JP2016088959A - Film type positive photosensitive adhesive composition, adhesive film, adhesive pattern, semiconductor wafer with adhesive layer, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive adhesive composition suitable as a film material to be used for a method for manufacturing a semiconductor device, the composition which exhibits excellent moisture resistance and flatness with little level unevenness after polished when a resin composition layer of the composition formed on a wafer is used as a resist for forming a wiring pattern and also as an adhesive for connecting elements, and which has no residue of a conductor on the adhesive layer and excellent reflow resistance, and to provide an adhesive film, an adhesive pattern, a semiconductor wafer with an adhesive layer and a semiconductor device using the above composition.SOLUTION: The positive photosensitive adhesive composition is supplied as a film material to be used for the following method of manufacturing a semiconductor device. The method includes the following steps in the described order: a step of forming a resin composition layer on a first semiconductor substrate; a step of partially removing the resin composition layer to form an opening for forming a connection terminal; a step of forming a conductor layer for forming a connection terminal on the opening; grinding an excessive portion of the conductor layer to separate each connection terminal in the opening from other connection terminals which have been formed as connected; and a step of connecting the first semiconductor substrate to a second semiconductor substrate.SELECTED DRAWING: None

Description

  The present invention relates to a positive photosensitive adhesive composition, and an adhesive film, an adhesive pattern, a semiconductor wafer with an adhesive layer, and a semiconductor device using the same.

  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 element and the semiconductor element mounting support member. This adhesive usually requires properties such as adhesiveness, thermocompression bonding, heat resistance, and moisture resistance, and when it is used in the form of a film, it needs further stickability.

  Depending on the function of the semiconductor package, the form, and the method for simplifying the assembly process, an adhesive having a photosensitivity capable of forming a pattern in addition to the above-described characteristics may be required. Photosensitivity is a function in which a portion irradiated with light is chemically changed and insolubilized or solubilized in an aqueous solution or an organic solvent. When this photosensitive photosensitive adhesive is used, a high-definition adhesive pattern can be formed by performing exposure and development processing through a photomask, and the formed adhesive pattern is deposited. It will have thermocompression bonding to the body.

  As a photosensitive adhesive composition, those based on a photoresist, a polyimide resin precursor (polyamic acid) (for example, Patent Documents 1 to 3), and those based on a low Tg polyimide resin are conventionally used. Known (Patent Document 4). From the viewpoint of working environment and wastewater treatment, the mainstream is one that can form a pattern with an alkaline developer.

  In the field of semiconductor mounting, a flip chip mounting method in which semiconductor elements are connected and / or a semiconductor element and a support member for mounting a semiconductor element 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, for the purpose of alleviating the stress, a method of sealing conductive bumps by filling a resin between connecting members is known (for example, Patent Document 5).

  In recent years, in the semiconductor mounting field, the miniaturization and integration of wiring and packages are approaching the limits. Therefore, a mounting technology using TSV (Through Silicon Via) in which electrodes are formed by penetrating a silicon chip and collectively connected is provided. Attention has been paid. However, the current process of stacking individual chips one by one has a problem that the process time becomes very long.

  As a technique for solving the above problem, a technique of directly forming a connection terminal on an adhesive layer on a wafer has been devised (for example, Patent Document 6). In Patent Document 6, a photosensitive resin composition containing a polyimide precursor soluble in an alkaline aqueous solution and a polybenzoxazole precursor is formed on a wafer by spin coating, and a barrier and copper are formed in an opening formed by exposure and development. A method is proposed in which a connection terminal is formed by plating after sputtering a seed, and two wafers smoothed by CMP polishing are stacked.

JP 2000-290501 A JP 2001-329233 A Japanese Patent Laid-Open No. 11-24257 International Publication No. 07/004569 Japanese Patent No. 3999840 JP 2012-69585 A

  When a method of directly forming a wiring on an organic film is used, the wiring may not be separated even after a CMP polishing process unless the underlying organic film has high flatness during film formation. For example, even if the organic film is a polishable film, if the flatness is remarkably poor, polishing for a long time is necessary, and the wiring part may be excessively polished or etched to become a concave shape, and wiring connection may not be possible. is there. Further, when the organic film is a film that is not polished by CMP, planarization tends to be difficult.

  Further, since the film formation using the conventional spin coating is insufficient in flatness, there is a problem that copper remains on the film unless the organic film as well as the wiring metal is polished by CMP.

However, when a polyimide or polybenzoxazole precursor is used for the organic film, it tends to become chemically very unstable and not polished when ring-closed. For this reason, it is necessary to keep it uncured or to a certain extent until the polishing step. However, since the polishing step is a wet process, an uncured organic film absorbs a large amount of water and swells. As a result, problems such as generation of a large amount of voids and contraction during curing in a state where wiring is formed on the film have occurred.
In the present invention, when the resin composition (adhesive) layer formed on the wafer is used as an adhesive at the time of resist formation and connection at the time of wiring formation, the moisture resistance and the flatness with few steps after CMP polishing are reduced. Provided is a positive photosensitive adhesive composition suitable as a film material for use in a method for manufacturing a semiconductor device which is excellent and has no conductor residue on an adhesive layer and has excellent reflow resistance. In addition, an adhesive film, an adhesive pattern, a semiconductor wafer with an adhesive layer, and a semiconductor device using the same are provided.

The present invention includes a step of forming a resin composition layer on a first semiconductor substrate, a step of removing a part of the resin composition layer to form an opening for forming a connection terminal, and the opening A step of forming a conductor layer for forming a connection terminal thereon, a step of grinding a surplus portion of the conductor layer to separate and form a connection terminal connected to the opening, and the first semiconductor substrate The surface is cured even after the photoreaction by using a positive photosensitive adhesive composition supplied as a film material used in a method for manufacturing a semiconductor device comprising the steps of connecting the semiconductor substrate and the second semiconductor substrate in this order. Thus, it has been found that the connection wiring can be separated and highly planarized in the CMP polishing process, and a good wafer laminate can be obtained.
The present invention also provides the positive photosensitive adhesive composition as described above, wherein the positive photosensitive adhesive composition contains (A) an alkali-soluble resin and (B) a compound that generates an acid by light. It is.
Moreover, this invention is said positive photosensitive adhesive composition whose compound which generate | occur | produces an acid by the said (B) light is a quinonediazide compound.
Moreover, this invention is a positive photosensitive adhesive composition as described above whose (A) alkali-soluble resin is a polyimide resin which has an alkali-soluble group as a terminal group or a side chain group.
The present invention also provides the positive photosensitive adhesive composition as described above, further comprising (C) a compound (thermal crosslinking agent) that crosslinks itself or a resin by heat.
In the present invention, the compound (C) that crosslinks itself or the resin by heat (C) is selected from a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group. The positive photosensitive adhesive composition as described above, comprising at least one compound.
Further, the present invention includes a base material and a resin composition layer formed on the base material, and the resin composition layer is formed using the positive photosensitive adhesive composition described above. It is an adhesive film.
The present invention also includes a resin composition comprising a semiconductor wafer and a resin composition layer laminated on the semiconductor wafer, wherein the resin composition layer is formed using the positive photosensitive adhesive composition described above. It is an adhesive pattern obtained by exposing a physical layer and developing the resin composition layer after exposure with an alkaline developer.
Further, the present invention comprises a semiconductor wafer and a resin composition layer laminated on the semiconductor wafer, and the resin composition layer is formed using the positive photosensitive adhesive composition described above. It is a semiconductor wafer with an adhesive layer.
Further, the present invention has 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 to each other by the positive photosensitive adhesive composition described above. A semiconductor device.

According to the present invention, when the resin composition layer formed on the wafer is used as an adhesive at the time of resist formation and connection at the time of wiring formation, it is excellent in moisture resistance in a wet process and is excellent with few steps after CMP polishing. It is possible to form a positive photosensitive adhesive composition having excellent flatness on a wafer, whereby copper (conductor) for wiring formation on a resin composition layer, which has been conventionally generated, can be used as a resin composition It is possible to suppress remaining on the layer and to form a favorable connection or a laminated structure.
Further, by using the present invention, the package can be miniaturized and the process can be simplified, the yield can be improved, and the cost can be reduced.

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 film of this invention. It is an end view which shows one Embodiment of the adhesive film 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. It is an end view which shows one form of the defect in the manufacturing method of the conventional semiconductor device.

  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.

(Semiconductor device)
FIG. 6 is an end view showing an embodiment of the semiconductor device of the present invention. In the semiconductor device 230 shown in FIG. 6, LSI wirings formed in two opposing semiconductor wafers 12 are electrically connected via connection terminals 9. The connection terminal 9 is formed in a portion where the insulating adhesive layer 1 is not disposed and is electrically independent.

  Hereinafter, the manufacturing method of the semiconductor device 230 shown in FIG. 6 will be described in detail with reference to FIGS. 7 and 8 and FIGS. 10 to 12 are end views showing one embodiment of a method for manufacturing a semiconductor device of the present invention. The method for manufacturing a semiconductor device according to this embodiment includes the following (first step) to ( (5th process) is provided.

  (First Step) A step of providing an adhesive layer (resin composition layer) 1 on a semiconductor wafer 12 having LSI wiring (FIGS. 7 and 8).

  (Second Step) A step of patterning the adhesive layer 1 so as to form an opening through which the connection terminal is exposed by exposure through the mask 4 and development (FIGS. 9 and 10).

  (Third step) A step of filling the conductor layer 9 'in the opening by sputtering and plating (FIG. 11).

  (Fourth Step) A step of removing the conductor layer 9 'formed excessively on the wafer by grinding such as CMP polishing and separating each connection terminal (FIG. 12).

  (Fifth step) A step of manufacturing the semiconductor device 230 by adjusting the positions of the two wafers manufactured in the above-described step so that the connection terminals 9 face each other.

Hereinafter, (first step) to (fifth step) will be described in detail.
(First step)
An adhesive layer (resin composition) 1 is laminated on a semiconductor wafer (first semiconductor substrate or second semiconductor substrate) 12 having LSI wiring shown in FIG. 7 (FIG. 8). As a laminating method, it is simple to prepare a film adhesive (adhesive film) that has been formed into a film in advance and affix it to a semiconductor wafer. A liquid varnish containing an adhesive composition may be applied on a semiconductor wafer and laminated by heat drying.

  The positive photosensitive adhesive composition according to the present embodiment is a positive photosensitive adhesive composition that has adhesiveness to an adherend after patterning by exposure and development and is capable of alkali development. More specifically, an adhesive pattern (resist pattern) formed by patterning a positive photosensitive adhesive composition by exposure and development has adhesiveness to adherends such as semiconductor chips and substrates. ing. For example, the adhesive pattern (resist pattern) and the adherend can be bonded by pressing the adherend to the adhesive pattern (resist pattern) while heating as necessary.

(Second step)
Actinic rays (typically ultraviolet rays) are applied to the adhesive layer 1 provided on the semiconductor wafer through a 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 patterned so that an opening exposing the connection portion of the LSI wiring is formed. (FIG. 10).

(Third step)
A conductive layer 9 'is formed by filling the openings of the obtained resist pattern with a conductive material (FIG. 11). As the filling method of the conductive material, when the conductive material is in a paste form, various methods such as gravure printing, pressing with a roll, and reduced pressure filling can be employed. Examples of the conductive material constituting the conductor layer used here include electrodes such as metals such as gold, silver, nickel, copper, platinum, and palladium, and metal oxides such as ruthenium oxide. When a metal that diffuses into a resin such as copper is used, a thin barrier layer made of titanium, tantalum, or the like is required. Therefore, a thin barrier layer is first formed by sputtering. Thereafter, a seed layer for plating a metal for forming a wiring is formed by sputtering, the seed layer is grown by plating, and a conductor layer is laminated on the adhesive layer 1 having an opening (FIG. 11).

(4th process)
The excess conductor layer laminated on the adhesive layer 1 is removed by a grinding process such as CMP polishing, and each connection terminal is separated (FIG. 12).

(5th process)
A process of manufacturing the semiconductor device 230 by bonding the wafer manufactured by the above process and another wafer together by adjusting the position so that the connection terminals 9 face each other. An adhesive layer or the like may be formed on another wafer by the same method as in the above step. Reliability can be improved by forming an adhesive layer or the like on another wafer.

  The semiconductor wafer 12 is bonded by, for example, a method in which the adhesive layer 1 (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.

With the above method, the semiconductor device 230 shown in FIG. 6 is obtained. A semiconductor chip and a semiconductor chip mounted structure, which are composed of a semiconductor wafer and a semiconductor mounting support member, and a structure in which the semiconductor chips are bonded to each other by the positive photosensitive adhesive composition of the present invention by separating them into pieces. A semiconductor device having a structure in which the supporting member for bonding is bonded can be 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.

  In the present specification, “sticking property” of a positive photosensitive adhesive composition refers to sticking property when a film-like adhesive obtained by forming a positive photosensitive adhesive composition into a film is used. means. The “high-temperature adhesiveness” of the positive photosensitive adhesive composition means adhesiveness under heating when the positive photosensitive adhesive composition is cured. “Pattern formability” of a positive photosensitive adhesive composition means that an adhesive layer made of the film-like adhesive formed on an adherend is exposed through a photomask and developed with an alkali developer. It means the accuracy of the adhesive pattern that is sometimes obtained. “Thermocompression bonding” of the positive photosensitive adhesive composition means the degree of adhesion when the above-mentioned adhesive pattern is heated (bonded) to semiconductor members or a support member or the like under heating. “Heat resistance” of the positive photosensitive adhesive composition means the peeling resistance when the adhesive pattern is thermocompression-bonded and cured between semiconductor wafers or a semiconductor wafer on a support member or the like and placed under a high temperature. . “Reflow resistance” means that the frame pattern of the positive photosensitive adhesive composition is thermocompressed and cured between semiconductor wafers or a semiconductor wafer on a support member, etc., and left for a predetermined time under high temperature and high humidity conditions. And it means the peel resistance after reflow heating.

<Positive photosensitive adhesive composition>
The positive photosensitive adhesive composition of the present embodiment contains (A) an alkali-soluble resin and (B) a compound that generates an acid by light.

<(A) component; alkali-soluble resin>
The Tg of the alkali-soluble resin as component (A) is preferably 150 ° C. or lower, and more preferably 120 ° C. or lower. When this Tg exceeds 150 ° C., a high temperature is required when a film-like adhesive obtained by forming a positive photosensitive adhesive composition into a film is bonded to an adherend, and the semiconductor wafer tends to be warped. There is. Moreover, the melt viscosity of the adhesive after pattern formation tends to increase, and the thermocompression bonding property tends to decrease.

  Moreover, it is preferable that the sticking temperature to the wafer surface of a film adhesive is 20-150 degreeC, and it is more preferable that it is 40-100 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 Tg is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 70 ° C. or higher. When the above Tg is less than 40 ° C., it is necessary to blend a large amount of other curing components in order to improve the elastic modulus after exposure and heat curing, and handling properties, storage stability, pattern formability, thermocompression bonding are required. , Heat resistance and low stress properties tend to be reduced.

  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. It is a tan δ peak temperature when measured under the conditions of / min, frequency 1 Hz, measurement temperature −150 to 300 ° C.

  The weight average molecular weight of the component (A) is preferably controlled within the range of 5,000 to 500,000, more preferably 10,000 to 300,000, and 10,000 to 100,000. More preferably. When the weight average molecular weight is within the above range, the strength, flexibility, and tackiness when the positive photosensitive adhesive composition is made into a sheet or film are good. Further, since the thermal fluidity is good, it is possible to ensure good embedding properties with respect to the wiring step (unevenness) on the substrate surface. When the weight average molecular weight is less than 5,000, the film formability tends to be insufficient. On the other hand, if the weight average molecular weight exceeds 500,000, the heat fluidity and the embedding tend to be insufficient, and the solubility of the positive photosensitive adhesive composition in an alkaline developer during pattern formation. Tends to be insufficient. Here, the “weight average molecular weight” means a 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. Furthermore, the heating temperature (thermocompression bonding temperature) when the semiconductor element is bonded and fixed to the semiconductor element mounting support member can be lowered, and high temperature adhesiveness can be imparted while suppressing an increase in warpage of the semiconductor element. it can. Further, it is possible to effectively impart sticking property, thermocompression bonding property and developability.

  (A) A component should just have a phenolic hydroxyl group as a terminal group, However, It is preferable that a 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, and a phenolic hydroxyl group, 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.

  Examples of the component (A) include polyester resins, polyether resins, polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, polyurethane resins, polyurethaneimide resins, polyurethaneamideimide resins, siloxane polyimide resins, and polyesterimides. Resins and their copolymers and their precursors (polyamide acid, etc.), polybenzoxazole resins, phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyester resins, polyether resins, polycarbonates Examples thereof include resins, polyether ketone resins, (meth) acrylic copolymers having a weight average molecular weight of 10,000 to 1,000,000, novolac resins, and phenol resins. These can be used alone or in combination of two or more.

  Among these, it is preferable that (A) component is a polyimide resin from a viewpoint of high temperature adhesiveness, heat resistance, and film formation. The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride, diamine, and 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 above condensation reaction is such that the total of diamine is 0.5 to 2.0 mol with respect to 1.0 mol of tetracarboxylic dianhydride. Preferably, it is 0.8-1.0 mol.

The mixing molar ratio of the tetracarboxylic dianhydride and the phenolic hydroxyl group-containing amine in the above condensation reaction is such that the total of the phenolic hydroxyl group-containing amine is 0.04 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.
In addition, the addition order of tetracarboxylic dianhydride, 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.

  Further, the reaction temperature in the condensation reaction is preferably 80 ° C. or lower, and more preferably 0 to 60 ° C. 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'-biphenyl tetracarboxylic 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-perylenetetracarbo Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic Acid dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic Acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2 , 3,6,7-tetrac Loronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride , Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methyl Phenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis ( , 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 dianhydride, 1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane) -2,3-dicarboxylic dianhydride, bicyclo- [2,2,2]- Oct-7- -2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-di Carboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride) 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3 Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, and tetracarboxylic dianhydride represented by the following general formula (1) Is 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 (4), (5), and (6), and a polyimide resin having a high Tg. From the viewpoint of obtaining good pattern forming properties and thermocompression bonding properties, a diamine represented by the following general formula (6) is more preferable.

In the general formula (6), 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 general 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 increased, it is possible to obtain good pattern forming properties, and it is possible to realize a positive photosensitive adhesive composition with further improved moisture resistance reliability.

  The diamine represented by the general formula (6) is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol% of the total diamine. 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 (7). 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 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 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%, still more preferably 10 to 80 mol% of the total diamine. 80 mol% is particularly preferable, and 30 to 70 mol% is particularly preferable.

There is no restriction | limiting in particular as another 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'-diaminodiphenyl 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-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4′- (1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) ) Phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- ( 3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) phene Nyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and aromatic diamines such as 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) Is 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 1 to 80 mol%, more preferably 10 to 80 mol%, still more preferably 10 to 60 mol% of the total diamine. If this amount is less than 1 mol%, it tends to be difficult to impart high-temperature adhesiveness and hot fluidity, while if it exceeds 80 mol%, the Tg of the polyimide resin becomes too low, There is a tendency that the self-supporting property is not sufficient.

  Furthermore, the aliphatic ether diamine preferably has a propylene ether skeleton represented by the following general formula (10) 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 general formula (10), 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 and adhesiveness in room temperature (25 degreeC).

  Specifically, as the siloxane diamine represented by the general formula (9), it is assumed that d in the general 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- , 3-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 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1 , 5-Bis (4-aminobutyl Trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, and 1,1,3,3,5 , 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like. 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. Moreover, it is preferable to set it as 1-80 mol% of the total diamine, and it is more preferable to set it as 2-50 mol%, and it is still more preferable to set it as 5-30 mol%. If it is less than 1 mol%, the effect of adding siloxane diamine is reduced, and if it exceeds 80 mol%, the compatibility with other components, high-temperature adhesion, and developability tend to be reduced.

  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 preferable 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. As a result, 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 compound represented by the following formula (11) 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 polyimide synthesis. Is particularly preferred.

  Polyimide resin having a phenolic hydroxyl group as a terminal group, in addition to pattern formability, thermocompression bonding, and high temperature adhesiveness, stability when the composition is in the form of a varnish or film, and protrusions and steps like connection terminals This is preferable because the embedding by application to a certain substrate or lamination 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 anhydride 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.

  In the positive photosensitive adhesive composition of the present embodiment, the content of the component (A) is preferably 10 to 90% by mass based on the total solid content of the positive photosensitive adhesive composition. More preferably, it is -80 mass%, It is still more preferable that it is 20-70 mass%, It is especially preferable that it is 30-60 mass%. If the content is less than 10% by mass, the developability during pattern formation tends to be insufficient, and the handleability such as tackiness tends to be insufficient. There exists a tendency for developability and adhesiveness to become insufficient.

  When the polyimide resin is poor in alkali solubility when the polyimide resin is blended as the component (A), even if a resin having a carboxyl group and / or a hydroxyl group or a resin having a hydrophilic group is added as a dissolution aid Good. The resin having a hydrophilic group is not particularly limited as long as it is an alkali-soluble resin, and examples thereof include resins having glycol groups such as ethylene glycol and propylene glycol groups.

<(B) component; compound which generates acid by light>
The positive photosensitive adhesive composition of the present invention includes (B) a compound capable of generating an acid by light together with the (A) 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. From the viewpoint of expressing good sensitivity and resolution, it is preferable to use a quinonediazide compound. Examples of the light include ionizing radiation and non-ionizing radiation. Specifically, excimer laser light such as ArF and KrF, electron beam, extreme ultraviolet light, vacuum ultraviolet light, X-ray, ion beam, i And ultraviolet light such as g-line.

The 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.
As the o-quinonediazide sulfonyl chloride, benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, etc. are used. be able to.

  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] ind , Tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  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) hexafluoropropane Bis (4-amino-3-hydroxyphenyl) hexafluoropropane or 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 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). This amount is preferably 0.01 to 50 parts by mass, and 0.01 to 20 parts by mass with respect to 100 parts by mass of component (A) in order to improve the sensitivity and resolution during exposure. It is more preferable, and it is still more preferable to set it as 0.5-20 mass parts.

<Component (C): Compound that crosslinks itself or resin by heat (thermal crosslinking agent)>
Further, the positive photosensitive adhesive composition of the present embodiment contains (C) a compound that crosslinks itself or a resin by heat (thermal crosslinking agent, hereinafter may be referred to as component (C)).

  In this embodiment, (C) the compound that crosslinks with itself or the resin by heat includes a compound having at least one methylol group, alkoxyalkyl group, epoxy group, oxetanyl group in the molecule. It is not limited to. Moreover, the compound which has a phenolic hydroxyl group, and the compound which has a hydroxymethylamino group are mentioned. The temperature at which the component (C) can be cross-linked is 150 so that the positive photosensitive adhesive composition is not cross-linked in each step of application, drying, exposure, and development in order to ensure fluidity during thermocompression bonding. It is preferable that the temperature is not lower than ° C. 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 particularly 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 improved.

  The 5% mass reduction temperature refers to a sample using a differential thermothermal gravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: TG / DTA6300), a heating rate of 10 ° C./min, a nitrogen flow (400 ml / min) is the 5% mass loss temperature as measured under.

  As the component (C), it is preferable to use an epoxy resin represented by the following formulas (12) and (13). 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 to 300 parts by mass and more preferably 10 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; hardening accelerator>
Furthermore, the positive photosensitive adhesive composition of the present embodiment may contain (D) a curing accelerator (hereinafter sometimes referred to as “component (D)”). The component (D) is not particularly limited as long as it accelerates curing and / or polymerization of the epoxy resin by heating. For example, imidazole compound, aromatic nitrogen-containing compound, dicyandiamide derivative, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate Can be mentioned. 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. The content of the component (D) in the positive photosensitive adhesive composition is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (C).

<Coupling agent>
Various coupling agents can also be added to the 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 having a thermosetting group such as an epoxy group and a radiation polymerizable group such as methacrylate and / or acrylate is preferably used. It is preferable that the usage-amount of the said coupling agent shall be 0.01-20 mass parts with respect to 100 mass parts of (A) component to use from the surface of the effect, heat resistance, and cost.

<Ion scavenger>
An ion scavenger can also be added to the 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 amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the effect of addition, heat resistance, cost, and the like.

<Filler component>
The positive photosensitive adhesive composition of the present embodiment may contain a filler component as necessary. Thereby, the viscosity of the adhesive, the physical properties of the cured product of the adhesive, and the like can be controlled. Specifically, for example, it is possible to suppress the generation of voids at the time of connection and to reduce the moisture absorption rate of the cured adhesive.

  As the filler component, an insulating inorganic filler, whisker, resin filler, or the like can be used. Moreover, as a filler component, 1 type may be used independently and 2 or more types may be used together.

  Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black (pigment), mica, and boron nitride. Among these, silica, alumina, titanium oxide, and boron nitride are preferable, and silica, alumina, and boron nitride are more preferable.

  Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.

  As a resin filler, the filler which consists of resin, such as a polyurethane and a polyimide, is mentioned, for example.

  Since the resin filler has a smaller coefficient of thermal expansion than organic components (such as epoxy resin and curing agent), it is excellent in the effect of improving connection reliability. Further, according to the resin filler, the viscosity of the adhesive can be easily adjusted. Moreover, since the resin filler is excellent in the function which relieves stress compared with an inorganic filler, according to the resin filler, peeling in a reflow test or the like can be further suppressed.

  Since the inorganic filler has a smaller coefficient of thermal expansion than that of the resin filler, the inorganic filler can realize a low coefficient of thermal expansion of the adhesive composition. In addition, since many inorganic fillers are general-purpose products whose particle size is controlled, they are also preferable for viscosity adjustment.

  Since the resin filler and the inorganic filler each have an advantageous effect, either one may be used depending on the application, or both may be mixed and used in order to exhibit both functions.

  The shape, particle size and content of the filler component are not particularly limited. Further, the filler component may be one whose physical properties are appropriately adjusted by surface treatment.

  The filler component is preferably composed of an insulator. If the filler component is composed of a conductive material (for example, solder, gold, silver, copper, etc.), the insulation reliability (particularly HAST resistance) may be reduced.

<Other ingredients>
You may mix | blend additives, such as antioxidant, a leveling agent, an ion trap agent, a flux agent, an elastomer, and a dissolution accelerator, with the positive photosensitive adhesive composition of this embodiment. These can be used individually by 1 type or in combination of 2 or more types. About these compounding quantities, what is necessary is just to adjust suitably so that the effect of each additive may express.

<Adhesive film (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 forming the 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 film 100 provided with the base material 3 and the adhesive bond layer 1 which consists of the said film adhesive formed on the base material 3 is obtained. FIG. 2 is an end view showing an embodiment of the adhesive film 100 of the present invention. The adhesive film 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 of this.

  FIG. 3 is an end view showing another embodiment of the adhesive film of the present invention. The adhesive film 110 shown in FIG. 3 is comprised from the base material 3, the adhesive bond layer 1 and the cover film 2 which consist of a film adhesive provided on one side of this.

  The film adhesive (adhesive layer) 1 can be obtained, for example, by the following method. First, component (A), component (B), component (C), and other components added as necessary are mixed in an organic solvent, and the mixture is kneaded to prepare a varnish. Next, this varnish is apply | coated on the base material 3, the layer of a varnish 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 film 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 film 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 mixing and kneading can be carried out 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 to 200 μm. If the thickness is less than 1 μm, the adhesive fixing function tends to be insufficient, and if it exceeds 200 μm, the residual volatile matter described later tends to increase.

The residual volatile content of the obtained varnish layer is preferably 10% by mass or less. If this residual volatile content exceeds 10% by mass, voids tend to remain inside the adhesive layer due to foaming due to solvent volatilization during assembly heating, and the moisture resistance tends to decrease. In addition, there is a tendency that peripheral materials or members are contaminated by volatile components generated during heating. 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 in length and 50 mm in width, 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, The residual volatile content (mass%) is obtained by the following formula.
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 such as a polyethylene terephthalate film, a polypropylene 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 a silicone type and a silica type.

(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.

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

The materials used in the examples and comparative examples are shown below.
[(A) component; alkali-soluble resin] A-1:
2,2-bis (3-amino-4-hydroxyphenyl) hexa, which is a diamine, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen displacement device (nitrogen inlet pipe) and a reflux condenser with a moisture receiver. 14.64 g (0.04 mol) of fluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366) (hereinafter referred to as “BIS-AP-AF”), polyoxypropylenediamine ( BASF Corporation, trade name: D-400, molecular weight: 433) (hereinafter referred to as “D-400”) 17.32 g (0.04 mol), 3,3 ′-(1,1,3,3- Tetramethyldisiloxane-1,3-diyl) bispropylamine (made by Toray Dow Corning Co., Ltd., trade name: BY16-871EG, molecular weight: 248.5) (hereinafter referred to as “BY16- 871EG ”), 2.485 g (0.01 mol) of m-aminophenol, 2.183 g (0.02 mol) of m-aminophenol, and 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as“ NMP ”) as a solvent. The diamine was dissolved in the solvent by stirring.

While cooling the flask in an ice bath, 31 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride (hereinafter referred to 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 polyimide resin A-1. GPC (gel permeation chromatography) measurement was performed on the obtained polyimide A-1 under the following conditions. As a result, the weight average molecular weight (Mw) in terms of polystyrene was 25,000. Moreover, Tg of A-1 was 75 degreeC. It was confirmed by ¹ H-NMR that there were no remaining carboxyl groups.

(GPC measurement conditions)
Device name: RI-8020 manufactured by Tosoh Corporation
Column: A150S + A160S
Detector: RI detector
Column temperature: 25 ° C
Eluent: THF (tetrahydrofuran)
Flow rate: 1 ml / min
Reference material: Polystyrene

In Table 1 and Table 2, each symbol means the following.
[Component (B): Compound that generates acid by light]
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-methyl Ethyl] phenyl] ethylidene] bisphenol ester [component (C); a compound that crosslinks itself or resin with heat]
C-1: Bisphenol F-type bisglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YDF-8170")
C-2: 1- [4- [1- (4-Glycidyloxy) -1-methylethyl] phenyl] -1,1-bis (4-glycidyloxyphenyl) ethane (Mitsui Chemicals, VG-3101) )
C-3: 4,4 ′-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene) -bisphenol (trade name “TrisP, manufactured by Honshu Chemical Industry Co., Ltd.) -PA-MF ")
[Other ingredients;]
E-1: EO-modified diisocyanate and triacrylate (manufactured by Toa Gosei Co., Ltd.)
I-819: BASF Corporation, trade name, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (5% mass loss temperature: 210 ° C., molecular extinction coefficient at 365 nm: 2300 ml / g · cm)
F: Supply form is film W: Supply form is varnish

<Preparation of positive photosensitive adhesive composition>
Using the resin and other compounds obtained above, each component was blended in the composition ratio (unit: parts by mass) shown in Table 1 below, and positive photosensitive adhesives of Examples 1 to 4 and Comparative Example 1 were used. An agent composition (varnish for forming an adhesive layer) was obtained.

<Adhesive film (film adhesive film)>
The obtained positive photosensitive adhesive composition was applied onto a substrate (peeling agent-treated PET (polyethylene terephthalate) film) so as to have a film thickness after drying of 20 μm, and 110 ° C. in an oven. Was heated for 20 minutes to form an adhesive layer made of a positive photosensitive adhesive composition on the substrate. Thus, the adhesive film which has a base material and the adhesive bond layer formed on the base material was obtained.

<Evaluation test>
The positive photosensitive adhesive compositions obtained in Examples 1 to 4 and Comparative Example 1 were evaluated by the method described in the evaluation test shown below. The results are shown in Table 2.

<Evaluation test>
On the silicon wafer (6 inch diameter, thickness 400 μm), the adhesive film is roll-pressed (temperature 80 ° C., line so that the adhesive layer is in contact with the back surface of the silicon wafer (surface opposite to the support base). The pressure was 4 kgf / cm, and the feeding speed was 0.5 m / min.
The following evaluation test was performed on the laminate obtained above.

<Pattern formability>
A sample in which a photosensitive adhesive composition was laminated on a silicon wafer was exposed from the resin layer side through a positive circular pattern mask. Next, after leaving on a hot plate, the substrate was removed, and development, washing with water, and drying were performed. In this way, an adhesive pattern of a positive photosensitive adhesive composition was formed on the silicon wafer. In addition, the circular pattern mask has a block in which circular patterns with an opening diameter / pitch of X / 2X (X is an integer in increments of 10 μm from 20 μm to 100 μm) are arranged in a grid pattern for each opening diameter / pitch. A mask with was used. “Aperture diameter” means the diameter of a circular pattern, and “pitch” means the distance between the centers of adjacent circular patterns.

  When the formed adhesive pattern is visually observed and a pattern having an opening diameter / pitch of 30 μm / 60 μm or less is formed, “A”, a pattern exceeding 30 μm / 60 μm and 60 μm / 120 μm or less is formed. The pattern forming property was evaluated as “B” when the pattern was formed, “C” when the pattern exceeding 60 μm / 120 μm and 100 μm / 200 μm was formed, and “D” when the pattern was not formed. The evaluation results are shown in Table 2.

<TMAH solubility>
It evaluated from the mode of melt | dissolution with respect to TMAH (tetramethylammonium hydroxide) in the case of pattern formation evaluation. The sample that was well dissolved and formed a pattern was evaluated as “A”, the pattern that could be formed but swelled was “B”, and the sample that did not dissolve and formed a pattern was evaluated as “C”. The evaluation results are shown in Table 2.

<Step after drying>
After the pattern formation test, washing with pure water for 3 minutes and drying on a 120 ° C. hot plate for 5 minutes were performed, and the surface level difference after drying was measured.
When the step on the surface of the adhesive pattern after drying is less than 0.5 μm, “A”, when it is 0.5 μm or more and less than 1.5 μm, “B”, and when 1.5 μm or more, “C” The subsequent step was evaluated. The evaluation results are shown in Table 2.

<Cu remaining after CMP>
A copper layer having a thickness of 5 μm was formed by sputtering on the surface of the sample for which the level difference after drying was evaluated, and then the surface was polished using a CMP polishing liquid for copper. After polishing, confirm the remaining state of copper on the surface of the adhesive pattern, "A" indicates that no copper remains other than the opening of the adhesive layer, and some openings are not separated by the remaining copper after shaving The state of the residue on the surface was evaluated with “B” as the state and “C” as the state where the copper remained on the entire surface. The evaluation results are shown in Table 2.

<Reflow resistance>
A laminate composed of a silicon wafer and an adhesive layer was cut into pieces of 5 mm length and 5 mm width. Using a printed circuit board (glass epoxy board length 15mm, width 15mm, thickness 0.15mm), it is composed of individualized silicon chips, adhesive pattern, and printed circuit board. Obtained. 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 less than 50%, and “C” indicating that peeling was 50% or more. . The evaluation results are shown in Table 2.

  In Comparative Example 1 having negative photosensitive characteristics, wiring formation and CMP polishing could be carried out satisfactorily, but the adhesive portion remaining after exposure and development was very hard due to photocuring, and the fluidity necessary for wiring connection was I have run out. Examples 1 to 4 having positive photosensitive characteristics with respect to these comparative examples have excellent solubility in TMHA and pattern formability, no step, no surface residue after sputtered copper polishing by CMP, A semiconductor device excellent in adhesive strength without voids can be obtained. The positive photosensitive adhesive composition of the present invention dissolves well in TMAH as a developer and does not swell so that a smooth Cu film can be formed on the film surface and the embedding property of a substrate with a connection terminal is also good. Therefore, it can be suitably used as a material for connection between semiconductor elements and / or connection between a semiconductor element and a semiconductor element mounting support member.

  Using two samples (opening diameter / pitch is X / 2X, X = 40 μm) used for the measurement of the surface residue after copper CMP, a solder paste is applied to the copper connection terminal in the opening, and 120 After drying at 10 ° C. for 10 minutes, the surfaces on which the copper connection terminals were formed in the openings were laminated and pressure-bonded at 150 ° C. for 10 seconds while being pressurized with 2 kgf. Thus, the sample of the semiconductor device laminated body which consists of a silicon wafer, the hardened | cured material layer of an adhesive bond layer, and a silicon wafer, and these are laminated | stacked in this order was obtained. A dicing film was pasted on one side, and a dicing saw was used to obtain a semiconductor device having a structure in which the semiconductor chips were bonded to each other so as to be about 3 mm square. This was treated for 168 hours at a temperature of 85 ° C. and a humidity of 60% RH, then placed in an environment of a temperature of 25 ° C. and a humidity of 50% RH, and then subjected to IR reflow at 250 ° C. for 10 seconds to check for peeling. As a result of visual observation and observation with an ultrasonic probe (SAT), no peeling was observed.

  Since the positive photosensitive adhesive composition of the present invention can form an adhesive pattern having sufficient moisture resistance reliability, it is suitably used as an adhesive used for manufacturing a high-definition semiconductor package. Utilizing this characteristic, wiring can be formed on the formed pattern and wafers can be bonded to each other. Such a manufacturing method has a strong influence on future miniaturization of the package, simplification of the process, cost reduction, etc., and the film adhesive and adhesive film of the present invention are preferably used for this method. Can do.

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

Claims (10)

Forming a resin composition layer on the first semiconductor substrate;
Removing a part of the resin composition layer to form an opening for forming a connection terminal;
Forming a conductor layer for forming a connection terminal on the opening;
Grinding the surplus portion of the conductor layer to separate and form connection terminals formed in the opening; and
Connecting the first semiconductor substrate and the second semiconductor substrate;
A positive-type photosensitive adhesive composition supplied as a film material used in a method for manufacturing a semiconductor device comprising:   The positive photosensitive adhesive composition according to claim 1, wherein the positive photosensitive adhesive composition contains (A) an alkali-soluble resin and (B) a compound that generates an acid by light.   The positive photosensitive adhesive composition according to claim 2, wherein the compound (B) that generates an acid by light is a quinonediazide compound.   The positive photosensitive adhesive composition according to claim 2 or 3, wherein the (A) alkali-soluble resin is a polyimide resin having an alkali-soluble group as a terminal group and a side chain group.   (C) The positive photosensitive adhesive composition as described in any one of Claims 1-4 which further contains the compound which bridge | crosslinks with itself or resin with a heat | fever.   The compound (C) that crosslinks itself or a resin by heat includes at least one compound selected from a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group. The positive photosensitive adhesive composition as described in any one of -5.   A positive photosensitive adhesive composition according to claim 1, comprising a base material and a resin composition layer formed on the base material, wherein the resin composition layer uses the positive photosensitive adhesive composition according to claim 1. An adhesive film is formed.   A semiconductor wafer and a resin composition layer laminated on the semiconductor wafer, wherein the resin composition layer uses the positive photosensitive adhesive composition according to any one of claims 1 to 6. An adhesive pattern obtained by exposing the resin composition layer to be formed, and developing the exposed resin composition layer with an alkali developer. A semiconductor wafer and a resin composition layer laminated on the semiconductor wafer;
The semiconductor wafer with an adhesive layer in which the said resin composition layer is formed using the positive photosensitive adhesive composition as described in any one of Claims 1-6.   The positive-type photosensitive adhesive composition according to any one of claims 1 to 6, wherein the semiconductor chips are bonded to each other and / or the semiconductor chip and the semiconductor chip mounting support member are bonded. A semiconductor device having a structure.

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