A negative photosensitive composition and use thereof

Abstract

The application discloses a negative photosensitive composition and application thereof. The negative photosensitive composition is composed of the following raw materials in a certain weight percentage: (A1) bismaleimide, (A2) polyimide precursor, (A3) polymerizable monomer containing unsaturated bond, (B) photopolymerization initiator, and (C) solvent. The composition can obtain a cured product film with convex-concave structure after photolithography and curing, and the cured product film can be used as a redistribution layer, an interlayer insulating buffer film, a covering coating or a surface protection film material in electronic devices.

Description

TECHNICAL FIELD

[0001] The present invention relates to a photosensitive dielectric material used in the field of electronic devices, and in particular to a negative photosensitive composition containing a bismaleimide, a polyimide precursor, and a polymerizable monomer containing an unsaturated bond, a cured product prepared therefrom, and the use thereof in semiconductor packaging and display manufacturing. BACKGROUND

[0002] The progress of science and technology has always been closely related to the development of material science, especially the semiconductor chips and display manufacturing that support many current frontier technology fields are closely dependent on the latest progress of material science. In recent years, the newly developed semiconductor chip and display manufacturing methods cannot be separated from high-performance organic polymer thin film materials; many new manufacturing processes in these fields require organic polymer materials to have good insulating properties, high mechanical properties, excellent adhesion, high temperature stability, low water absorption, high chemical corrosion resistance, and other characteristics. Traditional epoxy, phenolic, polyacrylate and other materials obviously cannot fully meet these requirements.

[0003] On the other hand, from the perspective of simplifying the process and reducing manufacturing costs, the manufacturing process of electronic devices such as chips / displayers is increasingly inclined to choose photosensitive organic polymer materials. The photosensitive properties of such materials will help to provide a thin film layer with different convex-concave patterns (also known as a relief pattern layer) at a lower cost. These relief pattern layers can provide an effective process solution for preparing deposited copper metal lines in the chip packaging process, thereby enabling the transmission of electrical signals between the chip and the external circuit. In addition, they can also be used as various types of insulating dielectric materials such as surface protective coatings, base layers, flat layers, pixel partition layers, adhesive materials, etc. in display manufacturing processes. In these applications, organic polymer dielectric materials can simultaneously play the roles of protection, insulation, wrapping, buffering, bonding, and metal migration prevention.

[0004] Due to the above comprehensive requirements, the photosensitivity of polyimide (PI), benzocyclobutene (BCB), polybenzoxazole (PBO) gradually became the current mainstream photosensitive dielectric film material. Each of the three materials has its own advantages, but has some shortcomings in practical application: the first photosensitive polyimide material is still the only choice for many processes, but it has the disadvantages of large water absorption and large film thickness loss in the post-curing process; the benzocyclobutene (BCB) material developed by Dow Electronic Chemicals Company has poor tensile properties and cannot solve the material stability problem in device deformation caused by long-term thermal expansion and contraction in some applications; photosensitive polybenzoxazole has been increasingly widely used in recent years due to its use of alkaline aqueous developer and high tensile strength, but it also has the problem of large film thickness loss in the process. Therefore, the existing photosensitive composition containing polyimide, benzocyclobutene, and polybenzoxazole, and the cured product prepared therefrom still have various inconveniences and defects, and need to be further improved.

[0005] On the basis of the aforementioned three types of high-performance photosensitive materials, the present application introduces a new type of negative photosensitive composition mainly composed of bismaleimide / polyimide ester; the thin film prepared using this composition is proved to have excellent mechanical properties, adhesion, long-term stability and resistance to chemical reagent corrosion. In addition, on the basis of maintaining high material mechanical properties, this new composition has the characteristics of good development and high resolution, thereby having great market demand and application prospect. SUMMARY

[0006] The main purpose of the present application is to overcome the defects of existing photosensitive dielectric materials and provide a new negative photosensitive composition. The solid thin film prepared from the composition has excellent mechanical properties, insulating properties, adhesion, high temperature stability, low water absorption, high chemical corrosion resistance and other advantages.

[0007] Another main purpose of the present application is to provide a patterned cured product prepared using the new negative photosensitive composition.

[0008] Still another purpose of the present application is to provide the application of the above-mentioned cured product in redistribution layer, interlayer insulating buffer film, cover coating or surface protection film.

[0009] Still another purpose of the present application is to use the above-mentioned cured product in related electronic products.

[0010] The purpose of the present application and the solution to its technical problems are realized by adopting the following technical scheme. A negative photosensitive composition contains:

[0011] (A1) a bismaleimide,

[0012] (A2) a polyimide precursor,

[0013] (A3) a polymerizable monomer containing an unsaturated bond,

[0014] (B) a photopolymerization initiator, and

[0015] (C) a solvent.

[0016] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0017]

[0018] wherein R1 is a divalent aromatic group selected from any one of the following structural units represented by the following general formula (2):

[0019]

[0020] Q in general formula (2) is a direct bond or a divalent organic group selected from O, S, CO, SO2, Si(CH3)2, CH(OH), (CH2) x (1≤x≤10), (CF2) y (1≤y≤10), C(CH3)2, C(CF3)2; m and n are each any integer between 1 and 50.

[0021] The negative photosensitive composition according to claims 1 to 2, wherein the (A2) component is a polyimide precursor structural unit containing an unsaturated bond represented by the following general formula (3):

[0022]

[0023] wherein X is a 4-valent organic group, and the -COOR3 group and the -CONH- group are each in the ortho position to each other, and the -COOR2 group and the -CO- group are each in the ortho position to each other; Y is a 2-valent organic group; p is any integer between 2 and 150; R2 and R3 are each independently a hydrogen atom, a 1-valent organic group represented by the following general formula (4), or a saturated aliphatic group having a carbon number of 1 to 6; and at least one of R2 and R3 is the 1-valent organic group represented by general formula (4).

[0024]

[0025] In general formula (4), q is any integer between 1 and 20, and R4, R5, and R6 are the same or different 1-valent organic groups selected from a hydrogen atom or an aliphatic hydrocarbon group having a carbon atom number of 1 to 3.

[0026] The negative photosensitive composition according to claims 1 to 3, wherein the (A3) component is a polymerizable monomer containing an unsaturated bond, and the polymerizable monomer containing an unsaturated bond is a group having two or more unsaturated double bonds.

[0027] The object and technical problem of the present application are also solved by the following technical solution. The negative photosensitive composition according to the present application further comprises:

[0028] The negative photosensitive composition according to claims 1 to 4, wherein the (B) component is a photopolymerization initiator.

[0029] The negative photosensitive composition according to claims 1 to 5, wherein the (C) component is an organic solvent, and comprises at least one compound selected from the group consisting of esters, ethers, ether-esters, ketones, ketone-ester-hydrocarbons, aromatic compounds, and / or halogenated hydrocarbons.

[0030] The negative photosensitive composition according to the present application can further comprise various functional optional components as needed in addition to the above-mentioned components. As the optional components, adhesion promoters, sensitizers, polymerization inhibitors, anti-discoloration agents, and leveling agents can be mentioned.

[0031] The object and technical problem of the present application are also solved by the following technical solution. The cured product having a relief pattern prepared from the negative photosensitive composition according to the present application is prepared by a method comprising:

[0032] (a) a step of applying the composition on a substrate and heating to remove the solvent to form a photosensitive resin film;

[0033] (b) a step of performing pattern exposure on the photosensitive resin film using a mask;

[0034] (c) a step of removing the unexposed area of the coating layer to obtain a resin cured product film having a relief pattern, and

[0035] (d) a step of performing a heating and curing treatment on the relief pattern resin film.

[0036] The object and technical problem of the present application are also solved by the following technical solution. The object and technical problem of the present application are also solved by the following technical solution.

[0037] The aforementioned cured product having a relief pattern, wherein the temperature of the heating treatment is 275-400°C.

[0038] The aforementioned cured product having a relief pattern, which is a cured product film having a microstructure relief pattern.

[0039] The application also achieves the above-mentioned purposes and solves the above-mentioned technical problems by the following technical solutions. The cured product with the relief pattern is applied to a redistribution layer, an interlayer insulating buffer film, a cover coating or a surface protection film.

[0040] The application also achieves the above-mentioned purposes and solves the above-mentioned technical problems by the following technical solutions. An electronic device containing the redistribution layer, the interlayer insulating buffer film, the cover coating or the surface protection film is provided.

[0041] As known from the above, the application discloses a negative photosensitive composition and application thereof. The negative photosensitive composition is composed of the following raw materials in a certain weight percentage: (A1) bismaleimide, (A2) polyimide precursor, (A3) polymerizable monomer containing unsaturated bond, (B) photopolymerization initiator and (C) solvent. The composition can obtain a cured product film with convex-concave structure after photolithography and curing, and the cured product film can be used as a redistribution layer, an interlayer insulating buffer film, a cover coating or a surface protection film material in an electronic device.

[0042] Compared with the prior art, the application has obvious advantages and beneficial effects. In order to achieve the above-mentioned purposes, the main technical contents of the application are as follows:

[0043] A negative photosensitive composition containing (A1) bismaleimide, (A2) polyimide precursor, (A3) polymerizable monomer containing unsaturated bond, (B) photopolymerization initiator and (C) solvent, a cured product prepared therefrom and application thereof in semiconductor packaging.

[0044] Through the above technical solutions, the negative photosensitive composition, the cured product prepared therefrom and application thereof in semiconductor packaging provided by the application have at least the following advantages:

[0045] In view of various defects required by traditional photosensitive dielectric materials, the negative photosensitive composition containing bismaleimide and polyimide precursor is used in the application. It is found that the composition can prepare a thin film with excellent performance and relief microstructure. Since the bismaleimide and polyimide precursor are introduced into the cured product film at the same time, the product inherits the advantages of high-temperature stability of bismaleimide and polyimide precursor; and is beneficial to preparing high-performance photosensitive polymerization dielectric materials with good developing property and high resolution. In addition, the resin composition has excellent adhesion to various substrates after curing. Finally, by using the polyimide precursor containing fluorine atoms and bismaleimide in the composition, the new materials have good light transmittance at I-line wavelength and can reduce the water absorption of the material, so that the cured product film prepared from the composition is more suitable for the requirements of current advanced packaging processes.

[0046] In summary, the technical scheme of the present application has the above-mentioned advantages and practical value, and no similar design has been published or used in similar products, and it is indeed innovative. It has greater improvement in formula and function, and produces good and practical effects. It has more functions than existing products, and is more suitable for practical use, and has wide industrial utilization value. It is a novel, progressive and practical new design.

[0047] The above description is only a summary of the technical scheme of the present application. In order to more clearly understand the technical means of the present application and can be implemented according to the content of the specification, the following will be described in detail with the preferred embodiments of the present application and with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 It is an embodiment of the present application, which relates to the manufacture of a redistribution layer. DETAILED DESCRIPTION

[0049] In order to further illustrate the technical means and effects taken by the present application to achieve the predetermined purpose, the specific embodiments of the negative photosensitive composition, the cured product prepared therefrom and the application thereof in semiconductor packaging according to the present application are described in detail as follows.

[0050] In the present specification, "(meth)acrylate" refers to "acrylate" and "methacrylate".

[0051] The photosensitive resin composition of the present application contains: (A1) a bismaleimide (hereinafter, also referred to as "(A1) component"), (A2) a polyimide precursor (hereinafter, also referred to as "(A2) component"), (A3) a polymerizable monomer containing an unsaturated bond (hereinafter, also referred to as "(A3) component"), (B) a photopolymerization initiator (hereinafter, also referred to as "(B) component"), and (C) a solvent (hereinafter, also referred to as "(C) component").

[0052] The photosensitive resin composition of the present application is a negative photosensitive resin composition. Hereinafter, the present application will be further specifically described by exemplifying each component of the composition. It should be noted that the present application is not limited by these examples, and those having ordinary knowledge in the art can make various modifications within the technical idea of the present application.

[0053] I. (A1) component: bismaleimide

[0054] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein the (A1) component is a bismaleimide structural unit represented by the following general formula (1):

[0055] The negative photosensitive composition according to claim 1, wherein

[0056] wherein R1 is a divalent aromatic group selected from any one of the structural units represented by the following general formula (2):

[0057]

[0058] Q in general formula (2) is a direct bond or a divalent organic group selected from O, S, CO, SO2, Si(CH3)2, CH(OH), (CH2) x (1≤x≤10), (CF2) y (1≤y≤10), C(CH3)2, C(CF3)2; m and n are each any integer between 1 and 50.

[0059] As the (Al) component, there is no particular limitation, and it is preferable to have a structure group represented by the following formula (5) that has high transmittance when i-line is used as a light source at the time of patterning and that can provide good flexibility:

[0060]

[0061] The (Al) component here can be used alone or in combination with two or more in the negative photosensitive composition.

[0062] II. (A2) component:

[0063] The negative photosensitive composition according to claims 1 to 2, the (A2) component is a polyimide precursor structure unit having an unsaturated bond represented by the following general formula (3):

[0064]

[0065] wherein X is a 4-valent organic group, and the -COOR2 group and the -CO- group are in the ortho position to each other, and the -COOR3 group and the -CONH- group are in the ortho position to each other; Y is a 2-valent organic group; p is any integer between 2 and 150; R2 and R3 are each independently a hydrogen atom, a 1-valent organic group represented by the following general formula (4), or a saturated aliphatic group having a carbon number of 1 to 6; wherein at least one of R2 and R3 is a 1-valent organic group represented by general formula (4).

[0066]

[0067] In formula (4), q is any integer between 1 and 20, and R4, R5, and R6 are the same or different 1-valent organic groups selected from hydrogen or aliphatic hydrocarbon groups having a carbon atom number of 1 to 3.

[0068] The component (A2) of the negative photosensitive composition described above, from the viewpoint of reducing the material stress, the X in the general formula (3) is preferably a divalent aromatic linking group, and can preferably contain a structural unit represented by the following general formula (6).

[0069]

[0070] The component (A2) of the negative photosensitive composition described above, from the viewpoint of reducing the material thermal expansion coefficient and increasing the glass transition temperature, the X in the general formula (3) is preferably a divalent aromatic linking group, and can preferably contain a structural unit represented by the following general formula (7).

[0071]

[0072] In addition, the transmittance of i-line directly affects the resolution of the photosensitive composition during the process. In order to obtain the optimal microstructure relief pattern under the same film thickness condition, the component (A2) of the negative photosensitive composition is preferably a polyimide monomer structure with good light transmittance, which can be achieved by selecting a diamine precursor containing fluorine element for Y in the component (A2). These fluorine-containing monomers are also beneficial to reducing the swelling effect of the solution on the film during development to inhibit bleeding from the surface, and can also reduce the water absorption of the cured composition. Therefore, the Y in the component (A2) of the negative photosensitive composition described above, from the comprehensive consideration of light transmittance and water absorption, is preferably a structural unit represented by the following general formula (8) containing a trifluoromethyl group.

[0073]

[0074] The film prepared from the negative photosensitive composition described above is usually developed using an organic solvent. Therefore, a polyimide precursor with high solubility in organic solvents is preferred, which requires that the weight average molecular weight of the polyimide precursor in the component (A2) of the present application is generally selected between 5,000 and 200,000. The weight average molecular weight is preferably between 10,000 and 150,000. Here, the molecular weight is determined by gel permeation chromatography (GPC) method and calculated using a standard polystyrene standard curve.

[0075] The synthesis method of the polyimide precursor described above is not particularly limited, and a synthesis method of a polyimide precursor is specifically described below in combination with several synthesis examples.

[0076] Synthesis Example 1:

[0077] First, a three-necked flask was charged with 4,4'-oxydiphthalic dianhydride (ODPA, 100 mmol), 2-hydroxyethyl methacrylate (HEMA, 200 mmol), and hydroquinone (0.110 g) dissolved in N-methyl-2-pyrrolidone (NMP, 198 g) dried by a drying machine, and esterification was carried out by stirring at room temperature (25°C) for 36 hours after adding a catalytic amount of 1,8-diazabicycloundec-5-ene (DBU), to obtain an ODPA(HEMA) solution.

[0078] Then, thionyl chloride (215 mmol) was added dropwise to the ODPA(HEMA) solution obtained in the above step in a flask equipped with a stirrer and a thermometer under ice-bath cooling conditions (the temperature of the reaction solution was maintained at 10°C or less). After the completion of the dropwise addition of thionyl chloride, the reaction was carried out for 1.5 hours under ice-bath cooling to obtain an acyl chloride solution of ODPA(HEMA).

[0079] Finally, a mixed solution containing 2,2'-bis(trifluoromethyl)benzidine (100.0 mmol), pyridine (436 mmol), hydroquinone (0.08 g), and N-methyl-2-pyrrolidone (NMP, 90 g) was added dropwise to the acyl chloride solution of ODPA(HEMA) in the flask described above using a dropping funnel while maintaining the temperature of the solution at 10°C or less. After the completion of the reaction, the reaction solution was dropped into a flask containing a large amount of distilled water, and the precipitate was collected by stirring and filtration, and then dried under reduced pressure to obtain a polyimide precursor (referred to as Polymer-1) having the following structure. The molecular weight thereof was 41,050, and the polydispersity (PD) was 1.61.

[0080]

[0081] The same synthesis method was employed, except that the diamine precursor was replaced with 4,4'-oxydianiline, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, respectively, to obtain the following polyimide precursors: Polymer-2 (molecular weight: 38,000, polydispersity: 1.57), Polymer-3 (molecular weight: 43,470, polydispersity: 1.57), and Polymer-4 (molecular weight: 49,010, polydispersity: 1.69), respectively.

[0082]

[0083] The (A2) component can be used alone or in combination with two or more in the negative photosensitive composition. The weight ratio of the (A2) component to the (Al) component in the negative photosensitive composition according to claims 1 to 3 is between 1:10 and 5:1, preferably between 1:3 and 3:1.

[0084] III. (A3) Component: Polymerizable monomer containing unsaturated bond

[0085] The (A3) component is a polymerizable monomer containing unsaturated bond in the negative photosensitive composition according to claims 1 to 3, and further the polymerizable monomer containing unsaturated bond is a group having two or more unsaturated double bonds. The polymerizable monomer is preferably a (meth)acrylate compound, and in order to increase the crosslinking density and the photosensitivity and to suppress the swelling of the pattern after development, the (meth)acrylate compound preferably has a (meth)acrylate compound having two or more polymerizable unsaturated double bonds represented by the following formula -9.

[0086]

[0087] The (A3) component can be used alone or in combination with two or more in the negative photosensitive composition. The weight ratio of the (A3) component to the sum of the other two Al and A2 components

(Al) + (A2)

[0088] IV. (B) Component: Photopolymerization initiator

[0089] The photoinitiator as the (B) component in the present application is a compound that generates radicals upon irradiation with light. The (B) component is at least one photoinitiator selected from, but not limited to, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoin derivatives, benzoin ethers, and oxime ester compounds in the negative photosensitive composition according to claims 1 to 4. From the viewpoint of sensitivity and imaging properties, the oxime ester compound represented by the following formula -10 is preferred.

[0090]

[0091] The negative photosensitive composition containing the oxime ester compound photoinitiator is crosslinked by radicals generated upon exposure through a mask after film formation, and the solubility of the exposed portion is significantly reduced. In the non-exposed portion, the photoinitiators do not undergo chemical reactions and thus maintain good solubility in the developer. As a result, there is a large difference (contrast) in the dissolution rate between the exposed area and the non-exposed area (dark area), and further a film having a microstructure relief pattern is obtained after the development step.

[0092] The (B) component in the negative photosensitive composition can be used alone, or two or more can be used in combination or in combination with a sensitizer. The weight ratio of the (B) component to the sum of the (Al) + (A2) + (A3) components is 1 : 15 to 1 : 200, preferably 1 : 20 to 1 : 150, in the negative photosensitive composition according to Claims 1 to 5. Within the above range, the exposed portion of the polymer is crosslinked to a good degree, and a practical relief pattern having a uniform film thickness is obtained.

[0093] V. (C) Component: Solvent Component

[0094] The (C) component in the negative photosensitive composition according to Claims 1 to 5 is an organic solvent, and includes at least one compound selected from the group consisting of esters, ethers, ether-esters, ketones, ketone-ester-hydrocarbons, aromatic compounds, and / or halogenated hydrocarbons. The (C) component dissolves the above (Al), (A2), (A3), and (B) components to form a varnish of the composition. In general, there is no particular limitation as long as the other components in the negative photosensitive composition are sufficiently dissolved. Some commonly used solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, ε-caprolactone, cyclopentanone, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl- 1,3-butanediol acetate, 1,3-butanediol acetate, cyclohexanone, tetrahydronaphthalene, tetrahydrofuran, and the like. Of these solvents, N-methyl-2-pyrrolidone, γ-butyrolactone, tetrahydronaphthalene, and cyclopentanone are preferably used from the viewpoints of solubility and superior coating properties of the resin film.

[0095] The (C) component in the negative photosensitive composition can be used alone, or two or more can be used in combination. The content of the (C) component is not particularly limited; from the viewpoints of controlling the film thickness and coating properties of the coating film, the weight ratio of the (C) component to the sum of the (Al) + (A2) + (A3) components is 10 : 1 to 1 : 2, preferably 8 : 1 to 2 : 3.

[0096] VI. Other Components of the Composition

[0097] The negative photosensitive composition of the present application can further contain other auxiliary components, such as cross-linking agents, corrosion inhibitors, tackifiers, sensitizers, polymerization inhibitors, nanoparticles, and surfactants, etc., as needed, in addition to the above-described (Al), (A2), (A3), (B), and (C) components. The principle of adding these auxiliary agents is not to substantially impair the basic physical properties of the final cured product film of the present application; and the addition of these auxiliary agents often improves the processing properties of the material or enhances certain aspects of the properties of the final cured film to make it more suitable for some specific processes. These components and their functions are described in detail below.

[0098] Cross-linking agent: The negative photosensitive composition of the present application can contain a cross-linking agent component. The cross-linking agent generally undergoes a cross-linking reaction with other components of the negative photosensitive composition during the curing step to strengthen the mechanical properties of the material. Therefore, a compound that does not react with other components of the negative photosensitive composition is preferred. The cross-linking agent component includes at least one alkoxyl compound, peroxide, epoxy compound, oxetane compound, or vinyl ether compound. From the viewpoint of the mechanical properties of the cured product film and the high reactivity at low temperature curing, a compound represented by the following formula (11) is preferred.

[0099]

[0100] To obtain the optimal resolution and chemical resistance of the cured film, the content of the cross-linking agent is preferably 3 to 50 parts by mass, and further preferably 5 to 40 parts by mass, relative to 100 parts by mass of the sum of the A components

(Al) + (A2) + (A3)

[0101] Anticorrosive agent - When the negative type photosensitive composition of the present application is applied to a copper or copper alloy substrate, in order to suppress discoloration and stability reduction due to copper corrosion, at least one compound containing a triazole ring, an imidazole ring, and a thiazole ring of Formula (12) having a carbon atom and a nitrogen atom can be added to the composition. As the azole compound, for example, 1H-triazole, 1H-benzotriazole, 2-(2H-benzotriazol-2-yl) p-cresol, 1,5-dimethyltriazole, 4,5-diethyl-lH-triazole, 4-tert-butyl-5-phenyl-lH-triazole, 5-ethyl-lH-triazole, 4,5-dimethyl-lH-triazole, 5-phenyl-lH-triazole, 5-hydroxyphenyl-lH-triazole, p-ethoxyphenyltriazole, 5-phenyl-l-(2-dimethylaminoethyl)triazole, 5-benzyl-lH-triazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 4-methyl-lH-benzotriazole, 4-carboxy-lH-benzotriazole, 5-methyl-lH-tetrazole, 5-phenyl-lH-tetrazole, tetrazole, 5-amino-tetrazole, 1-methyl-lH-tetrazole, and the like can be listed.

[0102]

[0103] In order to obtain the optimal metal corrosion resistance, the content of the anticorrosive agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the sum of the components (Al) + (A2) + (A3).

[0104] Adhesion promoter - In order to improve the adhesion of the cured product film formed from the negative photosensitive composition of the present application to a substrate, an adhesion aid (adhesion promoter) component can be arbitrarily blended in the negative photosensitive composition. The adhesion promoter can be selected from organosilane compounds or aluminum-based adhesion aids including tri(ethylacetoacetato)aluminum, tri(acetylacetone)aluminum, ethyl aluminum diisopropylate, and the like. From the viewpoint of improving adhesion to substrates such as copper, it is preferable to use organosilane compounds. The organosilane compounds include 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, triethoxysilylpropyl carbamate, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. These organosilane compounds can be used alone or in combination of two or more.

[0105] The content of the adhesion promoter component in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the sum of the A components

(A1) + (A2) + (A3)

[0106] Sensitizer - The negative photosensitive composition according to the present application can further contain a sensitizer. As the sensitizer, benzalmalononitrile, 4'-N,N-dimethylaminobenzalmalononitrile, 4'-acetylamino benzalmalononitrile-4-methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4'-bis(N-ethyl, N-methyl)benzophenone, 4,4'-bis-(diethylamino)benzophenone, and the like can be exemplified. These sensitizers can be used alone or in combination of two or more. The content of the sensitizer in the composition is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the sum of the A components

(A1) + (A2) + (A3)

[0107] Polymerization inhibitor - In order to increase the long-term storage stability of the negative photosensitive composition according to the present application, the negative photosensitive composition according to the present application can further contain a polymerization inhibitor. As the polymerization inhibitor, 2,6-di-t-butyl-p-cresol, m-dinitrobenzene, N-phenyl-2-naphthalene, nitrosamine, and the like can be exemplified. Here, the polymerization inhibitor can be used alone or in combination of two or more. The content of the polymerization inhibitor in the composition is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the sum of the A components [(Al) + (A2) + (A3)].

[0108] Nanoparticle - The resin composition according to the present application can further contain a nanoparticle. The addition of these nanoparticle materials to the composition particularly improves the performance of the cured product film in terms of optical properties, hardness, coefficient of thermal expansion, and the like. As the nanoparticle, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, and the like can be exemplified. These nanoparticle materials are preferably those having a particle diameter of 70 nm or less and having been surface-modified. The content of the nanoparticle is preferably 0.5 to 50 parts by mass, and more preferably 2 to 30 parts by mass, relative to 100 parts by mass of the (A) component.

[0109] Surfactant - In order to improve the coatability and surface smoothness at the time of spin coating, a surfactant can be added to the composition as a leveling agent. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Some examples that can be purchased directly from the market include Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals, Incorporated); silicone oxane-based KP341, KBM303, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.); fluorine-containing surfactants PolyFox PF-6320 (Omnova Solutions), Fluorad FC430, FC171 (manufactured by Sumitomo 3M Co., Ltd.), and the like. The content of the surfactant used is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the sum of the A components [(Al) + (A2) + (A3)].

[0110] Table-1 below is a more preferable example of the negative photosensitive composition according to the present application.

[0111] In these examples and tables, the sum of (A1) component, (A2) component, and (A3) component

(A1) + (A2) + (A3)

(A1) + (A2) + (A3)

[0112] In addition, in these examples, the specific information of other components used in addition to the aforementioned polyimide (A2) component is as follows:

[0113]

[0114]

[0115] (B-a): OXE-1 (BASF, Germany)

[0116] (B-b): TR-PBG-3057 (Qiangli New Material, Changzhou, China)

[0117] (B-c): TR-PBG-346 (Qiangli New Material, Changzhou, China)

[0118] (C-a): Tetralin

[0119] (C-b): 50% γ-butyrolactone + 30% tetralin + 20% ethyl lactate

[0120] (C-c): 50% N-methyl-2-pyrrolidone (NMP) + 50% tetralin

[0121] (D-a): 5-amino-tetrazole

[0122] (D-b): Tetrazole

[0123] (D-c): 1H-benzotriazole

[0124] (E-a): 3-(2,3-epoxypropoxy)propyltrimethoxysilane

[0125] (E-b): 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane

[0126] (E-c): γ-ureidopropyltriethoxysilane

[0127] (F-a): Hexamethoxymethylmelamine

[0128] (G-a): PF-6320 (fluorine-containing surfactant, Omnova Solutions) Example 1: The A1-b ingredient (60 parts by mass), the polymer-4 obtained in Synthesis Example 4 (20 parts by mass), the A3-a ingredient (20 parts by mass), and B-a (2 parts by mass) as a photoinitiator were dissolved in N-methyl-2-pyrrolidone (NMP) (C-a, 160 parts by mass), and D-a (1.5 parts by mass) as an anticorrosive agent and E-c (3 parts by mass) as an adhesion promoter were added to obtain a negative photosensitive resin composition according to the present application.

[0129] The preparation method of Examples 2 to 10 and Comparative Examples 1 and 2 was exactly the same as that of Example 1, except that the respective components or amounts used therein were different. The details are shown in Table-1 below.

[0130] Table-1

[0131]

[0132] NA: represents that the component is not contained in the composition.

[0133] The negative photosensitive composition (also referred to as varnish) obtained in the above examples / comparative examples was filtered through a polytetrafluoroethylene filter membrane to obtain a final negative photosensitive composition. The polytetrafluoroethylene filter membrane having a pore size of 0.45 to 3 micrometers can be selected according to the polymer concentration in the composition and the viscosity of the varnish. The varnish obtained in the above examples / comparative examples was coated on a copper wafer to form a negative photosensitive cured film according to the method described in claim 7 above.

[0134] Seven, method for manufacturing cured product and application

[0135] Hereinafter, embodiments of a method for manufacturing a patterned cured product, a cured product, a redistribution layer, an interlayer insulating buffer film, a cover coat or a surface protective film, and an electronic device according to the present application will be described in detail. Note that the present application is not limited to the following embodiments.

[0136] A method for manufacturing a patterned cured product using the negative photosensitive composition according to the present application includes the following steps:

[0137] (a) Resin film forming step: a step of forming a photosensitive resin film by coating the negative photosensitive composition described in claims 1 to 6 on a substrate and drying by heating to remove the solvent. As the substrate, semiconductor substrates such as Si substrates (silicon wafers), ceramic substrates, metal substrates (including copper substrates, aluminum substrates, copper alloy substrates, etc.), silicon nitride substrates, etc. can be listed. The coating method can employ spin coating, spray coating, dipping, etc., and from the viewpoint of controlling the film thickness, spin coating using a spin coater is preferred. The drying by heating can use a hot plate, an oven, etc. The drying temperature by heating is preferably 90 to 150°C, more preferably 90 to 130°C.

[0138] (b) Exposure step: a step of performing pattern exposure on the photosensitive resin film using a mask. The pattern exposure is, for example, exposure to a predetermined pattern through a photomask. The active light rays irradiated can include ultraviolet rays such as i-line, visible rays, radioactive rays, etc., and i-line is preferred. As the exposure device, a scanning exposure machine, a projection exposure machine, a step-and-repeat exposure machine, etc. can be used.

[0139] (c) Developing step: by performing the developing step, a resin film having a microstructure relief pattern can be obtained. In general, the developing is performed by a method such as dipping, spin spray, etc. In the case of using the negative photosensitive composition of the present application, the developing solution can remove the unexposed portions of the film to thereby obtain a relief pattern. The developing time is generally 10 seconds to 15 minutes, and from the viewpoint of improving the productivity and process control, 20 seconds to 5 minutes is preferred. As the developing solution, N-methyl-2-pyrrolidone, cyclopentanone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclohexanone, etc. can be selected. In each of the aforementioned developing solutions, a proper amount of a surfactant can be added as needed to enhance the developing effect. Of these developing solutions, cyclopentanone is preferred. After the developing, a rinsing solution can be used for cleaning to remove the developing solution, and thereby a pattern film can be obtained. As the rinsing solution, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in combination.

[0140] After the negative photosensitive composition is made into a solution, it is spin-coated on a substrate such as a silicon wafer, dried by heating to remove the solvent, and a resin film having a film thickness of about 10 micrometers is formed; then it is dipped in a cyclopentanone solvent at 20 to 25°C; and the ease of dissolving the component (A) in the organic developing solution is judged from the time required for the film to be completely dissolved.

[0141] (d) heating and curing step: The heating and curing step is a process of heating and curing the relief pattern resin film to obtain the optimum material properties. In this step, the relief pattern obtained by the development described above is heated and cured. The heating temperature is preferably 275 to 4000C using a hot plate or an oven. The heating time is usually 30 minutes to 4 hours, more preferably 30 minutes to 2 hours, considering the time required for the cross-linking reaction. The heating is usually performed in an atmosphere of an inert gas such as nitrogen or argon. The heating and curing is preferably performed in an atmosphere of high-purity nitrogen (≥99.999%) in consideration of the prevention of oxidation of the pattern resin film and the process cost.

[0142] The cured product of the present application is a cured film of the polymer resin obtained by the above-mentioned process. The cured film can be either a cured film having a relief pattern or a cured film without a pattern.

[0143] The cured film can be laminated in direct contact with a semiconductor element or can be laminated with other layers interposed therebetween. They can also be used to coat other materials such as metal wires to function as an insulating medium. Applications include, for example, redistribution layers, interlayer insulating buffer films, cap layers, or surface protective film materials.

[0144] The cured product of the present application is a cured film of the polymer resin obtained by the above-mentioned process. The cured film can be either a cured film having a relief pattern or a cured film without a pattern.

[0145] The cured film can be laminated in direct contact with a semiconductor element or can be laminated with other layers interposed therebetween. They can also be used to coat other materials such as metal wires to function as an insulating medium. Applications include, for example, redistribution layers, interlayer insulating buffer films, cap layers, or surface protective film materials.

[0146] The present application will be described below with reference to the accompanying drawings. Figure 1 A manufacturing method of a redistribution layer according to the present application will be described.

[0147] Figure 1 (Structure cross-sectional schematic diagram) is a construction of a redistribution layer structure using the composition of the present application and its embodiments. It should be noted that the film thickness and device size in the figure do not represent the actual proportions. In the present embodiment, the signal can be input / output between a chip (Al Pad: aluminum contact pad electrode) and the outside (Solder Bump: solder bump) by the design of a two-layer wiring structure. The two-layer wiring structure is realized by a copper redistribution layer lead (Cu RDL) wrapped in an insulating material polymer layer (polymer layer 1 and polymer layer 2). As shown in the figure, the signal is input / output between the chip and the outside through the redistribution layer lead (Cu RDL) and the polymer layer 1 and 2. Figure 1The copper leads connect the aluminum pad electrodes (Al Pads) and solder bumps on the chip. The solder bumps are connected to other packages or motherboards in the next process after packaging to achieve package-to-package or package-to-motherboard connections. The connection between the solder bumps and the copper leads is achieved through the UBM studs. The two layers of insulating material (polymer layer 1 and polymer layer 2) use the polysulfonamide cured film described in the present application. Through such design and construction, re-wiring and changing the position / size of the contact electrodes can be achieved. In addition, the polysulfonamide cured film here not only serves as an insulating dielectric material for wrapping the copper leads, but also plays a structural role in relieving internal stress. These materials need to have good long-term stability to maintain excellent stability and material recovery ability in the thermal expansion and contraction cycle and its accompanying stress changes caused by constant temperature changes.

[0148] Using one or more selected from the above redistribution layer, interlayer insulating buffer film, cover coating or surface protection film material, etc., a semiconductor package, multilayer circuit board, display circuit, etc. with high reliability and good stability can be manufactured.

[0149] Eight, evaluation of negative photosensitive resin composition

[0150] Evaluation of adhesion - The cured film in the present application is mainly used as an insulating material for wrapping copper leads, so good adhesion between the two materials is a key material parameter. The present application uses an American Society for Testing and Materials (ASTM) standard method to evaluate the adhesion of the material: D3359 Standard Test Methods for Measuring Adhesion by Tape Test. The specific operation details are as follows: the obtained relief-free pattern cured film (on the copper base layer) is cut into a 10x10 grid of small squares (each square has an area of 1mm*1mm) with a zigzag hatch knife in the vertical direction. According to the method described in ASTM D3359, the adhesive tape (produced by 3M) is attached to these small pieces of cured film, and the adhesive tape is peeled off. The number of small pieces of cured film peeled off from the substrate when the adhesive tape is peeled off is used to judge the adhesion of the material. In the present application, the following standard A or B is used to judge the adhesion of the material film to the copper substrate. The detailed results are listed in Table-2.

[0151] A: No peeled squares

[0152] B: At least 1 peeled square

[0153] As seen from Table 2 below, the cured product film obtained by the present application has excellent adhesion to copper substrates in general.

[0154] Evaluation of discoloration inhibition - For the cured film obtained by covering the copper metal, the appearance was evaluated by optical microscope and naked eye. If the cured film could well maintain the original color of the underlying copper metal film after curing, it was evaluated as A: discoloration was inhibited; if the color of the copper under the cured film was obviously changed to deep red / brown, it was evaluated as B: discoloration was not inhibited. The detailed results are listed in Table 2.

[0155] A: discoloration was inhibited

[0156] B: discoloration was not inhibited

[0157] In summary, the poly-sulfonamide cured product film proposed by the present application effectively solves the problem of poor adhesion of such materials to copper substrate materials, and has excellent protective effect on the copper metal of the substrate.

[0158] Table 2

[0159] Examples / Comparative Examples Adhesion Discoloration Inhibition Example #1 A A Example #2 A A Example #3 A A Example #4 A A Example #5 A A Example #6 A A Example #7 A A Example #8 A A Example #9 A A Example #10 A A Comparative Example #1 A B Comparative Example #2 B A Comparative Example #3 Failed to Film Failed to Film

[0160] The above description is only the preferred embodiments of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiments, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed methods and technical contents to make equivalent embodiments with equivalent changes, without departing from the technical solution of the present application. Any simple modification, equivalent change and modification of the above embodiments, which does not depart from the technical solution of the present application, and which is based on the technical essence of the present application, shall still fall within the scope of the present application.

Claims

1. A negative photosensitive composition comprising at least: (A1) a bismaleimide having either of the following structures: (A2) a polyimide precursor; (A3) a polymerizable monomer containing an unsaturated bond; (B) a photopolymerization initiator; and (C) a solvent.

2. The negative photosensitive composition according to claim 1, wherein the (A2) component is a polyimide precursor structure unit containing an unsaturated bond represented by the following general formula (3): ###0001### wherein X is a 4-valent organic group, and the -COOR2 group and the -CO- group are in the ortho position to each other, and the -COOR3 group and the -CONH- group are in the ortho position to each other; Y is a 2-valent organic group; p is any integer between 2 and 150; R2 and R3 are each independently a hydrogen atom, a 1-valent organic group represented by the following general formula (4), or a saturated aliphatic group having a carbon number of 1 to 6; and at least one of R2 and R3 is the 1-valent organic group represented by the general formula (4); ###0002### wherein q is any integer between 1 and 20, and R4, R5, and R6 are the same or different 1-valent organic groups selected from hydrogen or an aliphatic hydrocarbon group having a carbon atom number of 1 to 3. wherein 3. The negative photosensitive composition according to claim 1, wherein the (A3) component is a polymerizable monomer containing an unsaturated bond, and the polymerizable monomer containing an unsaturated bond is a group having two or more unsaturated double bonds.

4. The negative photosensitive composition according to claim 1, wherein the (B) component is a photopolymerization initiator.

5. The negative photosensitive composition according to claim 1, wherein the (C) component is an organic solvent including at least one compound selected from the group consisting of esters, ethers, ether-esters, ketones, aromatic compounds, and / or halogenated hydrocarbons.

6. A cured product having a relief pattern prepared from the negative photosensitive composition according to any one of claims 1 to 5, the preparation of the cured product comprising the steps of: (a) a step of applying the composition to a substrate and heating to remove the solvent to form a photosensitive resin film; (b) a step of performing pattern exposure on the photosensitive resin film using a mask; (c) a step of removing the coated area that has not been exposed to light to obtain a resin cured product film having a relief pattern, and (d) a step of performing a heat curing process on the resin film having a relief pattern.

7. The cured product having a relief pattern according to claim 6, wherein the temperature of the heat curing process is 275 to 400°C.

8. The cured product having a relief pattern according to claim 6, which is a cured product film having a microstructure relief pattern.

9. Use of the cured product having a relief pattern according to any one of claims 6 to 8 in a redistribution layer, an interlayer insulating buffer film, a cover coat, or a surface protective film.

10. An electronic device comprising the redistribution layer, the interlayer insulating buffer film, the cover coat, or the surface protective film according to claim 9. ​ ​

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