhesive composition without contamination. Furthermore, the in-plane film thickness including the edge of the substrate can be made uniform.

  Moreover, this invention exposes the adhesive bond layer which consists of the said film-form positive photosensitive adhesive composition laminated | stacked on the to-be-adhered body, and develops the exposed adhesive bond layer by an alkali developing solution. The resulting adhesive pattern is provided. As a result, a desired adhesive pattern can be formed, and the terminal portions can be arbitrarily exposed without contaminating the terminal portions existing in the semiconductor chip or the like.

  The present invention also provides a semiconductor wafer with an adhesive layer comprising a semiconductor wafer and an adhesive layer laminated on the semiconductor wafer, wherein the adhesive layer is made of the film-like positive photosensitive adhesive composition. provide.

  Further, the present invention provides a structure in which semiconductor chips are bonded to each other and / or a structure in which a semiconductor chip and a support member for mounting a semiconductor chip are bonded using the film-like positive photosensitive adhesive composition. A semiconductor device is provided.

  According to the present invention, appropriate fluidity can be expressed in the connection between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member. Therefore, a film-like positive photosensitive adhesive composition is used as a semiconductor wafer or the like. It is possible to provide a film-form positive photosensitive adhesive composition that is excellent in embedding property of the substrate with connection terminals, can improve the connectivity, and is excellent in reflow resistance and patternability. Moreover, the adhesive sheet using this film-form positive photosensitive adhesive composition, the semiconductor wafer with an adhesive layer, an adhesive pattern, and a semiconductor device can be provided. Furthermore, the circuit surface on which the film-like positive photosensitive adhesive composition of the present invention is formed can be exposed arbitrarily by the patterning regardless of the size of the connection terminal part or the height of the terminal. it can.

It is an end view which shows one Embodiment of the film adhesive of this invention. It is an end view which shows one Embodiment of the adhesive sheet of this invention. It is an end view which shows one Embodiment of the adhesive sheet of this invention. It is a top view which shows one Embodiment of the semiconductor wafer with an adhesive layer of this invention. FIG. 5 is an end view taken along line IV-IV in FIG. 4. It is an end elevation showing one embodiment of a semiconductor device of the present invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device of this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device of this invention. It is sectional drawing which shows one Embodiment of the manufacturing method of the semiconductor device of this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device of this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device of this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified, and the dimensional ratio in the drawing is not limited to the illustrated ratio.

  In this specification, “sticking property” refers to a film-like positive photosensitive adhesive composition (also referred to as a film-like adhesive) obtained by molding a positive-type photosensitive adhesive composition into a film. It means stickiness in case. The “high temperature adhesiveness” of the film-like positive photosensitive adhesive composition means the adhesiveness under heating when the film-like positive photosensitive adhesive composition is made into a cured product. “Pattern formability” of a film-form positive photosensitive adhesive composition means that an adhesive layer composed of the film-form adhesive formed on an adherend is exposed through a photomask and is exposed to an alkali developer. It means the accuracy of the adhesive pattern obtained when developed. “Thermocompression bonding” of the film-like positive photosensitive adhesive composition means the degree of adhesion when the adhesive pattern is pressure-bonded (thermocompression bonding) to a support member or the like under heating. “Heat resistance” of the film-like positive photosensitive adhesive composition means peeling resistance when the adhesive pattern is thermocompression-bonded and cured on a support member or the like and placed at a high temperature. “Reflow resistance” means that the film-like positive photosensitive adhesive composition is thermocompression-bonded and cured on a support member or the like, and is left to stand for a predetermined time under high-temperature and high-humidity conditions, followed by reflow heating. It means peeling resistance.

  In this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.

  In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended purpose of the process is achieved. included.

  The film-form positive photosensitive adhesive composition of this embodiment is used for connection between semiconductor chips or between a semiconductor chip and a support member for mounting a semiconductor chip, and the resin composition for the film-form adhesive is used as a film. A semiconductor wafer having a circuit surface, which is formed on the circuit surface, and after patterning by exposure and development, a semiconductor chip mounting support member, semiconductor chip or semiconductor wafer having a circuit surface It has the thermocompression bonding property to the adherend made of.

(Photosensitive resin composition)
The film-form positive photosensitive adhesive composition of this embodiment contains (A) an alkali-soluble resin and (B) a compound that generates an acid by light.

<(A) component>
The component (A) includes a polyimide resin having a phenolic hydroxyl group or a polyamide resin having a phenolic hydroxyl group. The component (A) is not particularly limited as long as it is a resin that is soluble in an alkaline aqueous solution, but has a polyimide resin having a phenolic hydroxyl group or a phenolic hydroxyl group based on the total mass of the component (A). The polyamide resin is preferably contained at least 10% by mass, and more preferably at least 20% by mass. The polyimide resin having a phenolic hydroxyl group or the polyamide resin having a phenolic hydroxyl group may be a precursor such as a corresponding polyamic acid. The alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. In general, an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight is used for development.

In addition, one criterion that the component (A) of the present invention is soluble in an alkaline developer will be described below.
A coating film having a thickness of about 5 μm formed by spin-coating a varnish obtained by dissolving the component (A) alone or together with the component (B) described below in an arbitrary solvent on a substrate such as a silicon wafer. And This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution and organic amine aqueous solution at 20 to 25 ° C. As a result, when it can be dissolved as a uniform solution, the component (A) is regarded as soluble in an alkaline developer.

  The Tg of the component (A) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and extremely preferably 100 ° C. or lower. When the Tg is 150 ° C. or less, the temperature at which the film-like adhesive obtained by forming the positive photosensitive adhesive composition into a film can be reduced, and the semiconductor wafer is hardly warped. Tend to be. Further, the melt viscosity of the adhesive after pattern formation does not become too high, and the thermocompression bondability tends to be improved.

  Moreover, it is preferable that the bonding temperature to the wafer back surface of a film adhesive is 20 to 150 degreeC, and it is more preferable that it is 40 to 100 degreeC. Within the above range, warping of the semiconductor wafer tends to be suppressed. In order to enable attachment at the above temperature, the Tg of the film adhesive is preferably set to 150 ° C. or lower. The lower limit of the Tg is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and extremely preferably 70 ° C. or higher. When the Tg is 40 ° C. or higher, it is not necessary to add a large amount of other curing components in order to improve the elastic modulus after exposure and heat-curing, and handleability, storage stability, pattern formability. , There is a tendency to ensure thermocompression bonding, heat resistance and low stress properties.

  From the viewpoint of further improving the connection reliability such as reflow resistance, the Tg of the alkali-soluble resin (A) is preferably 40 ° C to 150 ° C, more preferably 50 ° C to 120 ° C, and 60 ° C to 100 ° C. ° C is particularly preferred. (A) By setting the Tg of the alkali-soluble resin within the above range, sufficient thermocompression bonding property when the film-like positive photosensitive adhesive composition is bonded to the adherend can be secured, and the connection reliability is further improved. Can be made.

  Here, “Tg” of the component (A) means that the component (A) is made into a film, using a viscoelasticity analyzer (manufactured by Rheometrics, trade name: RSA-2), with a temperature rising rate of 5 ° C. / Min, frequency 1 Hz, measurement temperature −150 ° C. to 300 ° C. The tan δ peak temperature when measured.

  The weight average molecular weight of the component (A) is preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000, and most preferably from 10,000 to 100,000. . When the weight average molecular weight is within the above range, the strength, flexibility, and tackiness of the film-like positive photosensitive adhesive composition in the form of a sheet or film are improved. In addition, since the fluidity during heating is good, it is possible to ensure good embedding properties with respect to the wiring step (unevenness) on the substrate surface. On the other hand, when the weight average molecular weight is less than 5,000, the film formability tends to be insufficient. On the other hand, when the weight average molecular weight exceeds 500,000, the fluidity during heating and the embedding tend to be insufficient, and the alkaline developer of the film-form positive photosensitive adhesive composition when forming a pattern. There is a tendency that the solubility in is not sufficient. Here, the “weight average molecular weight” means the weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (manufactured by Shimadzu Corporation, trade name: C-R4A).

  By setting the Tg and the weight average molecular weight of the component (A) within the above ranges, the temperature for attaching to the wafer can be kept low. Further, the heating temperature (thermocompression bonding temperature) when the semiconductor chip is bonded and fixed to the semiconductor chip mounting support member can be lowered, and high temperature adhesiveness can be imparted while suppressing an increase in warpage of the semiconductor chip. it can. Further, it is possible to effectively impart sticking property, thermocompression bonding property and developability.

  The component (A) is, for example, a polyester resin, a polyether resin, a polyurethane resin, a copolymer or a precursor thereof, a polybenzoxazole resin, a phenoxy resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene A sulfide resin, a polycarbonate resin, a polyether ketone resin, a (meth) acrylic copolymer having a weight average molecular weight of 10,000 to 1,000,000, a novolac resin, or a phenol resin may be included. These can be used alone or in combination of two or more. In addition, the main chain and / or side chain of these resins may be provided with glycol groups such as ethylene glycol and propylene glycol, carboxyl groups and / or hydroxyl groups. In addition, from the viewpoint of heat resistance and film formability, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, and precursors thereof may be used. Moreover, it is preferable that the acrylic copolymer substituted by the phenol group is included from a viewpoint of pattern formation property and adhesiveness.

  From the viewpoint of high-temperature adhesiveness, heat resistance, and film formability, the component (A) is preferably a polyimide resin or a polyamide resin and a precursor thereof.

  Furthermore, among these, it is preferable that the said alkali-soluble resin has a phenolic hydroxyl group in a terminal group from a viewpoint of high temperature adhesiveness and pattern formation.

  The polyimide resin that can be suitably used in the present invention can be obtained, for example, by subjecting a tetracarboxylic dianhydride, a diamine, and a phenolic hydroxyl group-containing (monofunctional) amine to a condensation reaction by a known method.

  The mixing molar ratio of tetracarboxylic dianhydride and diamine in the condensation reaction is such that the total of diamine is 0.5 mol to 0.98 mol with respect to a total of 1.0 mol of tetracarboxylic dianhydride. Preferably, it is 0.6 mol to 0.95 mol.

The mixing molar ratio of the tetracarboxylic dianhydride and the phenolic hydroxyl group-containing amine in the condensation reaction is such that the total of the phenolic hydroxyl group-containing amine is 0.04 mol with respect to a total of 1.0 mol of the tetracarboxylic acid dianhydride. It is preferable that it is -1.0 mol, and it is more preferable that it is 0.1-0.8 mol.
The order of adding the tetracarboxylic acid anhydride, diamine, and phenolic hydroxyl group-containing amine may be arbitrary.

  In the condensation reaction, tetracarboxylic dianhydride is preferably used in excess of diamine. Thereby, the oligomer which has a residue derived from tetracarboxylic dianhydride at the end increases, and the residue derived from this tetracarboxylic dianhydride reacts with the amino group of the phenolic hydroxyl group-containing amine described later, A phenolic hydroxyl group is introduced as a terminal group.

  Moreover, the reaction temperature in the said condensation reaction has preferable 80 degrees C or less, and 0 to 60 degreeC is more preferable. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide resin precursor, is generated. In addition, in order to suppress the fall of the various characteristics of a resin composition, it is preferable that the above-mentioned tetracarboxylic dianhydride is what recrystallized and refined with acetic anhydride.

  The polyimide resin in the present embodiment means a resin having an imide group. Specific examples include polyimide resins, polyamideimide resins, polyurethaneimide resins, polyetherimide resins, polyurethaneamideimide resins, siloxane polyimide resins, and polyesterimide resins, but are not particularly limited thereto.

  The polyimide resin can be obtained by dehydrating and ring-closing the condensation reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed, a chemical ring closure method using a dehydrating agent, or the like.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, 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 Anhydride, 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-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic 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-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, 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 acid 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-tetracarboxylic 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 acid) Anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuran) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, and tetra represented by the following general formula (1) Carboxylic dianhydrides are mentioned. In the following general formula (1), a represents an integer of 2 to 20.

  The tetracarboxylic dianhydride represented by the general formula (1) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis. (Trimellitic 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 (trimellitic anhydride), 1,12- (dodecamechi) Emissions) bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), and 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

  Further, the tetracarboxylic dianhydride is represented by the following formula (2) or (3) from the viewpoint of providing good solubility in solvents and moisture resistance, and transparency to light having a wavelength of 365 nm. The tetracarboxylic dianhydride used is preferred.

  The above tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  As the diamine used as the raw material for the polyimide resin, it is preferable to use at least one diamine having no phenol group and having a phenolic hydroxyl group. By using a diamine having no phenol group and having a phenolic hydroxyl group, a phenolic hydroxyl group can be introduced as a side chain group of the polyimide resin. Examples of the diamine having no phenol group and having a phenolic hydroxyl group include aromatic diamines represented by the following formulas (5), (7) and (A-1), and a polyimide resin having a high Tg. Sometimes, from the viewpoint of obtaining good pattern forming properties and thermocompression bonding, a diamine represented by the following general formula (A-1) is more preferable.

In the formula, R ²¹ represents a single bond or a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group having 1 to 30 carbon atoms, or a divalent hydrocarbon having 1 to 30 carbon atoms in which part or all of hydrogen has been substituted with a halogen atom. Group, — (C═O) —, —SO ₂ —, —O—, —S—, —NH— (C═O) —, — (C═O) —O—, the following general formula (B-1) And a group represented by the following general formula (B-2). In the formula, n represents an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.

R ²¹ is preferably —C (CF ₃ ) ₂ — or —C (CH ₃ ) ₂ — from the viewpoint of pattern formation when the Tg of the polyimide resin is increased. By using the diamine having such a group, aggregation of polyimide imide groups can be suppressed at the time of pattern formation, and the pattern formability can be improved by allowing the alkali developer to easily permeate. Thereby, even if the Tg of polyimide is raised, it becomes possible to obtain a good pattern forming property, and it is possible to realize a film-like positive photosensitive adhesive composition with further improved moisture resistance reliability.

  The diamine represented by the general formula (A-1) is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, more preferably 30 to 70 mol% of the total diamine. More preferably, it is made into%. When a carboxyl group-containing resin is used as the polyimide resin, the acid value of the thermoplastic resin tends to be greatly reduced by reacting with the epoxy resin compounded during heating and drying. In contrast, when the side chain of the polyimide resin is a phenolic hydroxyl group, the reaction with the epoxy resin is less likely to proceed than in the case of a carboxyl group. As a result, in addition to pattern formability, thermocompression bonding, and high temperature adhesiveness, it is considered that the stability of the composition in the form of a varnish or film is improved.

  In the present embodiment, the diamine having a phenolic hydroxyl group preferably includes a diphenol diamine having a fluoroalkyl group represented by the following formula. By introducing the fluoroalkyl group into the polyimide chain, the molecular chain cohesive force between the polyimides decreases, and the developer easily penetrates. As a result, the pattern formability (dissolvability and thinning) of the film-like positive photosensitive adhesive composition is further improved. Moreover, thermocompression-bonding property can be improved by reducing the cohesive force of polyimide, and even if the Tg of polyimide is increased, good pattern forming property can be obtained. As a result, it is possible to realize a film-like positive photosensitive adhesive composition having further improved moisture resistance reliability and reflow resistance.

  The diphenoldiamine having a fluoroalkyl group is preferably 5 to 100 mol%, more preferably 10 to 90 mol%, more preferably 10 to 80 mol% of the total diamine. Is more preferable, 20 mol% to 80 mol% is particularly preferable, and 30 mol% to 70 mol% is extremely preferable.

There is no restriction | limiting in particular as other diamine used as a raw material of the said polyimide resin, 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′-diaminodiphenylmethane, 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′-diaminodiphenyl Sulfon, 3, 4'- Aminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 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-amino) Phenyl) 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-phenylene) Bis (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-aminophenoxy) phenyl ) Sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfur Aromatic diamines such as phenone, bis (4- (4-aminophenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and 3,5-diaminobenzoic acid, 1,3-bis (Aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (8), and siloxane diamine represented by the following general formula (9) Can be mentioned. In the following general formula (8), R ¹ , R ² and R ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 2 to 80. In the following general formula (9), R ⁴ and R ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently A C1-C5 alkyl group, a phenyl group, or a phenoxy group is shown, d shows the integer of 1-5. The phenylene group may have a substituent.

  Among the diamines, the aliphatic ether diamines represented by the general formula (8) are preferable in view of imparting compatibility with other components, organic solvent solubility, and alkali solubility, and ethylene glycol and / or propylene glycol type. Diamine is more preferred.

  Specific examples of such aliphatic ether diamines include Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, EDR- manufactured by Sun Techno Chemical Co., Ltd. 148, aliphatic diamines such as polyoxyalkylene diamines such as polyether amines D-230, D-400, and D-2000 manufactured by BASF. These diamines are preferably from 1 mol% to 80 mol%, more preferably from 10 mol% to 80 mol%, still more preferably from 10 mol% to 60 mol% of the total diamine. If this amount is 1 mol% or more, the high-temperature adhesiveness and fluidity during heating tend to be easily imparted. On the other hand, if it is 80 mol% or less, the Tg of the polyimide resin does not become too low, Self-supporting tendency tends to be maintained.

  Furthermore, the aliphatic ether diamine preferably has a propylene ether skeleton represented by the following structural formula and has a molecular weight of 300 to 600 from the viewpoint of pattern formation. When such a diamine is used, the amount is preferably 80 mol% or less, and 60 mol% or less of the total diamine, from the viewpoints of film self-supporting property, high-temperature adhesiveness, reflow resistance, and moisture resistance reliability. It is more preferable that Moreover, it is preferable that it is 10 mol% or more of all the diamine from a viewpoint of sticking property, thermocompression bonding property, and high temperature adhesiveness, and it is more preferable that it is 20 mol% or more. When this amount is in the above range, the Tg of the polyimide can be adjusted to the above range, and it is possible to impart sticking property, thermocompression bonding property, high temperature adhesion property, reflow resistance, and hermetic sealing property. Become. In the following structural formula, m represents an integer of 3 to 7.

  Moreover, the siloxane diamine represented by the said General formula (9) is preferable from a viewpoint of improving the adhesiveness at room temperature, and adhesiveness.

  Specifically, as the siloxane diamine represented by the general formula (9), it is assumed that d in the formula (9) 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, and 1,3-dimethyl-1, -Dimethoxy-1,3-bis (4-aminobutyl) disiloxane, and the like, where d 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, , 1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5 -Bis (4-aminobutyl) to Siloxane, 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, and 1,1,3,3,5, Examples include 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane. The siloxane diamine represented by the general formula (9) is available, for example, as BY16-871EG (trade name, manufactured by Toray Dow Corning Co., Ltd.).

  The said diamine can be used individually by 1 type or in combination of 2 or more types. The amount of the diamine is preferably 1 mol% to 80 mol%, more preferably 2 mol% to 50 mol%, and more preferably 5 mol% to 30 mol% of the total diamine. Further preferred. When it is 1 mol% or more, it becomes easy to obtain the effect of adding siloxane diamine, and when it is 80 mol% or less, compatibility with other components, high-temperature adhesiveness, and developability tend to be improved.

  Moreover, when determining the composition of the polyimide resin, it is preferable to design the Tg to be 150 ° C. or lower as described above. As the diamine that is a raw material of the polyimide resin, the general formula (8) It is particularly preferred to use the aliphatic ether diamine represented.

  When a phenolic hydroxyl group-containing amine is used during the synthesis of the polyimide resin, a phenolic hydroxyl group can be introduced as a terminal group by a reaction between the residue derived from tetracarboxylic acid and the amino group of the phenolic hydroxyl group-containing amine. it can. Thereby, the weight average molecular weight of the polymer can be lowered, and the developability at the time of pattern formation and the thermocompression bonding property can be improved.

  As the phenolic hydroxyl group-containing amine, aminophenol derivatives are preferred. Examples of aminophenol derivatives include o-aminophenol, m-aminophenol, p-aminophenol, aminocresols such as 2-amino-m-cresol, and aminomethoxybenzenes such as 2-amino-4-methoxybenzene, 4 Examples include -hydroxydimethylanilines such as -hydroxy-2,5-dimethylaniline, and the like, and a compound represented by the following formula (13) is preferable. Among them, those having a hydroxyl group at the meta position of the amino group are preferred from the viewpoint of solubility in an alkaline developer and stability in varnish, and among these, m-aminophenol is easy to introduce during polyimide synthesis. More preferable.

  The polyimide resin having a phenolic hydroxyl group as a terminal group has stability and connection when the film-like positive photosensitive adhesive composition is in the form of a varnish or a film in addition to pattern formation, thermocompression bonding and high-temperature adhesiveness. This is preferable because embedding (flatness) by applying or laminating to a substrate having protrusions or steps like a terminal is improved.

  The polyimide resin mentioned above can be used individually by 1 type or in mixture of 2 or more types as needed.

  From the viewpoint of photocurability, the polyimide resin preferably has a transmittance of 10% or more, more preferably 20% or more, for light having a wavelength of 365 nm when formed into a 30 μm film. Such a polyimide resin is represented by, for example, an acid dianhydride represented by the above formula (2), an aliphatic ether diamine represented by the above general formula (8) and / or the above general formula (9). It can be synthesized by reacting with siloxane diamine.

  Examples of the polyamide resin that can be preferably used as the component (A) include those having a structural unit represented by the following general formula (I).

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

  The amide unit containing a hydroxyl group represented by the general formula (I) is finally excellent in heat resistance, mechanical properties, and electrical properties due to dehydration and ring closure at the time of curing. The oxazole represented by the following general formula (X) It is preferably converted into a body.

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

The alkaline aqueous solution-soluble polyamide that can be used in the present invention may have the structural unit represented by the above general formula (I), but the solubility of the polyamide in the alkaline aqueous solution is mainly derived from the phenolic hydroxyl group. The amide unit containing a hydroxyl group represented by the general formula (I) is preferably contained in a certain proportion or more.
As such a thing, alkaline aqueous solution soluble polyamide represented by following formula (4) is mentioned.

（式（４）中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である。）

(In Formula (4), U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent a mole fraction, and the sum of j and k is 100 mol%. And j is 60 to 100 mol%, and k is 40 to 0 mol%.)

  As for the molar fraction of j and k in Formula (4), it is more preferable that j is 80-100 mol% and k is 20-0 mol%.

(Tetravalent organic group represented by U)
The tetravalent organic group represented by U is generally a residue of dihydroxydiamine that reacts with a dicarboxylic acid to form a polyamide structure, and is preferably a tetravalent aromatic group having 6 to 6 carbon atoms. 40 is preferable, and a tetravalent aromatic group having 6 to 40 carbon atoms is more preferable. Here, the aromatic group is a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent hydrocarbon group having 1 to 30 carbon atoms in which part or all of hydrogen is substituted by a halogen atom,-(C ═O) —, —SO ₂ —, —O—, —S—, —NH— (C═O) —, — (C═O) —O—, etc. There may be. The tetravalent aromatic group is a dihydroxydiamine having a structure in which all four bonding sites are present on the aromatic ring and the two hydroxyl groups are respectively located at the ortho positions of the amine bonded to U. The residue of a phenolic hydroxyl group-containing diamine is particularly preferred.

  The phenolic hydroxyl group-containing diamine is preferably one represented by the following general formula (A-1).

In the general formula (A-1), R ²¹ represents a single bond or a divalent organic group. Here, as the divalent organic group, for example, a divalent hydrocarbon group having 1 to 30 carbon atoms, or a divalent hydrocarbon having 1 to 30 carbon atoms in which a part or all of hydrogen is substituted by a halogen atom. Group, — (C═O) —, —SO ₂ —, —O—, —S—, —NH— (C═O) —, — (C═O) —O—, the following general formula (B-1) And a group represented by the following general formula (B-2). In general formulas (B-1) and (B-2), n represents an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.

R ²¹ is preferably —C (CF ₃ ) ₂ — or —C (CH ₃ ) ₂ — from the viewpoint of pattern formation. By using a phenolic hydroxyl group-containing diamine having such a group, aggregation of alkali aqueous solution-soluble polyamides can be suppressed during pattern formation, and pattern forming properties can be improved by allowing the alkali developer to easily permeate. As a result, it is possible to realize a film-like positive photosensitive adhesive composition with further improved moisture resistance reliability.

  The phenolic hydroxyl group-containing diamine represented by the general formula (A-1) is preferably 10 mol% to 80 mol% of the total diamine, more preferably 20 mol% to 80 mol%, and more preferably 30 mol%. It is more preferable to set it as% -70 mol%.

  In this embodiment, it is preferable that the phenolic hydroxyl group-containing diamine includes a fluoroalkyl group represented by the following formula (C-1). By introducing the fluoroalkyl group into the polyamide chain, the molecular chain cohesive force between the polyamides decreases, and the developer easily penetrates. As a result, the pattern formability (dissolvability and thinning) of the film-like positive photosensitive adhesive composition is further improved. Moreover, the thermocompression bonding property can be improved by reducing the cohesive strength of the polyamide, and even if the Tg of the polyamide is increased, it is possible to obtain a good pattern forming property. As a result, it is possible to realize a film-like positive photosensitive adhesive composition having further improved moisture resistance reliability and reflow resistance.

  The phenolic hydroxyl group-containing diamine having a fluoroalkyl group is preferably 5 mol% to 100 mol% of the total phenolic hydroxyl group-containing diamine, more preferably 10 mol% to 90 mol%, more preferably 10 mol% to It is more preferable to set it as 80 mol%, it is especially preferable to set it as 20 mol%-80 mol%, and it is very preferable to set it as 30 mol%-70 mol%.

(Divalent organic group represented by W)
The divalent organic group represented by W is generally a residue of a diamine that reacts with a dicarboxylic acid to form a polyamide structure, and represents a residue other than the dihydroxydiamine represented by U described above. A divalent aromatic group or an aliphatic group is preferable, and the number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms. Here, an aromatic group is synonymous with the aromatic group described by the tetravalent organic group represented by said U.

Such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p- Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- And aromatic diamine compounds such as (4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name).
These compounds can be used alone or in combination of two or more.

(Divalent organic group represented by V)
The divalent organic group represented by V is a dicarboxylic acid residue that forms a polyamide structure by reacting with the above-described dihydroxydiamine or diamine, and is preferably a divalent aromatic group. The thing of 6-40 is preferable and a C6-C40 bivalent aromatic group is more preferable from a heat resistant viewpoint of a cured film. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred. Here, an aromatic group is synonymous with the aromatic group described by the tetravalent organic group represented by said U.

  Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether (4,4′-diphenyl ether dicarboxylic acid), 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) ) Aromatic dicarboxylic acids such as propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid Etc. can be mentioned.

  In addition, when V is a divalent organic group having an alkylene chain having 2 to 30 carbon atoms, it is preferable in that sufficient physical properties can be obtained even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower.

  Examples of such dicarboxylic acids include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, and 2,2-dimethylsuccinic acid. Acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethyl Glutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1 9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, Tricosane diacid, tetracosane diacid, pentacosane diacid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontane diacid, hentriacontan diacid, dotriacontane diacid, diglycolic acid, below The dicarboxylic acid etc. which are represented by General formula (6) are mentioned. However, dicarboxylic acid is not limited to these. These compounds can be used alone or in combination of two or more.

（式（６）中、Ｚは炭素数１〜６の炭化水素基、式中ｎは１〜６の整数である。）

(In Formula (6), Z is a C1-C6 hydrocarbon group, and n is an integer of 1-6 in Formula.)

  From the viewpoints of developability, cured film properties and adhesiveness, the dicarboxylic acid is more preferably a dicarboxylic acid having an alkylene chain having 2 to 15 carbon atoms, particularly preferably a structure represented by the following general formula (II) It is a dicarboxylic acid having In formula, n shows the integer of 1-14.

  The dicarboxylic acid having an alkylene chain having 2 to 15 carbon atoms as described above or a dicarboxylic acid derivative described later is preferably 10 to 100 mol% of the whole dicarboxylic acid or the whole dicarboxylic acid derivative.

  Those having a phenolic hydroxyl group as the terminal group of the polyamide resin are preferred, but it is preferred that the side chain group also has an alkali-soluble group. Examples of the alkali-soluble group include an ethylene glycol group, a carboxyl group, a hydroxyl group, a sulfonyl group, a phenolic hydroxyl group, and the like, and a phenolic hydroxyl group is preferable. Furthermore, it is more preferable that the alkali-soluble group in the component (A) is only a phenolic hydroxyl group.

  When a phenolic hydroxyl group-containing amine is used during the synthesis of the polyamide resin, a phenolic hydroxyl group can be introduced as a terminal group by the reaction of the dicarboxylic acid residue with the amino group of the phenolic hydroxyl group-containing amine. Thereby, the weight average molecular weight of the polymer can be lowered, and the developability at the time of pattern formation and the thermocompression bonding property can be improved.

  As the phenolic hydroxyl group-containing amine, aminophenol derivatives are preferred. Examples of aminophenol derivatives include o-aminophenol, m-aminophenol, p-aminophenol, aminocresols such as 2-amino-m-cresol, and aminomethoxybenzenes such as 2-amino-4-methoxybenzene, 4 Examples thereof include hydroxydimethylanilines such as -hydroxy-2,5-dimethylaniline, and a compound represented by the following formula (13) is preferable. Among them, those having a hydroxyl group at the meta position of the amino group are preferred from the viewpoint of solubility in an alkali developer and stability at the time of varnish, and among these, m-aminophenol is easy to introduce during polyamide synthesis. Is particularly preferred.

  The polyamide resin having a phenolic hydroxyl group as a terminal group is, in addition to pattern-forming properties, thermocompression bonding properties and high-temperature adhesiveness, stability when the film-like positive photosensitive adhesive composition is in the form of varnish or film, and This is preferable because the embedding (flatness) by applying or laminating to a substrate having protrusions or steps like a connection terminal is improved.

In the present invention, the alkaline aqueous solution-soluble polyamide resin having the structural unit represented by the general formula (I) can be synthesized by reacting the above-described phenolic hydroxyl group-containing diamine with a dicarboxylic acid derivative.
Here, the dicarboxylic acid derivative represents a compound in which the hydroxyl group of the dicarboxylic acid is substituted with an atom other than carbon and hydrogen. The dicarboxylic acid derivative is preferably a dihalide derivative substituted with a halogen atom, and more preferably a dichloride derivative substituted with a chlorine atom.

The dichloride derivative can be synthesized by reacting a dicarboxylic acid with a halogenating agent.
As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

Examples of the method for synthesizing the dichloride derivative include a method in which a dicarboxylic acid and the halogenating agent are reacted in a solvent, and a method in which the dicarboxylic acid is reacted in an excess of a halogenating agent.
As the solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 molar equivalents, more preferably 1.7 to 2.5 molar equivalents relative to the dicarboxylic acid. When making it react in an agent, 4.0-50 molar equivalent is preferable and 5.0-20 molar equivalent is more preferable.
The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

The reaction between the dichloride derivative and the phenolic hydroxyl group-containing diamine is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent.
As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used.
As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  The molecular weight of the component (A) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, in terms of weight average molecular weight, from the viewpoint of the balance between developability and cured film properties. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  In the film-form positive photosensitive adhesive composition of the present embodiment, the content of the component (A) is 10% by mass to 90% by mass based on the total solid content of the film-form positive photosensitive adhesive composition. It is preferably 15% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and most preferably 30% by mass to 60% by mass. When the content is 10% by mass or more, the developability during pattern formation tends to be sufficient, and the handleability such as tackiness tends to be sufficient. When the content is 90% by mass or less, the pattern is formed. There is a tendency that the developability and adhesiveness of the film become sufficient.

(B) component:
The film-form positive photosensitive adhesive composition of this invention contains the compound which generate | occur | produces an acid by (B) light with the said alkali-soluble resin. The compound that generates an acid by light has a function of generating an acid by light irradiation and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. Here, examples of the actinic rays used for the light irradiation that induces acid generation of the component (B) include ultraviolet rays, visible rays, and radiation. Examples of the photoacid generator include a quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, and the like, and a quinonediazide compound is preferably used from the viewpoint of developing good sensitivity and resolution. It is preferable to use a quinonediazide compound.

The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chloride and a hydroxy compound or an amino compound to a condensation reaction in the presence of a dehydrochlorinating agent.
Examples of the o-quinonediazide sulfonyl chloride include 1,2-benzoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide. -4-sulfonyl chloride and the like can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2 , 3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′ , 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1 , 3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] Nden, tris (4-hydroxyphenyl) methane, can be used tris (4-hydroxyphenyl) ethane and the like.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino -4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3 -Amino-4-hydroxyphenyl) hexafluoropropyl Bread, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

  The reaction between the o-quinonediazide sulfonyl chloride and the hydroxy compound or amino compound is formulated so that the total of hydroxy and amino groups is 0.5 to 1 equivalent per mole of o-quinonediazide sulfonyl chloride. Is preferred. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent for the above reaction, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the film-like positive photosensitive adhesive composition of the present invention, a compound capable of generating an acid by light is used as the component (B) together with the alkali-soluble resin used as the component (A). The amount of the compound that generates an acid by light is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component (A) in order to improve the sensitivity and resolution during exposure. The amount is more preferably 01 to 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

<(C) component>
Furthermore, the film-form positive photosensitive adhesive composition of this embodiment contains (C) a compound (hereinafter also referred to as component (C)) that crosslinks itself or a resin by heat. Here, “resin” refers to, for example, the “(A) alkali-soluble resin”.

  Examples of the compound (C) used in the present invention that crosslinks itself or a resin by heat include compounds having at least one methylol group, alkoxyalkyl group, epoxy group, oxetanyl group in the molecule. It is not limited to. The temperature at which the component (C) can be crosslinked is such that the film-like positive photosensitive adhesive composition does not proceed with crosslinking in each step of coating, drying, exposure and development in order to ensure fluidity during thermocompression bonding. The temperature is preferably 150 ° C. or higher.

  Among these, a compound having an epoxy group is preferable from the viewpoint of excellent reliability. As the compound having an epoxy group, those containing at least two epoxy groups in the molecule are preferable from the viewpoint of high-temperature adhesiveness and reflow resistance, and from the viewpoint of pattern forming property and thermocompression bonding property, room temperature ( A glycidyl ether type epoxy resin having a liquid state or a semi-solid state at 25 ° C., specifically a softening temperature of 50 ° C. or less is more preferable. Such a resin is not particularly limited. For example, glycidyl ether of bisphenol A type, AD type, S type, or F type, glycidyl ether of hydrogenated bisphenol A type, glycidyl ether of ethylene oxide adduct bisphenol A type, Examples include propylene oxide adduct bisphenol A type glycidyl ether, trifunctional type or tetrafunctional type glycidyl ether, glycidyl ester of dimer acid, and trifunctional type or tetrafunctional type glycidylamine. These can be used alone or in combination of two or more.

  As the component (C), the 5% mass reduction temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, and extremely preferably 260 ° C. or higher. preferable. When the 5% mass reduction temperature is 150 ° C. or higher, the low outgassing property, the high temperature adhesiveness, and the reflow resistance are further improved.

  The 5% mass reduction temperature means that the sample was heated at a rate of 10 ° C./min with a nitrogen flow (400 ml / min) using a differential thermogravimetric simultaneous measurement apparatus (product name: TG / DTA6300, manufactured by SII Nanotechnology). min) is the 5% mass loss temperature as measured under.

  As the component (C), an epoxy resin represented by the following structural formula is preferably used. By using such an epoxy resin, 5% mass reduction temperature, pattern formability, high temperature adhesion, reflow resistance, and moisture resistance reliability can be sufficiently imparted.

  In addition, as the component (C), it is preferable to use a high-purity product in which impurity ions, alkali metal ions, alkaline earth metal ions, and halogen ions, particularly chlorine ions, are reduced to 300 ppm or less. It is possible to prevent electromigration and corrosion of metal conductor circuits.

  The content of the component (C) is preferably 5 parts by mass to 300 parts by mass and more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). When the content is 300 parts by mass or less, the solubility in an alkaline aqueous solution is improved, and the pattern formability tends to be improved. On the other hand, when the content is less than 5 parts by mass, sufficient thermocompression bonding property and high temperature adhesiveness tend to be difficult to obtain.

<(D) component>
The film-form positive photosensitive adhesive composition of this embodiment may further contain (D) a curing accelerator (hereinafter also referred to as (D) component). The component (D) is not particularly limited as long as it accelerates the curing and / or polymerization of the component (C) by heating. When the component (C) is an epoxy resin, for example, aromatic nitrogen-containing compound, dicyandiamide derivative, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and 1,8-diazabicyclo [5.4.0] An example is undecene-7-tetraphenylborate. Among them, imidazole compounds and salts thereof are preferable because they can achieve both an acceleration effect and stability. Particularly effective and preferable examples include 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-ethyl-4-methylimidazole-tetraphenylborate. It is preferable that content in the film-form positive photosensitive adhesive composition of these (D) components is 0.01 mass part-50 mass parts with respect to 100 mass parts of (C) component.

  Various coupling agents can also be added to the film-form positive photosensitive adhesive composition of the present embodiment. By using the coupling agent, interfacial bonding between different materials is improved. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based. Among them, a silane-based coupling agent is preferable because of its high effect, and a thermosetting group such as an epoxy group, and methacrylate and / or Or the compound which has radiation polymerizable groups, such as an acrylate, is more preferable. The boiling point and / or decomposition temperature of the silane coupling agent is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. That is, a silane coupling agent having a boiling point of 200 ° C. or higher and / or a decomposition temperature and a thermosetting group such as an epoxy group or a radiation polymerizable group such as methacrylate and / or acrylate is particularly preferable. The content of the coupling agent is preferably 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the component (A) to be used because the effect, heat resistance, and cost are further improved. .

  An ion scavenger can be further added to the film-like positive photosensitive adhesive composition of the present embodiment. The ion scavenger adsorbs ionic impurities and improves insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, a triazine thiol compound, a phenol-based reducing agent, etc., a compound known as a copper damage preventer for preventing copper from ionizing and dissolving, a powder Bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, tin-based, and mixed inorganic compounds thereof.

  Specific examples of the ion scavenger include, but are not limited to, inorganic ion scavengers manufactured by Toa Gosei Co., Ltd., trade names: IXE-300 (antimony), IXE-500 (bismuth), IXE-600 (antimony) , Bismuth mixed system), IXE-700 (magnesium and aluminum mixed system), IXE-800 (zirconium based), and IXE-1100 (calcium based). These can be used individually by 1 type or in mixture of 2 or more types. The content of the ion scavenger is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the effect of addition, heat resistance, and cost are further improved.

(Film adhesive)
A film adhesive can be obtained by forming the positive photosensitive adhesive composition into a film. FIG. 1 is an end view showing an embodiment of the film adhesive of the present invention. A film adhesive 1 shown in FIG. 1 is obtained by molding the above film positive photosensitive adhesive composition into a film.

  The film adhesive 1 is formed into a film shape by, for example, applying the positive photosensitive adhesive composition on the substrate 3 shown in FIG. 2 and drying it. Thus, the adhesive sheet 100 provided with the base material 3 and the adhesive layer 1 formed on the base material 3 using the film-like adhesive is obtained. FIG. 2 is an end view showing an embodiment of the adhesive sheet 100 of the present invention. The adhesive sheet 100 shown in FIG. 2 is comprised from the base material 3 and the adhesive bond layer 1 which consists of a film adhesive provided on the one side.

  FIG. 3 is an end view showing another embodiment of the adhesive sheet of the present invention. The adhesive sheet 110 shown in FIG. 3 includes a base material 3, an adhesive layer 1 made of a film adhesive provided on one surface of the base material 3, and a cover film 2.

  The film adhesive 1 can be obtained, for example, by the following method. First, component (A), component (B), component (C), component (D) and other components added as necessary are mixed in an organic solvent, and the mixture is kneaded to prepare a varnish. To do. Next, the said varnish is apply | coated on the base material 3, a varnish layer is formed, and after drying a varnish layer by heating, the base material 3 is removed. At this time, the substrate 3 can be stored or used in the state of the adhesive sheet 100 without removing the substrate 3. Further, the cover film 2 can be laminated on the surface opposite to the surface on which the base material 3 of the adhesive layer 1 is provided, and then stored or used in the state of the adhesive sheet 110.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as it can uniformly dissolve or disperse the material. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone (N-methyl-2-pyrrolidone).

  The above mixing and kneading can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill. The drying by heating is performed at a temperature at which the component (B) does not sufficiently react and under conditions where the solvent is sufficiently volatilized. Specifically, the “temperature at which the component (B) does not sufficiently react” refers to DSC (for example, product name: DSC-7, manufactured by Perkin Elmer Co., Ltd.), sample amount: 10 mg, temperature rise The temperature is equal to or lower than the peak temperature of the heat of reaction when measured under the conditions of speed: 5 ° C./min and measurement atmosphere: air. Specifically, the varnish layer is dried by heating at 60 to 180 ° C. for 0.1 to 90 minutes. The thickness of the varnish layer before drying is preferably 1 μm to 200 μm. If this thickness is 1 μm or more, the adhesive fixing function tends to be sufficient, and if it is 200 μm or less, the residual volatile matter described later tends to decrease.

  The residual volatile content of the obtained varnish layer is preferably 10% by mass or less. When the residual volatile content is 10% by mass or less, voids hardly remain inside the adhesive layer due to foaming due to solvent volatilization during assembly heating, and the moisture resistance tends to be improved. In addition, there is a tendency that the possibility of contamination of surrounding materials or members due to volatile components generated during heating is reduced. In addition, the measurement conditions of said residual volatile component are as follows. That is, for the film-like adhesive 1 cut to a size of 50 mm × 50 mm, the initial mass is M1, and the mass after heating the film-like adhesive 1 in an oven at 160 ° C. for 3 hours is M2, and the following formula To obtain the remaining volatile content (%). Residual volatile content (%) = [(M1-M2) / M1] × 100

  The substrate 3 is not particularly limited as long as it can withstand the above-described drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, and a methylpentene film can be used as the substrate 3. The film as the base material 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 silicone or silica.

  According to the film-form positive photosensitive adhesive composition of the present embodiment, by having the above configuration, a film is formed on the circuit surface of a semiconductor wafer having a circuit surface, and after patterning by exposure and development, the circuit surface It is possible to have thermocompression bonding property to an adherend composed of a semiconductor chip mounting support member, a semiconductor chip or a semiconductor wafer.

  The above “having thermocompression bonding to the adherend” means that the adherend is heated at 150 ° C. to 180 ° C. at 0.2 MPa to 1.0 MPa for one minute with respect to the patterned adhesive layer. It means that a pressure-bonded sample is prepared and the die shear strength at room temperature of this sample is 1 MPa or more. Here, the die shear strength at room temperature is a sample after thermocompression bonding under the above conditions, using a shear adhesion tester (Dage, product name: Dage-4000) on a 25 ° C. hot platen, The maximum stress when an external force in the shearing direction was applied to the adherend under the conditions of measurement speed: 100 μm / second and measurement height: 50 μm.

(Semiconductor wafer with adhesive layer)
FIG. 4 is a top view showing an embodiment of a semiconductor wafer with an adhesive layer of the present invention, and FIG. 5 is an end view taken along line IV-IV of FIG. A semiconductor wafer 20 with an adhesive layer shown in FIGS. 4 and 5 includes a semiconductor wafer 8 and a film adhesive (adhesive layer) 1 provided on one surface thereof.

  The semiconductor wafer 20 with an adhesive layer is obtained by laminating the film adhesive 1 on the semiconductor wafer 8 while heating. The film adhesive 1 can be attached to the semiconductor wafer 8 at a low temperature of about room temperature (25 ° C.) to 150 ° C., for example.

(Semiconductor device)
FIG. 6 is an end view showing an embodiment of the semiconductor device of the present invention. A semiconductor device 230 shown in FIG. 6 includes a support member (first adherend) 13 having a connection electrode portion (first connection portion: not shown) and a connection terminal (second connection portion: not shown). A semiconductor chip (second adherend) 14, an adhesive layer 1 made of an insulating material, and a conductive layer 9 made of a conductive material. The support member 13 has a circuit surface 18 that faces the semiconductor chip 14, and is disposed at a predetermined interval from the semiconductor chip 14. The adhesive layer 1 is formed between and in contact with the support member 13 and the semiconductor chip 14 and has a predetermined pattern. The conductive layer 9 is formed in a portion where the adhesive layer 1 is not disposed between the support member 13 and the semiconductor chip 14. The connection terminal of the semiconductor chip 14 is electrically connected to the connection electrode portion of the support member 13 through the conductive layer 9.

  Hereinafter, the manufacturing method of the semiconductor device 230 shown in FIG. 6 will be described in detail with reference to FIGS. 7, 8 and 10 to 12 are end views showing an embodiment of a method for manufacturing a semiconductor device of the present invention, and FIG. 9 is a cross-sectional view showing an embodiment of a method for manufacturing a semiconductor device of the present invention. is there. The manufacturing method of the semiconductor device of the present embodiment includes the following (first step) to (fifth step).

  (First Step) A step of providing the adhesive layer 1 on the semiconductor wafer 12 having the connecting electrode portion (FIGS. 7 and 8).

  (2nd process) The process which patterns the adhesive bond layer 1 so that the opening 11 which a connection terminal exposes may be formed by exposure and image development (FIG.9 and FIG.10).

  (Third step) A step of filling the opening 11 with a conductive material to form the conductive layer 9 (FIG. 11).

  (4th process) The laminated body of the semiconductor wafer 12, the adhesive bond layer 1, and the conductive layer 9 is cut | disconnected for every semiconductor chip (dicing) process (FIG. 12).

  (Fifth step) The supporting member 13 having the connecting electrode portion is directly bonded to the adhesive layer 1 side of the laminated body of the semiconductor chip 14 and the adhesive layer 1 singulated, and the connecting electrode of the supporting member 13 A step of electrically connecting the connecting portion and the connection terminal of the semiconductor chip 14 via the conductive layer 9 (FIG. 6).

Hereinafter, (first step) to (fifth step) will be described in detail.
(First step)
The adhesive layer 1 is laminated on the circuit surface of the semiconductor wafer composed of the semiconductor wafer 12 having the connection electrode portion shown in FIG. 7 (FIG. 8). As a laminating method, a method of preparing a film adhesive previously formed into a film shape and sticking it to a semiconductor wafer is simple.

  The film-form positive photosensitive adhesive composition according to this embodiment has an adhesive property to an adherend after patterning by exposure and development, and is capable of alkali development. It is a thing. More specifically, a resist pattern formed by patterning a film-like positive photosensitive adhesive composition by exposure and development has adhesion to an adherend such as a semiconductor chip or a substrate. For example, the resist pattern and the adherend can be bonded to each other by pressing the adherend to the resist pattern while heating as necessary.

(Second step)
Actinic rays (typically ultraviolet rays) are irradiated onto the adhesive layer 1 provided on the semiconductor wafer 12 through the mask 4 having openings formed at predetermined positions (FIG. 9). Thereby, the adhesive layer 1 is exposed in a predetermined pattern.

  After the exposure, the exposed portion of the adhesive layer 1 is removed by development using an alkaline developer, so that the adhesive layer 1 is formed so that the opening 11 through which the connection terminal of the semiconductor wafer 12 is exposed is formed. Patterning is performed (FIG. 10). At this time, it is preferable that the entire surface is exposed again after the development because void generation can be reduced in the subsequent process.

(Third step)
A conductive layer 9 is formed by filling the openings 11 of the obtained resist pattern with a conductive material (FIG. 11). As a method for filling the conductive material, various methods such as gravure printing, pressing with a roll, and vacuum filling can be employed. The conductive material used here is an electrode material made of a metal oxide such as solder, gold, silver, nickel, copper, platinum, palladium, or a metal oxide such as ruthenium oxide, or, for example, a conductive bump. Examples include those containing at least particles and a resin component. Examples of the conductive particles include conductive particles such as metals such as gold, silver, nickel, copper, platinum, and palladium, metal oxides such as ruthenium oxide, and organometallic compounds. Moreover, as a resin component, curable resin compositions mentioned above, such as an epoxy resin and its hardening | curing agent, are used, for example.

(4th process)
A laminated body of the semiconductor wafer 12, the adhesive layer 1, and the conductive layer 9 is cut into the semiconductor chips 14 by dicing (FIG. 12).

(5th process)
The support member 13 having the connection electrode portion is directly bonded to the adhesive layer 1 side of the laminated body of the semiconductor chip 14 and the adhesive layer 1, and the connection electrode portion of the support member 13 and the semiconductor chip 14. These connection terminals are electrically connected through the conductive layer 9. A patterned adhesive layer (buffer coat film) may be formed on the circuit surface of the semiconductor chip 14 opposite to the adhesive layer 1.

  The semiconductor chip 14 is bonded by, for example, a method in which the adhesive layer 1 (film-like positive photosensitive adhesive composition) is thermocompression bonded while being heated to a temperature at which fluidity is exhibited. After thermocompression bonding, the adhesive layer 1 may be heated as necessary to further advance the curing reaction.

  It is preferable to attach a back surface protective film to the circuit surface (back surface) opposite to the adhesive layer 1 in the semiconductor chip 14.

  With the above method, the semiconductor device 230 shown in FIG. 6 is obtained. The method for manufacturing a semiconductor device of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the gist of the present invention.

  For example, in the fourth step, in the fourth step, a laminate of the semiconductor wafer 12 and the adhesive layer 1 is formed on the wafer-sized support member 13, and an adhesive of the laminate of the semiconductor wafer 12 and the adhesive layer 1 is used. While directly bonding to the layer 1 side, the connection terminal of the support member 13 and the connection electrode portion of the semiconductor wafer 12 are electrically connected via the conductive layer 9, and in the fifth step, the semiconductor wafer 12 and the adhesive are connected. The stacked body of the layer 1 and the support member 13 may be cut for each semiconductor chip 14.

  The above manufacturing method is preferable in terms of work efficiency because the process up to the connection between the semiconductor wafer 12 and the support member 13 (fourth process) can be performed in the wafer size. In addition, it is preferable to affix a back surface protective film on the circuit surface (back surface) opposite to the adhesive layer 1 in the semiconductor wafer 12.

Further, the support member 13 may be a semiconductor chip or a semiconductor wafer. In this case, the semiconductor device (semiconductor laminated body) is formed by bonding the semiconductor wafers to each other, or bonding the semiconductor chip 14 to the semiconductor wafer (support member 13) or the semiconductor chips. ) Can be configured. It is also possible to form a through electrode in this laminate.
Moreover, the said manufacturing method can also use the semiconductor wafer in which the conductive layer 9 is already formed in the electrode part for a connection in a 1st process. In this case, the opening 11 can be performed in the second step so that the conductive layer 9 is exposed, and the third step can be omitted to proceed to the fourth step.

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

<(A) Component: Alkaline Aqueous Soluble Polyamide> (Synthesis Example 1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methyl-2-pyrrolidone were charged, and the flask was cooled to 5 ° C. Thereafter, 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a 4,4′-diphenyl ether dicarboxylic acid chloride solution. Subsequently, 87.5 g of N-methyl-2-pyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Glass Co., Ltd.) was charged. Product name: BIS-AP-AF) (18.30 g, 50 mmol) was dissolved by stirring. Thereafter, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., the 4,4′-diphenyl ether dicarboxylic acid chloride solution was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain carboxyl group-terminated polyhydroxyamide (hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 17,600 and a dispersity of 1.6 determined by GPC standard polystyrene conversion.

(Synthesis Example 2)
A polyhydroxyamide (hereinafter referred to as polymer II) was prepared under the same conditions as in Synthesis Example 1 except that 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was replaced with equimolar sebacic acid. Synthesized. The obtained polymer II had a weight average molecular weight of 28,700 and a dispersity of 2.2 determined by standard polystyrene conversion.

(Synthesis Example 3)
Polyhydroxyamide (hereinafter referred to as polymer III) under the same conditions as in Synthesis Example 1 except that 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was replaced with an equimolar amount of dodecanedioic acid. Was synthesized. The obtained polymer III had a weight average molecular weight of 27,200 and a dispersity of 1.9 determined by standard polystyrene conversion.

(Synthesis Example 4)
In Synthesis Example 1, bis (3-amino-4-hydroxyphenyl) hexafluoropropane and m-aminophenol 2.183 g (20 mmol) were further added, and the conditions were the same as in Synthesis Example 1 except that the mixture was stirred and dissolved. Were synthesized. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 15,800 and a dispersity of 2.1 determined by standard polystyrene conversion. The polymer IV was confirmed to have no residual carboxyl group by ¹ H-NMR measurement, and the alkali-soluble group was only a phenolic hydroxyl group.

(Synthesis Example 5)
In Synthesis Example 2, the same conditions as in Synthesis Example 2 except that 2.183 g (20 mmol) of m-aminophenol was further added together with bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and dissolved by stirring. Were synthesized. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 24,100 and a dispersity of 2.0 determined by standard polystyrene conversion. It was confirmed that the polymer V had no remaining carboxyl group by ¹ H-NMR measurement, and the alkali-soluble group was only a phenolic hydroxyl group.

(Synthesis Example 6)
In Synthesis Example 3, 2.183 g (20 mmol) of m-aminophenol was further added together with bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and dissolved by stirring. The others were synthesized under the same conditions as in Synthesis Example 3. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 22,700 and a dispersity of 2.1 determined by standard polystyrene conversion. The polymer VI was confirmed by ¹ H-NMR measurement to have no residual carboxyl group, and the alkali-soluble group was only a phenolic hydroxyl group.

(Synthesis Example 7)
2,2-bis (3-amino-4-hydroxyphenyl), which is a diamine, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen displacement device (nitrogen inlet tube), and reflux condenser with moisture receiver. 14.64 g (0.04 mol) of hexafluoropropane, 17.32 g (0.04 mol) of D-400 (manufactured by BASF, trade name: D-400, molecular weight: 433), and BY16-871EG (Toray Dow) 2.485 g (0.01 mol), m-aminophenol 2.183 g (0.02 mol), N-methyl-2 as a solvent, manufactured by Corning Co., Ltd., trade name: BY16-871EG, molecular weight: 248.5) -Pyrrolidone (hereinafter abbreviated as “NMP”) 80 g was charged and stirred to dissolve the diamine in the solvent.
Here, BY16-871EG is 3,3 ′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl) bispropylamine, and D-400 is polyoxypropylenediamine. .

While cooling the flask in an ice bath, 31 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”) was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas and kept for 5 hours to obtain a polyimide resin (hereinafter referred to as polymer VII). When the GPC measurement of the polymer VII was performed, it was weight average molecular weight (Mw) = 25,000 in polystyrene conversion. The Tg of polymer VII was 75 ° C. It was confirmed by ¹ H-NMR that there were no remaining carboxyl groups.

(Synthesis Example 8)
2,2-bis (3-amino-4-hydroxyphenyl), which is a diamine, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen displacement device (nitrogen inlet tube), and reflux condenser with moisture receiver. Hexafluoropropane 21.96 g (0.06 mol), D-400 8.66 g (0.02 mol), BY16-871EG 2.485 g (0.01 mol), m-aminophenol 2.183 g (0. 02 mol) and 80 g of NMP as a solvent were charged and stirred to dissolve the diamine in the solvent.

While cooling the flask in an ice bath, 31 g (0.1 mol) of ODPA was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas and kept for 5 hours to obtain a polyimide resin (hereinafter referred to as polymer VIII). When the GPC measurement of the polymer VIII was performed, it was weight average molecular weight (Mw) = 28,000 in polystyrene conversion. The Tg of polymer VIII was 100 ° C. It was confirmed by ¹ H-NMR that there were no remaining carboxyl groups.

(Synthesis Example 9)
A flask was charged with 35.6 g of 4-hydroxyphenyl methacrylate, 78.0 g of 2-hydroxyethyl methacrylate, 20.0 g of methyl methacrylate, 300 g of N, N-dimethylformamide, and 6.43 g of azoisobutyronitrile. For 6 hours at 80 ° C. After adding 200 g of methanol to the obtained reaction liquid, the acrylic polymer (Polymer IX) precipitated by slowly dropping into 1000 g of ion-exchanged water was filtered and dried. When the GPC measurement of the obtained polymer IX was performed, the weight average molecular weight (Mw) was 22,000 in polystyrene conversion.

(Synthesis Example 10)
10.8 g (100 mmol) of p-phenylenediamine was dissolved in 150 ml of N-methyl-2-pyrrolidone, and then 29.4 g (100 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. ) Was added for polymerization to obtain a polyamic acid having a weight average molecular weight of 41,400 determined by standard polystyrene conversion. This is polymer X.

(Synthesis Example 11)
100 parts by mass of a mixture of p-tert-butoxystyrene and styrene (molar ratio 85:15) was dissolved in 150 parts by mass of propylene glycol monomethyl ether. Furthermore, the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere, and 4 parts by mass of azobisisobutyronitrile was added, followed by stirring at a rotation speed of 160 rpm for 10 hours. Subsequently, after adding sulfuric acid to the reaction solution, the reaction temperature was maintained at 90 ° C. and stirred for 10 hours, and p-tert-butoxystyrene was further deprotected to obtain hydroxystyrene. Ethyl acetate was added to the obtained hydroxystyrene, washing with water was repeated 5 times, the ethyl acetate phase was separated, and the solvent was removed to obtain a p-hydroxystyrene / styrene copolymer (polymer XI).

  The polystyrene equivalent weight average molecular weight (Mw) obtained was 10,000. As a result of 13C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and styrene was 85:15.

  Polymers I to IX and XI were soluble in an alkaline aqueous solution (2.38 wt% tetramethylammonium hydroxide aqueous solution), whereas polymer X was insoluble.

(Measurement conditions of weight average molecular weight by GPC standard polystyrene conversion)
Measuring device; Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the sample.
Measurement temperature: 23 ° C

<Preparation of film adhesive composition>
Using the resin and other compounds obtained above, each component was blended at the composition ratios (unit: parts by mass) shown in Table 1 and Table 3 below. Examples 1 to 15, Reference Examples and Comparative Example 1 -3 film-like adhesive compositions were obtained.

In Table 1 and Table 3, each symbol means the following.
B-1: Tris (1,2-naphthoquinone-2-diazide-5-sulfonic acid) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene ] Bisphenol ester B-2: Tris (1,2-naphthoquinone-2-diazide-4-sulfonic acid) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] Phenyl] ethylidene] bisphenol ester C-1: YDF-870GS: manufactured by Toto Kasei Co., Ltd., bisphenol F type bisglycidyl ether C-2: manufactured by TCI, 2,2-bis (4-glycidyloxyphenyl) propane (bisphenol A type bis Glycidyl ether)
C-3: VG-3101: manufactured by Mitsui Chemicals, 1- [4- [1- (4-glycidyloxy) -1-methylethyl] phenyl] -1,1-bis (4-glycidyloxyphenyl) ethane C- 4: TCI, isocyanuric acid triglycidyl ester D-1: 2-phenyl-4-methyl-5-hydroxymethylimidazole B′-3: I-819: Ciba Japan, bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide C′-5: manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate NMP: N-methyl-2-pyrrolidone

  B'-3 is not a compound that generates an acid by light, but a compound that generates a radical species by light. C′-5 is not a compound that crosslinks itself or a resin by heat, but a compound that crosslinks itself or a resin by the action of a radical.

  Moreover, the film-like adhesive composition obtained in Examples 1-15, the reference example, and Comparative Examples 1-3 was evaluated by the method as described in the evaluation test mentioned later. The results are shown in Tables 2 and 4.

Pattern formation could not be performed in Comparative Example 1 in which component B was not used and Comparative Example 2 in which an alkali-soluble resin was not used (a resin insoluble in alkali was used).
Moreover, although the comparative example 3 which does not correspond to the resin composition of this invention can form a pattern, it resulted in a generally inferior compared with the Example of this invention in another characteristic.
Further, it is understood that the reference example not using the polyimide resin having a phenolic hydroxyl group or the polyamide resin having a phenolic hydroxyl group generally has a B evaluation as a whole as compared with the examples, and is particularly inferior in connectivity. It was.

<Film adhesive sheet>
The adhesive composition obtained by blending each component at the composition ratio shown in Table 1 and Table 3 above, each substrate (release agent-treated PET film) so that the film thickness after drying is 40 μm. It apply | coated on top, and it heated at 80 degreeC for 20 minute (s) in oven, followed by heating at 120 degreeC for 20 minutes, and formed the adhesive bond layer which consists of a film adhesive composition on a base material. Thus, the adhesive sheet which has a base material and the adhesive bond layer formed on the base material was obtained.

<Evaluation test>
A silicon wafer (6 inch diameter, 400 μm thickness) is placed on a support base, and the adhesive sheet is rolled on the silicon wafer so that the adhesive layer is in contact with the back surface (the surface opposite to the support base) of the silicon wafer. Lamination was performed under pressure (temperature 80 ° C., linear pressure 39 N / cm (4 kgf / cm), feed rate 0.5 m / min). The base material (PET film) was peeled and removed to expose the adhesive layer.
The following evaluation test was performed on the laminate obtained above.

(Void generation evaluation)
The said laminated body was separated into pieces with a size of 3 mm × 3 mm. After the separated laminate was dried on a hot plate at 120 ° C. for 10 minutes, the laminate was laminated on a glass substrate (10 mm × 10 mm × 0.55 mm) so that the adhesive layer was in contact with the glass substrate, The pressure was applied at 150 ° C. for 10 seconds while applying a pressure of 20 N (2 kgf). Thus, the sample of the laminated body by which the silicon wafer, the hardened | cured material layer, and the glass substrate were laminated | stacked in this order was obtained.

  The obtained sample was heated in an oven at 180 ° C. for 3 hours and observed through glass, and it was confirmed whether voids were generated at the interface between the cured product layer and the glass substrate. Evaluation was performed with “A” indicating no generation of voids, “B” indicating generation of small voids, and “C” indicating generation of large voids or a large number of voids.

(Pattern formability)
In the same manner as the void evaluation test, an adhesive layer was laminated on the silicon wafer. The obtained laminate was exposed from the adhesive side through a positive pattern mask in the same manner as in the above test. Next, in the same manner as in the above test, after standing on a hot plate, the substrate was removed, and development, washing with water, and drying were performed. In this way, an adhesive pattern of the film adhesive composition was formed on the silicon wafer.

  When the formed adhesive pattern is visually observed, a line width / space width = a thin line pattern of less than 30 μm / 30 μm is formed as “A”, and a thin line pattern of 30 μm / 30 μm to 60 μm / 60 μm is formed The pattern forming property is defined as “B” when the pattern is formed, “C” when the fine line pattern of 60 μm / 60 μm or more and less than 400 μm / 400 μm is formed, and “D” when the thin line pattern is not formed. Evaluation was performed. In addition, even when the crack was confirmed in the fine line pattern, it was determined that the fine line pattern was not formed.

(Fillability of the board with connection terminals)
Silicon chips with connection terminals (gold bumps) on a support base (1 cm x 1 cm, thickness 400 μm, terminals are 40 μm x 40 μm, height 40 μm, 100 μm pitch and exist at equal intervals in two rows along the chip peripheral) The adhesive sheet was laminated thereon by a vacuum laminator (temperature 80 ° C., pressure 0.5 MPa, time 30 seconds) so that the adhesive layer was in contact with the terminal side of the silicon wafer. After the substrate (PET film) was peeled and removed, the appearance of the exposed adhesive layer was observed with an optical microscope, and it was confirmed whether or not lamination was possible without generation of voids. “A” indicates that no void is generated around the terminal, “B” indicates that void is observed only in the periphery of the terminal, and “C” indicates that void is noticeable not only around the terminal but also on the entire surface. ).

(Initial conductivity (connectivity))
The silicon chip with connection terminals on which the adhesive layer is formed is flip-chip mounting apparatus FCB3 (manufactured by Panasonic Corporation, trade name), and a glass epoxy substrate (glass epoxy substrate: 400 μm thickness, copper wiring: 15 μm thickness, solder ball ( (Tin-silver) Height: 28 μm thickness, with solder resist, manufactured by Hitachi Chemical Co., Ltd.) (mounting conditions: pressure bonding temperature of film adhesive 250 ° C., pressure bonding time T: 10 seconds, 0.5 MPa). As a result, a semiconductor device similar to that shown in FIG. 6 was obtained.

  After the semiconductor devices were connected in a daisy chain, the connection resistance value was measured with a multimeter (manufactured by ADVANTEST) to evaluate whether or not the initial conduction after mounting was possible (conductivity). When the connection resistance value is 5 to 20Ω, “A” is set, and when the connection resistance value is other than “B”, the connection resistance value is not displayed due to a complete connection failure even in part. Was evaluated as “C”.

(Step embedding when mounting)
Each sample after mounting is observed with an ultrasonic exploration imaging apparatus (trade name: HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd.), and color correction and two-gradation using image processing software Adobe Photoshop (registered trademark) The film portion and the void portion on the film were identified by the above, and the ratio of the area occupied by the void portion on the film to the area of the film portion was calculated as a “void generation rate” using the following formula (1) by the histogram. . The sample with a void generation rate of 20% or less was set as “A”, and the sample with a void generation rate of more than 20% was set as “B” to evaluate the step burying property during mounting.
Void generation rate = (area of void part) / (area of film part) × 100 (1)

(Reflow resistance)
In the same manner as in the void evaluation test, the laminate composed of the silicon wafer and the adhesive layer was separated into pieces of 5 mm × 5 mm. A sample of a laminate consisting of a silicon substrate, an adhesive pattern, and a printed circuit board that are separated into pieces using a printed circuit board (glass epoxy substrate 15 mm × 15 mm × 0.15 mm) instead of a glass substrate, and these are stacked in this order. Got. The obtained sample was heated in an oven at 180 ° C. for 3 hours. The heated sample was treated for 168 hours under conditions of a temperature of 85 ° C. and a humidity of 60%, then placed in an environment of a temperature of 25 ° C. and a humidity of 50%, and then subjected to IR reflow at 250 ° C. for 10 seconds, followed by peeling. The presence or absence of this was observed with an appearance observation and an ultrasonic probe (SAT). Reflow resistance was evaluated with “A” indicating no peeling at all, “B” indicating that peeling was observed by SAT imaging, and “C” indicating that peeling was clearly observed in appearance observation. went.

<Film adhesive sheet>
The positive-type photosensitive adhesive composition obtained by blending each component at the composition ratio of Example 1 shown in Table 1 and Comparative Examples 5 and 6 shown in Table 3 has a film thickness after drying of 40 μm. Each was coated on a substrate (peeling agent-treated PET film). Next, the base material and the copper plate are placed in an oven, heated at a copper plate temperature of 80 ° C. for 20 minutes, and then heated at 100 ° C. for 20 minutes to form a film-form positive photosensitive adhesive composition on the base material. An adhesive layer was formed. Thus, the adhesive sheet which has a base material and the adhesive bond layer formed on the base material was obtained.

<Evaluation test>
By the above-described methods, the void generation property, the pattern formation property, the embedding property of the substrate with connection terminals, the connectivity, the step embedding property during mounting, and the reflow resistance were evaluated. The evaluation results are shown in Table 5.

  Further, Comparative Examples 5 and 6 that do not use a polyimide resin having a phenolic hydroxyl group or a polyamide resin having a phenolic hydroxyl group generally have a B evaluation as a whole as compared to the examples, and in particular, a substrate with a connection terminal. It turned out that it is inferior to the embedding property.

  DESCRIPTION OF SYMBOLS 1 ... Film adhesive (adhesive layer), 2 ... Cover film, 3 ... Base material, 4 ... Mask, 8 ... Semiconductor wafer, 9 ... Conductive layer, 11 ... Opening, 12 ... Semiconductor wafer, 13 ... Support member, DESCRIPTION OF SYMBOLS 14 ... Semiconductor chip, 18 ... Circuit surface, 20 ... Semiconductor wafer with an adhesive layer, 100, 110 ... Adhesive sheet, 230 ... Semiconductor device.

Claims (9)

(A) an alkali-soluble resin, and (B) a compound that generates an acid by light,
A film-like positive photosensitive adhesive composition used as an underfill material for bonding between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member,
The film-form positive photosensitive adhesive composition in which the (A) alkali-soluble resin contains a polyimide resin having a phenolic hydroxyl group or a polyamide resin having a phenolic hydroxyl group.   The film-form positive photosensitive adhesive composition according to claim 1, wherein the compound (B) that generates an acid by light is a quinonediazide compound.   The film-form positive photosensitive adhesive composition according to claim 1 or 2, wherein the terminal group of the (A) alkali-soluble resin is a phenolic hydroxyl group.   (C) The film-form positive photosensitive adhesive composition as described in any one of Claims 1-3 which further contains the compound which bridge | crosslinks with itself or resin with a heat | fever.   The film-form positive photosensitive adhesive composition according to claim 4, wherein (C) the compound that crosslinks itself or a resin by heat is a compound having an epoxy group. A substrate and an adhesive layer formed on the substrate;
The adhesive sheet which the said adhesive bond layer consists of a film-form positive photosensitive adhesive composition as described in any one of Claims 1-5.   The adhesive layer which consists of a film-form positive photosensitive adhesive composition as described in any one of Claims 1-5 laminated | stacked on the to-be-adhered body is exposed, and the said adhesive bond layer after exposure is alkali-developed. An adhesive pattern obtained by developing with a liquid. A semiconductor wafer and an adhesive layer laminated on the semiconductor wafer;
The semiconductor wafer with an adhesive layer in which the said adhesive bond layer consists of a film-form positive photosensitive adhesive composition as described in any one of Claims 1-5.   The film-like positive photosensitive adhesive composition according to any one of claims 1 to 5, wherein the semiconductor chips are bonded to each other and / or the semiconductor chip and the semiconductor chip mounting support member are bonded. Semiconductor device having the above structure.

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