JP2017122742A - Positive photosensitive adhesive composition, adhesive pattern, semiconductor wafer with adhesive layer, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive adhesive composition that can express appropriate flowability in connection between semiconductor chips or between a semiconductor chip and a support member for mounting the semiconductor chip thereon, and also reduces the occurence of voids.SOLUTION: This invention relates to a positive photosensitive adhesive composition comprising (A) an alkali-soluble resin, (B) a compound that generates acid by light, (C) a heat crosslinking agent and (D) a curing accelerator.SELECTED DRAWING: None

Description

  The present invention relates to a positive photosensitive adhesive composition, 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.

  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.

  In recent years, in the field of semiconductor mounting, a flip chip mounting method in which semiconductor chips and / or a semiconductor chip and a semiconductor chip mounting support member 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).

Japanese Patent No. 3999840 International Publication No. 2011/049011 Japanese Patent No. 5176768 Japanese Patent No. 5077023

  The use of a negative photosensitive adhesive composition as a connection material between semiconductor chips and / or a connection material between a semiconductor chip and a semiconductor chip mounting support member has been studied (for example, Patent Document 2). . However, since the photocrosslinking reaction is used in the exposure process, the fluidity may be insufficient in the connection between the semiconductor chip and the support member for mounting the semiconductor chip. It may be difficult to take.

  On the other hand, a positive photosensitive insulating resin composition capable of expressing appropriate fluidity in connection between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member is disclosed (for example, Patent Document 3). ). However, in the heating at the time of connection, the remaining compound having a quinonediazide group is decomposed to generate gas, which may cause a void. Moreover, the method of decomposing | disassembling a quinonediazide group containing compound beforehand by heat processing or exposure processing before a connection is disclosed (for example, patent document 4). However, the decomposed gas may remain in the composition and cause voids.

  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 support member for mounting a semiconductor chip, and has few voids. An object is to provide a positive photosensitive adhesive composition.

  In order to solve the above-described problems, the present invention provides a positive photosensitive resin containing (A) an alkali-soluble resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) a curing accelerator. An adhesive composition is provided.

  By having the above configuration, it is possible to exhibit appropriate fluidity in the connection between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member, and the connection is made in a state where there is little generation of gas causing voids. Can be improved.

  (B) The compound that generates an acid by light is preferably an o-quinonediazide compound. Thereby, the pattern forming property and the storage stability are excellent, and in particular, the influence of sensitivity, resolution and oxygen inhibition can be reduced.

  Moreover, it is preferable that (D) hardening accelerator is an imidazole type hardening accelerator. This makes it possible to more effectively reduce the gas generated by the decomposition of the compound that generates an acid by (B) light during heating.

  In addition, (D) the curing accelerator is preferably blended with a liquid bisphenol A type epoxy resin, and the starting temperature of the curing exotherm when the temperature is raised is preferably 130 ° C. or lower. This makes it possible to more effectively reduce the gas generated by the decomposition of the compound that generates an acid by (B) light during heating.

  The thermal crosslinking agent (C) includes at least one compound selected from a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, a compound having an epoxy group, and a compound having an oxetanyl group. preferable. Thereby, developability, sensitivity, and heat resistance can be improved, and mechanical properties (for example, shear adhesive force) can be improved.

  The present invention also provides an adhesive pattern obtained by exposing and developing an adhesive layer formed from the positive photosensitive adhesive composition laminated on an adherend. Thereby, it is possible to obtain a good connection without entrapment of the resin when connecting the semiconductor chips or between the semiconductor chip and the semiconductor chip mounting support member.

  The present invention also includes a semiconductor wafer and an adhesive layer laminated on the semiconductor wafer, wherein the adhesive layer is a layer formed from the positive photosensitive adhesive composition. Provided semiconductor wafer. As a result, it is possible to exhibit good step embedding by expressing appropriate fluidity in the connection between the semiconductor chips or between the semiconductor chip and the semiconductor chip mounting support member, and it is possible to obtain a good connection.

  The present invention also provides a semiconductor device having a structure in which semiconductor chips are bonded to each other by the positive photosensitive adhesive composition or a structure in which a semiconductor chip and a support member for mounting a semiconductor chip are connected. To do. Thereby, the connection between the semiconductor chips or between the semiconductor chip and the semiconductor chip mounting support member is improved, and the connection reliability is also improved.

  According to the present invention, a positive-type photosensitive adhesive composition that can exhibit appropriate fluidity in connection between semiconductor chips or between a semiconductor chip and a semiconductor chip mounting support member, and further has few voids. Can be provided. Moreover, according to this invention, the adhesive pattern using the positive photosensitive adhesive composition, the semiconductor wafer with an adhesive layer, and a semiconductor device can be provided.

It is an end view which shows one Embodiment (film form) of the adhesive agent 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.

  Preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment. In addition, in the present specification, when a numerical range is expressed using “to”, a range including the numerical values described before and after that as the minimum value and the maximum value, respectively, is indicated. In this specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylic acid”. The term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of components present in the composition unless there is a specific notice when there are a plurality of substances corresponding to the respective components in the composition. 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 the present embodiment, 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.

[Positive photosensitive adhesive composition]
The present invention relates to a positive photosensitive adhesive composition containing (A) an alkali-soluble resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) a curing accelerator. By configuring the positive photosensitive adhesive composition as described above, appropriate fluidity can be expressed in the connection between the semiconductor chips or between the semiconductor chip and the semiconductor chip mounting support member. A small amount of positive photosensitive adhesive composition can be provided.

  The present inventors found that the positive photosensitive adhesive composition of the present embodiment is excellent in a fluid because of a photo-crosslinking reaction widely used for negative photosensitive materials in patterning processes such as exposure and development. This is thought to be due to not using a high molecular weight reaction such as. In addition, the inventors of the positive photosensitive adhesive composition according to the embodiment are less likely to generate voids by using (C) a thermal crosslinking agent and (D) a curing accelerator, and (B) by light. This is thought to be due to the ability to reduce the decomposition of the acid-generating compound. (B) Although many compounds that generate an acid by light decompose at a temperature lower than the curing reaction temperature, the present inventors have used (D) a positive accelerator before the decomposition temperature by using a curing accelerator. Since the curing reaction of the photosensitive adhesive composition can be initiated, it is believed that (B) decomposition of the compound that generates an acid by light can be suppressed.

  For example, when the decomposition temperature of the o-quinonediazide compound is 150 ° C. and the curing start temperature is 150 ° C. or higher, the decomposition of the o-quinonediazide compound starts before the curing reaction starts, and as a result, there is a concern that voids are generated. The On the other hand, by using a curing accelerator, the curing reaction is accelerated, the decomposition of the o-quinonediazide compound can be suppressed, and the generation of voids can be reduced.

  First, each component contained in the positive photosensitive adhesive composition will be described.

<(A) component: alkali-soluble resin>
The component (A) is not particularly limited as long as it is a resin that is soluble in an alkaline aqueous solution. 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 mass is used for development.

  Moreover, it can be confirmed as follows that the component (A) is soluble in an alkali developer.

  A coating film having a film thickness of about 5 μm is formed by spin-coating a varnish obtained by dissolving the component (A) alone or together with the component (B) described later in an arbitrary solvent on a substrate such as a silicon wafer. And This is immersed in either a TMAH aqueous solution, a metal hydroxide aqueous solution or an organic amine aqueous solution at 20 to 25 ° C. As a result, when the coating film can be dissolved uniformly, the component (A) is considered soluble in the alkaline developer.

  The Tg of the component (A) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower. When the Tg is 150 ° C. or less, the temperature when the film-like adhesive in the form of a positive photosensitive adhesive composition is bonded to an adherend can be reduced, and the semiconductor wafer is less likely to warp, There is a tendency that the melt viscosity of the adhesive after pattern formation does not become too high and the thermocompression bonding property is improved.

  From the viewpoint of further improving connection reliability such as reflow resistance, the Tg of the component (A) is preferably 40 ° C to 150 ° C, more preferably 50 ° C to 120 ° C, and 60 ° C to 100 ° C. It is more preferable that it is ° C. (A) By making Tg of a component into the said range, sufficient thermocompression-bonding property at the time of bonding a film-form positive photosensitive adhesive composition to a to-be-adhered body can be ensured, and connection reliability is further improved. Can do.

  Here, the Tg of the component (A) is a viscoelasticity analyzer (Rheometrics Scientific F.E. Co., Ltd., trade name: ARES) for the film-formed component (A). It is a tan δ peak temperature when measured under conditions of a temperature rising rate of 5 ° C./minute, a frequency of 1 Hz, and a measurement temperature of −150 ° C. to 300 ° C.

  The molecular weight of the component (A) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000, and more preferably 2,000 to 100,000, considering the balance of solubility in alkaline aqueous solution, photosensitive properties, and mechanical properties of the cured film. More preferably. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

  In the positive photosensitive adhesive composition of the present embodiment, the content of the component (A) is preferably 10% by mass to 90% by mass based on the total solid content of the photosensitive adhesive composition. It is more preferably from 80% by mass to 80% by mass, and further preferably from 30% by mass to 80% by mass. When the content of the component (A) is 10% by mass or more, the developability during pattern formation tends to be sufficient, and the handling properties such as tackiness tend to be sufficient, and the content is 90% by mass or less. And there exists a tendency for the developability and adhesiveness at the time of pattern formation to become enough. In addition, solid content refers to the component in compositions other than the substances which volatilize, such as a water | moisture content and the solvent mentioned later. That is, the solid content does not necessarily mean that the solid content includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C. Here, the substance that volatilizes refers to a substance having a boiling point of 260 ° C. or lower under atmospheric pressure.

  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 polyesterimide resins. , Polybenzoxazole resins, copolymers thereof and precursors thereof (polyamide acid, etc.), phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polycarbonate resins, polyether ketone resins, ( A meth) acrylic copolymer, a novolak resin, and a phenol resin are mentioned. 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 a glycol group such as ethylene glycol or propylene glycol, a carboxyl group, and / or a hydroxyl group.

  Among these, it is preferable that (A) component is a polyimide resin, a polyamide resin, a novolak resin, or a phenol resin from a viewpoint of high temperature adhesiveness, heat resistance, and film formation.

  From the viewpoint of high temperature adhesiveness and pattern formability, the alkali-soluble resin preferably has a phenolic hydroxyl group at the terminal group.

(Polyimide resin)
The polyimide resin according to this embodiment can be obtained, for example, by subjecting a tetracarboxylic dianhydride, a diamine, and a phenolic hydroxyl group-containing monoamine 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.

  In the above condensation reaction, the mixing molar ratio of the tetracarboxylic dianhydride and the phenolic hydroxyl group-containing monoamine is 0.04 mol of the total of the phenolic hydroxyl group-containing monoamine 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 the condensation reaction, tetracarboxylic dianhydride is preferably used in excess of diamine. Thereby, the oligomer which has the 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 monoamine described later, A phenolic hydroxyl group is introduced as a terminal group. The order of adding tetracarboxylic dianhydride, diamine, and phenolic hydroxyl group-containing monoamine may be arbitrary.

  The reaction temperature in the condensation reaction is preferably 80 ° C. or less, and more preferably 0 ° C. 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 deterioration of various characteristics of the positive photosensitive adhesive composition, the above tetracarboxylic dianhydride is preferably recrystallized and purified with acetic anhydride.

  The polyimide resin according to this embodiment means a resin having an imide group, and specifically, a polyimide resin, a polyamideimide resin, a polyurethaneimide resin, a polyetherimide resin, a polyurethaneamideimide resin, a siloxane polyimide resin, a polyester. Although an imide resin etc. are mentioned, it is not specifically limited to these.

  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, for example, a thermal ring closure method using heat treatment, 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 tetracarboxylic acid represented by the following general formula (1) An acid dianhydride 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 ( Trimellitate anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1 , 6- (Hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) ) Bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) ) Bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride) and 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

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

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

  As the diamine used as a 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 formula (5), (7) or (A-1). From the viewpoint of obtaining good pattern formability and thermocompression bonding when a polyimide resin having a high Tg is used, 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, a divalent hydrocarbon group having 1 to 30 carbon atoms in which part or all of hydrogen is substituted with a halogen atom, — (C═O) —, —SO ₂ —, —O—, —S—, —NH— (C═O) —, — (C═O) —O—, with 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 increased, it is possible to obtain a good pattern forming property, and it is possible to realize a 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 this embodiment, it is preferable that the diamine which has a phenolic hydroxyl group contains the diphenol diamine which has a fluoroalkyl group represented by a following formula (C-1). 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 (dissolvable developability, thinning) of the positive photosensitive adhesive composition is further improved. Further, the decrease in the cohesive strength of the polyimide can improve the thermocompression bonding property, and even if the Tg of the polyimide is increased, it is possible to obtain a good pattern forming property. This makes it possible to realize a positive photosensitive adhesive composition with 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 most 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 Sulfone, 3,4'-di Minodiphenyl 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-amino) Phenoxy) 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-aminophenoxy) phenyl) Sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, Aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 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). 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 each independently represent carbon. An alkyl group, a phenyl group or a phenoxy group represented by formulas 1 to 5 is shown, and d represents an integer of 1 to 5. The phenylene group may have a substituent.

  Among the diamines, the aliphatic ether diamines represented by the general formula (8) are preferable from the viewpoint of imparting compatibility with other components, organic solvent solubility, and alkali solubility, and ethylene glycol and / or propylene glycol diamines. Is more preferable.

  Specific examples of such aliphatic ether diamines include Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, and EDR manufactured by Sun Techno Chemical Co., Ltd. -148, BASF (manufactured) polyetheramine D-230, D-400, polyoxyalkylene diamine such as D-2000, and the like. These diamines are preferably 1 mol% to 80 mol% of all diamines, more preferably 10 mol% to 80 mol%, and still more preferably 10 mol% to 60 mol%. If this amount is 1 mol% or more, it tends to be easy to impart high temperature adhesiveness and hot fluidity, whereas 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.

  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 thereof is preferably 80 mol% or less of the total diamine, from the viewpoint of film self-supporting property, high-temperature adhesiveness, reflow resistance and moisture resistance reliability, and is 60 mol% or less. More preferably. 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. . 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 and adhesiveness in room temperature.

  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, 1,3-dimethyl-1,3- Methoxy-1,3-bis (4-aminobutyl) disiloxane and the like, where d is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-amino) Phenyl) 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) trishi Xanthone, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5 -Bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5 -Hexapropyl-1,5-bis (3-aminopropyl) trisiloxane 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. 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 the amount is less than 1 mol%, the effect of adding siloxane diamine is reduced, and when the amount is more than 80 mol%, the compatibility with other components, high-temperature adhesiveness, and developability tend to decrease.

  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 monoamine 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 monoamine. it can. Thereby, the weight average molecular weight of the polymer can be lowered, and the developability and thermocompression property at the time of pattern formation can be improved.

  As the phenolic hydroxyl group-containing monoamine, 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 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 is not only pattern-forming, thermocompression-bonding, and high-temperature adhesiveness, but also has stability and connection terminals when the positive photosensitive adhesive composition is in the form of a varnish or film. Since the embedding property (flatness) by applying or laminating to a substrate having protrusions or steps is improved, it is preferable.

  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.

(Polyamide resin)
Examples of the polyamide resin according to the present embodiment 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 polyamide resin according to the present embodiment 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. It is preferable that an amide unit containing a hydroxyl group represented by I) is contained in a certain proportion or more.

  As such a thing, the polyamide resin which has a structure represented by following formula (4) is mentioned.

  In the 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%. Yes, j is 60 to 100 mol%, and k is 40 to 0 mol%. As for the molar fraction of j and k, it is more preferable that j is 80-100 mol% and k is 20-0 mol%.

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., in which two or more aromatic rings are linked. It 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.

  As the phenolic hydroxyl group-containing diamine, a diamine represented by the following general formula (A-1) is 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, a divalent hydrocarbon group having 1 to 30 carbon atoms in which part or all of hydrogen is substituted with a halogen atom, — (C═O) —, —SO ₂ —, —O—, —S—, —NH— (C═O) —, — (C═O) —O—, with 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. 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. This makes it possible to realize a 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%. % To 70 mol% is more preferable.

  In this embodiment, it is preferable that phenolic hydroxyl group containing diamine contains the diphenol diamine which has a fluoroalkyl group represented by a 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 (dissolvable developability, thinning) of the positive photosensitive adhesive composition is further improved. In addition, due to the decrease in the cohesive strength of the polyamide, the thermocompression bonding property can be improved, and even if the Tg of the polyamide is increased, good pattern forming properties can be obtained. This makes it possible to realize a positive photosensitive adhesive composition with 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 most preferable to set it as 30 mol%-70 mol%.

  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.

  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, and 1,2-cyclobutane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarbo Or the like can be mentioned acid.

  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 the 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 entire dicarboxylic acid or the entire 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 monoamine 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 monoamine. Thereby, the weight average molecular weight of the polymer can be lowered, and the developability and thermocompression property at the time of pattern formation can be improved.

  As the phenolic hydroxyl group-containing monoamine, 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. More preferable.

  The polyamide resin having a phenolic hydroxyl group as a terminal group is not only pattern-forming, thermocompression-bonding and high-temperature adhesiveness, but also has stability and connection terminals when the positive photosensitive adhesive composition is in the form of varnish or film. This is preferable because the embedding (flatness) by coating or laminating on a substrate having protrusions or steps is improved.

  The 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 derivative 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, for example, 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 ° C. to 70 ° C., more preferably 0 ° C. 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 ° C. to 30 ° C., more preferably 0 ° C. to 20 ° C.

(Phenolic resin)
Examples of the phenol resin include novolak resin, resol resin, polyhydroxystyrene, polyhydroxyamide (polybenzoxazole precursor), poly (hydroxyphenylene) ether, polynaphthol, and the like. Among these, a novolak resin or a resin having a structural unit represented by the following general formula (31) is preferable from the viewpoint of cost and small volume shrinkage at the time of curing.

［一般式（３１）中、Ｒ^３１は水素原子又はメチル基を示し、Ｒ^３２は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ａは０〜３の整数を示し、ｂは１〜３の整数を示す。］

[In General Formula (31), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , A represents an integer of 0 to 3, and b represents an integer of 1 to 3. ]

  The phenol resin is obtained by polymerizing a monomer or the like that gives the structural unit represented by the general formula (31).

In the general formula (31), examples of the alkyl group having 1 to 10 carbon atoms represented by R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group and decyl group are mentioned. These groups may be linear or branched. Moreover, as a C6-C10 aryl group, a phenyl group and a naphthyl group are mentioned, for example. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, heptoxy group, octoxy group, nonoxy group and decoxy group. These groups may be linear or branched.

  Examples of the monomer that gives the structural unit represented by the general formula (31) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenyl. Phenol is mentioned. These monomers can be used alone or in combination of two or more.

  The method for obtaining the phenol resin is not particularly limited. For example, the hydroxyl group of the monomer that gives the structural unit represented by the general formula (31) is protected with a t-butyl group, an acetyl group, or the like to form a monomer in which the hydroxyl group is protected. Polymers obtained by polymerizing hydroxyl-protected monomers are obtained, and the obtained polymer is further deprotected by a known method (such as deprotection under an acid catalyst to convert to a hydroxystyrene-based structural unit). Can be obtained.

  The phenol resin may be a polymer or copolymer consisting only of a monomer that gives the structural unit represented by the general formula (31), a monomer that gives the structural unit represented by the general formula (31), and the others It may be a copolymer with the monomer. When the phenol resin is a copolymer, the proportion of the structural unit represented by the general formula (31) in the copolymer is 100 mol% of the phenol resin from the viewpoint of solubility in an alkaline developer in the exposed area. 10-100 mol% is preferable, 20-97 mol% is more preferable, 30-95 mol% is still more preferable, 50-95 mol% is especially preferable.

  The phenol resin may further be a phenol resin having a structural unit represented by the following general formula (26) from the viewpoint of further improving the dissolution inhibition property of the unexposed portion with respect to the alkaline developer.

一般式（２６）中、Ｒ^１０は水素原子又はメチル基を示し、Ｒ^１１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ｃは０〜３の整数を示す。

In General Formula (26), R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, c shows the integer of 0-3.

Examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the alkoxy group having 1 to 10 carbon atoms represented by R ¹¹ are the same as those of R ³² .

  The phenol resin having the structural unit represented by the general formula (26) can be obtained by using a monomer that gives the structural unit represented by the general formula (26). Examples of the monomer that gives the structural unit represented by the general formula (26) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, and m-methoxystyrene. And aromatic vinyl compounds such as p-methoxystyrene. These monomers can be used alone or in combination of two or more.

  When the phenol resin is a phenol resin having the structural unit represented by the general formula (26), it is represented by the general formula (26) from the viewpoint of the inhibition of dissolution of the unexposed portion with respect to the alkaline developer and the mechanical properties of the cured film. The proportion of the structural unit is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and particularly preferably 5 to 50 mol% with respect to 100 mol% of the phenol resin.

  Further, the phenol resin may be a phenol resin having a structural unit represented by the following general formula (27).

一般式（２７）中、Ｒ^１２は水素原子又はメチル基を示し、Ｒ^１３は炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を示す。

In General Formula (27), R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms.

  The phenol resin having the structural unit represented by the general formula (27) can be obtained by using a monomer that gives the structural unit represented by the general formula (27). Examples of the monomer that gives the structural unit represented by the general formula (27) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth). Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, (meth) acrylic acid Hydroxyoctyl, hydroxymethy (meth) acrylate And (meth) acrylic acid hydroxy decyl. These monomers can be used alone or in combination of two or more.

  When the phenol resin is a phenol resin having the structural unit represented by the general formula (27), it is represented by the general formula (27) from the viewpoints of dissolution inhibition with respect to an alkaline developer in an unexposed area and mechanical properties of the cured film. The proportion of the structural unit is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and particularly preferably 5 to 50 mol% with respect to 100 mol% of the phenol resin.

  The phenol resin has a structural unit represented by the general formula (31) and a structural unit represented by the general formula (26) from the viewpoints of dissolution inhibition with respect to the alkaline developer in the unexposed area and mechanical properties of the cured film. Phenol resin, phenol resin having a structural unit represented by the general formula (31) and a structural unit represented by the general formula (27), a structural unit represented by the general formula (31) and the general formula (26) It is preferable that it is a phenol resin which has a structural unit represented, and a structural unit represented by General formula (27). From the viewpoint of more manifesting the effects of the present invention, a phenol resin having a structural unit represented by the general formula (31) and a structural unit represented by the general formula (26) or (27) is more preferable.

<(B) component: Compound that generates acid by light>
The compound (B) that generates an acid by receiving light (by receiving light) functions as a photosensitive agent in the positive photosensitive adhesive composition. The component (B) has a function of generating acid upon irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution. Here, examples of the actinic rays used for the light irradiation for inducing acid generation of the component (B) include ultraviolet rays, visible rays, and radiation. As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. (B) A component may consist only of 1 type in these compounds, and may be comprised including 2 or more types. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  As the o-quinonediazide compound, for example, a compound obtained by subjecting o-quinonediazidesulfonyl chloride, a hydroxy compound and / or an amino compound to a condensation reaction in the presence of a dehydrochlorinating agent can be used.

  Examples of the o-quinonediazide sulfonyl chloride include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6-sulfonyl chloride. It is done.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl). ) -1-methylethyl} phenyl] ethane, 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-trihydroxypheny) ) Propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane and tris (4-hydroxyphenyl) ethane.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 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) hexafluo Propane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

  Among these, from the viewpoint of reactivity when synthesizing an o-quinonediazide compound and from the viewpoint of an appropriate absorption wavelength range when exposing a resin film formed from a positive photosensitive adhesive composition, 1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and naphthoquinone-1,2-diazide-5-sulfonyl chloride Obtained by condensation reaction of tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane with naphthoquinone-1,2-diazido-5-sulfonyl chloride Is preferred.

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

  In the blending of o-quinonediazide sulfonyl chloride with a hydroxy compound and / or amino compound, the total number of moles of hydroxy group and amino group is 0.5 to 1 mole per mole of o-quinonediazide sulfonyl chloride. It is preferable to be blended as described above. A preferable blending ratio of the dehydrochlorinating agent and o-quinonediazidesulfonyl chloride is in the range of 0.95 / 1 mol to 1 / 0.95 mol equivalent.

  In addition, the preferable reaction temperature of the above-mentioned reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

  The content of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. 5-50 mass parts is more preferable, 5-30 mass parts is still more preferable, and it is especially preferable to set it as 5-20 mass parts.

<(C) component: thermal crosslinking agent>
(C) The thermal crosslinking agent which is a component means the compound which bridge | crosslinks itself or resin with a heat | fever. The compound that crosslinks itself or the resin by heat is not particularly limited as long as it is a compound having a thermally crosslinkable group. Examples of component (C) include, but are not limited to, compounds having a phenolic hydroxyl group, compounds having a hydroxymethylamino group, compounds having an epoxy group, and compounds having an oxetanyl group.

  The “compound having a phenolic hydroxyl group” as used herein does not include (A) an alkali-soluble resin. The compound having a phenolic hydroxyl group as a thermal crosslinking agent can increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution as well as the thermal crosslinking agent, and improve the sensitivity. The weight average molecular weight of such a compound having a phenolic hydroxyl group is preferably 2000 or less, more preferably 94 to 2000 in consideration of the balance of solubility in an alkaline aqueous solution, photosensitive property and mechanical property. 108 to 2000 is more preferable, and 108 to 1500 is particularly preferable.

  As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the compound represented by the following general formula (28) is effective in promoting the dissolution of the exposed area and melting when the photosensitive adhesive film is cured. It is preferable because it is excellent in the balance of the effect of preventing the above.

［一般式（２８）中、Ｘは単結合又は２価の有機基を示し、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７はそれぞれ独立に水素原子又は１価の有機基を示し、ｓ及びｔはそれぞれ独立に１〜３の整数を示し、ｕ及びｖはそれぞれ独立に０〜３の整数を示す。］

[In General Formula (28), X represents a single bond or a divalent organic group, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a monovalent organic group, and s and t Each independently represents an integer of 1 to 3, and u and v each independently represents an integer of 0 to 3. ]

In general formula (28), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include, for example, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. An arylene group having 6 to 30 carbon atoms such as a group, a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, and an amide bond Is mentioned. Furthermore, as monovalent organic groups represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ , for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group, and a carbon such as a vinyl group Examples include C2-C30 aryl groups such as alkenyl groups of 2 to 10 and phenyl groups, and groups in which some or all of hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms.

  Examples of the compound represented by the general formula (28) include 1,1-bis {3,5-bis (methoxymethyl) -4-hydroxyphenyl} methane (trade name “TMOM” manufactured by Honshu Chemical Industry Co., Ltd.). -Pp-BPF ").

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) ( N-hydroxymethyl) urea-containing nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, and a butyl group, and may contain an oligomer component that is partially self-condensed. Specific examples of the compound having a hydroxymethylamino group include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril and tetrakis (methoxymethyl) urea. Can be mentioned.

  A conventionally well-known thing can be used as a compound which has an epoxy group. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type. Epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, glycidyl amines, heterocyclic epoxy resins, polyalkylene glycol diglycidyl ethers, and various polyfunctional epoxy resins can be used.

  As the component (C), in addition to the compounds described above, for example, bis [3,4-bis (hydroxymethyl) phenyl] ether, 1,3,5-tris (1-hydroxy-1-methylethyl) benzene, and the like Aromatic compounds having a hydroxymethyl group, compounds having a maleimide group such as bis (4-maleimidophenyl) methane, 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, A polyfunctional (meth) acrylate compound, a compound having an oxetanyl group, a compound having a vinyl group, and a blocked isocyanate compound can also be used.

  Among the components (C) described above, it is preferable to use a compound having an epoxy group or a hydroxymethylamino group from the viewpoint that sensitivity and heat resistance can be further improved, and an epoxy from the point that resolution and coating film elongation can be further improved. A compound having a group is more preferred.

  The content of the component (C) is preferably 0.5 to 80 parts by mass, preferably 10 to 70 parts by mass with respect to 100 parts by mass of the component (A), because the development residue is small and the curing reaction by heating is compatible. Is more preferable, and 15-60 mass parts is still more preferable.

<(D) component: hardening accelerator>
The (D) component curing accelerator is for accelerating the crosslinking and curing of the (C) component. For example, a phenol resin-based curing accelerator, an acid anhydride-based curing accelerator, an amine-based curing accelerator, and an imidazole-based compound. A hardening accelerator and a phosphine type hardening accelerator are mentioned.

  By using the curing accelerator, the curing reaction of the positive photosensitive adhesive composition can be started before the temperature at which the component (B) is decomposed by heating, and therefore the decomposition of the component (B) can be suppressed. I believe.

  The decomposition temperature of component (B) is preferably not less than the reaction start temperature of the positive photosensitive adhesive composition, and more preferably not less than the curing reaction peak temperature of the positive photosensitive adhesive composition.

  Note that the curing reaction peak temperature of the positive photosensitive adhesive composition is the peak of the exothermic or endothermic peak when the composition is heated at a heating rate of 10 ° C./min using a suggested scanning calorimeter DSC. It is the top temperature. The reaction start temperature of the positive photosensitive adhesive composition is a rising curve of an exothermic or endothermic peak when the composition is heated at a temperature rising rate of 10 ° C./min using a suggested scanning calorimeter DSC. This is the temperature at the intersection of the tangent and temperature axis where the slope of the peak is steepest.

  Specifically, when the component (B) is an o-quinonediazide compound (decomposition temperature 150 ° C.), the curing reaction peak temperature of the positive photosensitive adhesive composition is preferably 150 ° C. or less, more preferably 140 ° C. or less. The reaction start temperature of the positive photosensitive adhesive composition is more preferably 150 ° C. or lower, and particularly preferably 130 ° C. or lower.

  Specifically, examples of the curing accelerator that promotes crosslinking and curing of the component (C) include imidazole-based curing accelerators. Examples of the imidazole curing accelerator include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 - Mino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 , 3-Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Midazorin, 2-phenyl-imidazoline, and adducts of an epoxy resin and imidazoles like.

  Among these, compounds that are blended with a liquid bisphenol A type epoxy resin and have a starting temperature of curing exotherm when the temperature is raised are preferably 130 ° C. or less, such as 2-methylimidazole, 2-undecylimidazole, and 2-heptadecyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium Trimellate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct and 2 -Phenylimidazole isocyanuric acid adduct is preferred.

  Further, from the viewpoint of suppressing voids, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1- Benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4 -Diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 1-cyanoethyl-2-methylimidazole and 2,4-diamino-6- [2'-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine isocyanuric acid adduct is more preferred.

  These can be used alone or in combination of two or more. Moreover, you may use these as a latent hardening | curing agent which encapsulated these.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, as for content of an imidazole series hardening accelerator, 0.1-10 mass parts is more preferable, and 2-8 mass parts is still more preferable. . If the content of the imidazole curing accelerator is 0.1 parts by mass or more, the curability tends to be improved, and if it is 20 parts by mass or less, the adhesive for a semiconductor is cured before a metal bond is formed. There is a tendency that poor connection is unlikely to occur.

<Other ingredients>
In addition to the components (A) to (D), the positive photosensitive adhesive composition of the present embodiment includes an elastomer, a compound that generates an acid upon heating, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a surface activity. An agent, a leveling agent or a fluxing agent may be contained.

(Elastomer)
A conventionally known elastomer can be used as the elastomer, but the glass transition temperature (Tg) of the polymer constituting the elastomer is preferably 20 ° C. or lower.

  Examples of such elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, silicone elastomers, and acrylic resin elastomers. The elastomer may be a fine particle elastomer. These elastomers can be used alone or in combination of two or more.

  As for content in the case of using an elastomer, 1-60 mass parts is preferable with respect to 100 mass parts of (A) component, 3-40 mass parts is more preferable, and 5-30 mass parts is still more preferable.

(Compound that generates acid by heating)
By using a compound that generates an acid by heating, it becomes possible to generate an acid when the resin film after pattern formation is heated, and a reaction between the component (A) and the component (C), that is, a thermal crosslinking reaction is performed. It is accelerated and the heat resistance of the cured film is improved. Moreover, since the compound which produces | generates an acid by heating generate | occur | produces an acid also by light irradiation, the solubility to the alkaline aqueous solution of an exposure part increases. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed area and the exposed area is further increased, and the resolution is further improved.

  It is preferable that the compound which produces | generates an acid by such a heating is what produces | generates an acid by heating to 50-250 degreeC, for example. Specific examples of the compound that generates an acid by heating include a salt formed from a strong acid such as an onium salt and a base, and imide sulfonate.

  When using the compound which produces | generates an acid by heating, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, 0.2-20 mass parts is more preferable, 0.5 More preferably, it is 10 mass parts.

(Dissolution promoter)
By blending the dissolution accelerator in the above-mentioned positive photosensitive adhesive composition, the dissolution rate of the exposed area when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. A conventionally well-known thing can be used as a dissolution promoter. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, a sulfonamide group and the like.

  Content in the case of using such a dissolution promoter can be determined by the dissolution rate with respect to the aqueous alkali solution, and can be, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of component (A).

(Dissolution inhibitor)
A dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. In the case of using a dissolution inhibitor, the content is preferably 0.01 to 20 parts by mass, and 0.01 to 15 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of sensitivity and the allowable range of development time. More preferably, 0.05-10 mass parts is still more preferable.

(Coupling agent)
By mix | blending a coupling agent with a positive photosensitive adhesive composition, the adhesiveness with the board | substrate of the cured film formed can be improved more. Examples of the coupling agent include organic silane compounds and aluminum chelate compounds. Moreover, as an organic silane compound, urea propyl triethoxysilane is mentioned, for example.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using a coupling agent, 0.5-10 mass parts is more preferable.

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent into the positive photosensitive adhesive composition, the coating property can be further improved. Specifically, for example, by containing a surfactant or a leveling agent, striation (film thickness unevenness) can be further prevented, and developability can be further improved. Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include, for example, Megafax F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd., trade name), Florard FC430, FC431 (Sumitomo 3M Limited, trade name), organosiloxane polymer KP341, Examples thereof include KBM303, KBM403, and KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using surfactant or a leveling agent, 0.01-3 mass parts is more preferable.

  The positive photosensitive adhesive composition of this embodiment can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH). Furthermore, by using the positive photosensitive adhesive composition of the present embodiment described above, it is possible to form a cured film having good adhesion and thermal shock with sufficiently high sensitivity and resolution.

(Film adhesive)
A film-like adhesive can be obtained by molding a composition containing the above-described components on 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 a composition containing each of the above components into a film.

  The film adhesive 1 is formed into a film shape by, for example, applying a solution of the composition containing each of the above-described components onto the substrate 3 shown in FIG. Thus, the adhesive sheet 100 provided with the base material 3 and the adhesive layer 1 made of the film-like adhesive formed on the base material 3 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 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 1 can be obtained, for example, by the following method. First, component (A), component (B), component (C), component (D) and other components 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 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.

  Examples of the organic solvent include acetone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypupionate, N-methyl-2- Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethyl phosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether , Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, toluene, benzene, xylene, methyl ethyl ketone Tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane and ethyl acetate. These organic solvents can be used alone or in combination of two or more. Among these, it is preferable to use methyl ethyl ketone, ethyl lactate or propylene glycol monomethyl ether acetate from the viewpoint of solubility and uniformity of the coating film.

  Mixing and kneading of the varnish 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 the heating is performed at a temperature at which the component (C) does not sufficiently react and under conditions where the solvent is sufficiently volatilized. The above “temperature at which the component (C) does not sufficiently react” is specifically DSC (for example, product name: DSC-7, manufactured by Perkin Elmer), 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 50 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 20% by mass or less. When the residual volatile content is 20% 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 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.

(Liquid adhesive)
The positive photosensitive adhesive composition of this embodiment may be used in liquid form. The blending, mixing and kneading of the varnish may be the same as the above-described film adhesive method. The liquid positive type photosensitive adhesive composition for adhesive is applied onto the substrate 12 and spin-coated using a spinner or the like to form a coating film. Although there is no restriction | limiting in particular in the thickness of a coating film, 1 micrometer-200 micrometers are preferable. 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 content tends to decrease, and the flatness of the coating film also tends to be good. The substrate on which this coating film has been formed is dried using a hot plate, oven, or the like. Although there is no restriction | limiting in particular in drying temperature and drying time, It is preferable to carry out for 1 to 10 minutes at 50 to 180 degreeC. Thereby, a photosensitive adhesive film is formed on the support substrate.

  The adhesive pattern according to this embodiment can be obtained by exposing and developing an adhesive layer formed from the positive photosensitive adhesive composition laminated on the adherend.

[Semiconductor wafer with adhesive layer]
The semiconductor wafer with an adhesive layer according to the present embodiment includes a semiconductor wafer and an adhesive layer laminated on the semiconductor wafer. The adhesive layer is a layer formed from the positive photosensitive adhesive composition.

  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 an 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.

  The semiconductor wafer 20 with an adhesive layer is coated with a liquid positive photosensitive adhesive composition for adhesive on the semiconductor wafer 8, spin-coated using a spinner or the like, and dried using a hot plate, oven, or the like. Alternatively, a method of laminating the adhesive layer 1 on the semiconductor wafer 8 may be used.

[Semiconductor device]
The semiconductor device according to the present embodiment 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 by the positive photosensitive adhesive composition. .

  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 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 between the support member 13 and the semiconductor chip 14 where the adhesive layer 1 is not disposed. 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).
(Second Step) A step of patterning the adhesive layer 1 by exposure and development so as to form the opening 11 through which the connection terminal is exposed (FIGS. 9 and 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 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 singulated, and the connection electrode of the support 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.

  In addition, the laminating method is to apply a liquid positive photosensitive adhesive composition for adhesive to the semiconductor wafer 12, spin coat using a spinner or the like, dry using a hot plate, oven, etc. The method of laminating the adhesive layer 1 on 12 may be used.

  The positive photosensitive adhesive composition for an adhesive according to the present embodiment has an adhesive property to an adherend after being patterned by exposure and development, and is capable of alkaline development. It is a composition. More specifically, a resist pattern formed by patterning a positive photosensitive adhesive composition for an adhesive 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). After the development, the entire surface may be exposed again or heated. It is preferable that the entire surface is exposed again after 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, indentation with a roll, and filling under reduced pressure can be adopted. 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 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, and the connecting electrode portion of the supporting member 13 and the semiconductor chip 14. These connection terminals are electrically connected through the conductive layer 9. Note that an adhesive layer (buffer coat film) on which a pattern is formed 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 (positive photosensitive resin composition for film adhesive) is thermocompression-bonded while being heated to such a temperature as to exhibit fluidity. 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 adhering to the layer 1 side, the connection terminal of the support member 13 and the connection electrode portion of the semiconductor wafer 12 may be electrically connected via the conductive layer 9. Furthermore, in the fifth step, the laminated body of the semiconductor wafer 12, the adhesive 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, patterning can be performed so that the conductive layer 9 is exposed in the second step, and the third step can be omitted to proceed to the fourth step.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis Example 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. 8.66 g (0.02 mol) of fluoropropane 21.96 g (0.06 mol), D-400 (manufactured by BASF, trade name: D-400, molecular weight: 433), BY16-871EG (Toray Dow Corning Co., Ltd.) 2.485 g (0.01 mol) of product name: BY16-871EG, molecular weight: 248.5), 2.183 g (0.02 mol) of m-aminophenol, N-methyl-2-pyrrolidone as a solvent 80 g of (NMP) was charged and stirred to dissolve the diamine in the solvent.
While the flask was cooled in an ice bath, 31 g (0.1 mol) of 4,4′-oxydiphthalic dianhydride (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 A1. About the obtained polyimide resin A1, when the GPC measurement was performed based on the following measurement conditions, the weight average molecular weight (Mw) was 28000 in polystyrene conversion. Moreover, Tg was 100 degreeC. It was confirmed by ¹ H-NMR that there were no remaining carboxyl groups.

(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), H3PO4 (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm
Measurement was performed using 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the sample.
Measurement temperature: 23 ° C

[(A) component: alkali-soluble resin]
A1: Polyimide resin A1 produced in Synthesis Example 1, Mw = 28000, Tg = 100 ° C.
A2: Polyhydroxystyrene resin (hydroxystyrene / styrene (molar ratio) = 85/15, Mw = 10000, manufactured by Toho Chemical Co., Ltd., trade name “C100A15S”).
A3: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, Mw = 12000, Tg = 150 to 170 ° C., trade name “Asahi Organic Materials Co., Ltd.” EP4020G ").
In addition, the weight average molecular weight (Mw) of A2 and A3 was measured based on the following measurement conditions.

(Measurement conditions of weight average molecular weight in terms of GPC standard polystyrene of A2 and A3)
Measuring device: RI monitor L-3300 manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Autosampler: Hitachi, Ltd. L-7200
Measurement condition: Column TSK guard column HXL-L, TSK GEL GMHXL-L x 2 manufactured by Tosoh Corporation Eluent: THF
Flow rate: 1.0 mL / min, detector: RI
It measured using the solution of 1 mL of solvent with respect to 1.0 mg of samples.

[Component (B): Compound that generates acid by light]
B1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Ester (esterification rate: about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”).

[(C) component: thermal crosslinking agent]
C1: Polyfunctional epoxy resin (trade name “1032H60” manufactured by Mitsubishi Chemical Corporation).
C2: Bisphenol F type epoxy resin (trade name “YL983U” manufactured by Mitsubishi Chemical Corporation).
C3: Epoxy resin (trade name “YL7175-1000B80” manufactured by Mitsubishi Chemical Corporation).

[(D) component: curing accelerator]
D1: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name “2E4MZ]).
D2: 2-undecylimidazole (trade name “C11Z” manufactured by Shikoku Kasei Co., Ltd.).
D3: 2-phenyl-4-methyl-5-hydroxymethylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name “2P4MHZ-PW”).

[(B ′) component: photoradical generator]
B′2: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF, trade name “I-189”).

(Examples 1-5 and Comparative Examples 1-3)
Each component and the solvent, methyl ethyl ketone, were blended in the blending amounts (unit: parts by mass) shown in Table 1 so that the solid content was 65% of the total weight. Examples 1 to 5 and Comparative Examples 1 to 3 A photosensitive adhesive composition was prepared.

  The obtained photosensitive adhesive composition was applied onto a substrate (peeling agent-treated PET film) so that the film thickness after drying was 25 μm or 45 μm, and heated in an oven at 70 ° C. for 10 minutes. And the adhesive bond layer which consists of a film-form photosensitive adhesive composition was formed on the base material. Thus, the adhesive sheet which has a base material and the adhesive bond layer formed on the base material was obtained.

<Evaluation of photosensitive adhesive composition>
About the photosensitive adhesive composition of Examples 1-5 and Comparative Examples 1-3, evaluation shown below was performed.

(Preparation of evaluation sample)
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 70 ° C., linear pressure 39 N / cm (4 kgf / cm), feed rate 0.5 m / min). Subsequently, the base material (PET film) was peeled and removed to expose the adhesive layer, thereby preparing an evaluation sample.

(Photosensitive characteristics)
In the same manner as in the production of the evaluation sample, the laminates in which an adhesive layer having a thickness of 25 μm was laminated on a silicon wafer were compared in Examples 1 to 5 and Comparative Examples 2 and 3 through a positive pattern mask. In Example 1, exposure was performed from the adhesive layer side through a negative pattern mask. The exposure was performed at 1000 mJ / cm ² using a high-precision parallel exposure machine (trade name: EXM-1172-B-∞, manufactured by Oak Seisakusho). Subsequently, after developing using 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, it washed with water and dried. In this way, an adhesive pattern of the photosensitive adhesive composition was formed on the silicon wafer.

  The formed adhesive pattern was visually observed, and the photosensitive characteristics were evaluated as ◯ when a dot pattern having a diameter of 60 μm or less was opened, and as x when the dot pattern was not opened.

(Connectivity)
A silicon chip with connection terminals (solder bumps) (chip size: length 7.3 mm × width 7.3 mm × height 755 μm, bump height: copper pillar + solder about 45 μm, number of bumps 328) is placed on the support base. On top of this, an adhesive sheet having a thickness of 45 μm was laminated 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. The obtained laminate was exposed from the adhesive layer side through a glass mask using a mask exposure machine (manufactured by Mikasa, Mask Aligner MA-20). For Examples 1 to 5 and Comparative Examples 2 and 3, a positive-type dot pattern glass mask with a diameter of 60 μm was used, and for Comparative Example 1, a negative-type dot pattern glass mask with a diameter of φ60 μm was used. It exposed so that the connection terminal part of a chip might open. The exposure amount was set to the minimum exposure amount at which a dot pattern having a diameter of 60 μm opened. After exposure, development is performed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), followed by rinsing with water, and a silicon chip with an adhesive layer in which the connection terminal portion of the silicon chip is opened with a diameter of 60 μm Got.

  The silicon chip with connection terminals formed with the adhesive layer prepared above is flip-chip mounting apparatus FCB3 (trade name, manufactured by Panasonic Corporation), and a glass epoxy substrate (glass epoxy substrate: 0.4 mm thick, copper wiring: 9 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 daisy chain connection between the glass epoxy substrate and the semiconductor chip with the gold bump as described above, the connection resistance value was measured with a multimeter (manufactured by ADVANTEST) to evaluate the possibility of initial conduction after mounting (conductivity). . The case where the connection resistance value was displayed was evaluated as ◯, and the case where the connection resistance value was not displayed due to the occurrence of connection failure was evaluated as x.

(Liquidity)
After the mounting test, when the silicon chip was viewed from above, the flowability was evaluated when the photosensitive adhesive composition protruded from before the mounting, and the flowability x when the photosensitive adhesive composition did not protrude.

(Void generation)
In the same manner as in the production of the evaluation sample, a laminate in which an adhesive layer having a thickness of 45 μm was laminated on a silicon wafer was separated into pieces having a size of 2 mm × 2 mm. Laminate the glass substrate so that the adhesive layer of the separated laminate is in contact with the glass substrate (10 mm × 10 mm × 0.55 mm), and press-fit at 100 ° C. for 30 seconds while pressing with 20 N (2 kgf), and then Crimping was performed at 150 ° C. for 30 seconds. 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 is observed through the glass. The void at the interface between the cured product layer and the glass substrate is less than 30% of the entire surface of the glass substrate. Evaluation was performed by setting the larger one as x. In addition, in the said evaluation, when it is (circle) or (triangle | delta), it can be said that the photosensitive adhesive composition is favorable about void generating property.

  As is apparent from Table 1, it was confirmed that the positive photosensitive adhesive compositions of Examples 1 to 5 were excellent in photosensitive characteristics, connectivity and fluidity, and generated less voids.

  On the other hand, an adhesive pattern could not be formed in Comparative Example 1 using a photoradical generator instead of the component (B). In Comparative Example 2 in which the component (C) was not used and in Comparative Example 3 in which the component (D) was not used, generation of voids could not be reduced.

  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 positive photosensitive adhesive composition comprising (A) an alkali-soluble resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) a curing accelerator.   The positive photosensitive adhesive composition according to claim 1, wherein the compound that generates an acid by (B) light is an o-quinonediazide compound.   The positive photosensitive adhesive composition according to claim 1 or 2, wherein the (D) curing accelerator is an imidazole curing accelerator.   The said (D) hardening accelerator mix | blends with a liquid bisphenol A type epoxy resin, and the start temperature of hardening heat_generation | fever when it heats up is 130 degrees C or less, As described in any one of Claims 1-3. Positive photosensitive adhesive composition.   The (C) thermal crosslinking agent includes at least one compound selected from the group consisting of a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, a compound having an epoxy group, and a compound having an oxetanyl group, The positive photosensitive adhesive composition as described in any one of Claims 1-4.   An adhesive pattern obtained by exposing and developing an adhesive layer formed from the positive photosensitive adhesive composition according to any one of claims 1 to 5 laminated on an adherend. . A semiconductor wafer and an adhesive layer laminated on the semiconductor wafer;
The semiconductor wafer with an adhesive layer whose said adhesive bond layer is a layer formed from the positive photosensitive adhesive composition as described in any one of Claims 1-5.   A semiconductor device having a structure in which semiconductor chips are bonded to each other by the positive photosensitive adhesive composition according to claim 1.   A semiconductor device having a structure in which a semiconductor chip and a support member for mounting a semiconductor chip are bonded by the positive photosensitive adhesive composition according to claim 1.

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