CN111704720A

CN111704720A - Aromatic polyamide sulfonamide polymers, negative-type photosensitive compositions containing aromatic polyamide sulfonamide polymers, and uses thereof

Info

Publication number: CN111704720A
Application number: CN202010589483.9A
Authority: CN
Inventors: 崔庆洲
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-06-24
Filing date: 2020-06-24
Publication date: 2020-09-25

Abstract

The invention discloses an aromatic polymer (aromatic polyamide sulfamide polymer) with a main chain containing both amido bond and sulfamide bond, a negative photosensitive composition (polyamide sulfamide composition) containing the aromatic polyamide sulfamide polymer and application thereof. The negative photosensitive composition comprises the following raw materials in percentage by weight: an aromatic polyamide sulfonamide polymer, a photoacid generator, a crosslinking agent, and a solvent. The composition can prepare a polyamide sulfamide cured film under the condition of lower curing temperature (less than or equal to 250 ℃), and the cured 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.

Description

Aromatic polyamide sulfonamide polymers, negative-type photosensitive compositions containing aromatic polyamide sulfonamide polymers, and uses thereof

Technical Field

The present invention relates to a photosensitive dielectric material used in the field of electronic devices, and more particularly, to a negative photosensitive composition containing an aromatic polyamide sulfonamide polymer, a cured product prepared therefrom, and use thereof in semiconductor packaging and display manufacturing.

Background

Advances in science and technology have been associated with advances in material science, particularly with recent advances in material science that have supported much of the current state of the art in semiconductor chip and display manufacturing. Recently developed methods for manufacturing semiconductor chips and displays do not require high performance organic polymer materials, and these new methods require that the organic polymer materials have the characteristics of good insulating properties, high mechanical properties, excellent adhesion, high temperature stability, low water absorption, high chemical resistance, and the like. Traditional epoxy, phenolic, polyacrylate and other materials obviously cannot meet the requirements.

On the other hand, the manufacturing process of electronic devices such as chip/display devices is more and more apt to select a photosensitive organic polymer material from the viewpoint of simplification of the process and reduction of the manufacturing cost. The photosensitive properties of these materials would facilitate the provision of a different patterned thin film layer (also known as an embossed pattern layer) at a lower cost, which is combined with copper-based metals during chip packaging, thereby enabling electrical signal transmission within the chip microstructure. In addition, they can be used as surface protective coatings, adhesive materials, base/planarization layers, and other various types of insulating dielectric materials in display manufacturing processes. In these applications, the organic polymeric material provides protection, insulation, encapsulation, cushioning, adhesion, and metal migration resistance.

Due to the above comprehensive requirements, three materials, i.e., Polyimide (PI), Polybenzoxazole (PBO), and benzocyclobutene (BCB), which are photosensitive, are becoming the main photosensitive polymeric materials at present. These three materials have different ages, but all have some disadvantages in practical application: the first-appearing photosensitive polyimide materials are still not the second choice in many process steps, but have the disadvantages of larger water absorption, larger film thickness loss in the post-curing process and use of organic developing solution which is not friendly to the environment; benzocyclobutene (BCB) materials developed by the Dow's electronics chemical company in the United states have poor tensile properties, and the problem of material stability in device deformation caused by long-term expansion with heat and contraction with cold cannot be solved in some applications; the photosensitive polybenzoxazole has been widely used in recent years due to the use of an alkaline aqueous solution developer and a good tensile strength, but it cannot solve the problem that the material has a large film thickness loss in the process. Accordingly, there are various inconveniences and disadvantages in the conventional photosensitive composition containing polyimide, polybenzoxazole and benzocyclobutene and the cured product thereof, and further improvement is desired.

Based on the three types of high performance photosensitive materials mentioned above, a new class of polysulfonamide polymers has been successfully developed in recent years, which have been demonstrated to have excellent mechanical properties, adhesion, long-term stability, and resistance to chemical agents. In addition, the polysulfonamide polymers can be used for preparing positive or negative photosensitive dielectric materials according to a photochemical mechanism in a formula; in particular, the negative polysulfonamide composite overcomes the problem of large film thickness loss of the traditional material in the application, and has great market demand and application prospect.

The invention provides a novel polyamide sulfonamide polymer and a composition material thereof on the basis of the polyamide sulfonamide polymer. Because the amide group and the sulfonamide group which are formed according to a certain proportion are simultaneously introduced into the polymer, the mixed polymer material integrates the structural characteristics and the performance of polyamide and polysulfonamide and has the advantages of the two materials. On the basis of keeping higher mechanical properties of the material, the solubility of the polyamide sulfamide polymer material in an alkaline developer is very high, thereby being beneficial to preparing a photosensitive polymeric material with good developability and high resolution. In addition, the resin composition has excellent adhesion to various substrates even under the condition of curing at low temperature, thereby being suitable for preparing low-temperature crosslinking type high-performance photosensitive dielectric materials.

Disclosure of Invention

The main purpose of the present invention is to overcome the defects of the existing photosensitive dielectric material, and to provide a novel polyamide sulfonamide polymer, wherein the aromatic polyamide sulfonamide polymer has the advantages of excellent mechanical properties, insulating properties, adhesion, high-temperature stability, low water absorption, high chemical corrosion resistance, etc.

Another main object of the present invention is to provide compositions containing polyamide sulfonamide polymers, which can provide effective crosslinking ability and excellent lithographic performance under a low-temperature (250 ℃ or lower) heat treatment condition, thereby producing cured products having a relief microstructure.

Another object of the present invention is to provide a composition containing a polyamide sulfonamide polymer, which greatly improves the disadvantage of the conventional positive photosensitive material that the film thickness loss is large, by utilizing the advantage of the chemical reaction of negative crosslinking that the film thickness loss is small during the development process.

Still another object of the present invention is to provide a pattern cured product prepared from the above novel photosensitive polyamidesulfonamide composition.

It is still another object of the present invention to provide a use of the cured product in a redistribution layer, an interlayer insulating buffer film, a cap coat or a surface protective film.

It is still another object of the present invention to use the cured product in related electronic products.

The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. An aromatic polyamide sulfonamide polymer characterized in that the structure contains an amide bond repeating unit represented by the following general formula (1), a sulfonamide bond repeating unit represented by the general formula (2), and an amide bond sulfonamide bond mixed repeating unit represented by the general formula (3) at the same time:

wherein m, n and p represent the number of structural units in the polymer and are integers of 1-99; the ratio between m, n and p satisfies the relationship of 1:1: 2. The three structural units are randomly arranged in disorder in the polymer.

W in the polyamide sulfonamide polymer of the general formula (1), (2) or (3) is a divalent aromatic linking group which may be any one selected from the following general formulae (4), (5) or (6);

wherein R is₁，R₂，R₃，R₄Each represents a hydrogen atom or a monovalent radicalAn organic group;

wherein Q represents a direct bond or other 2-valent 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)₂Substituted or unsubstituted (-o, -m, -p) phenylene, phenylene ether (C)₆H₄-O-C₆H₄)_s(1≤s≤10)；

Wherein T represents a direct bond or other 2-valent organic group selected from O, S, CO and SO₂、Si(CH₃)₂、CH(OH)、(CH₂)_x(1≤x≤10)、(CF₂)_y(1≤y≤10)、 C(CH₃)₂、C(CF₃)₂Substituted or unsubstituted (-o, -m, -p) phenylene, phenylene ether (C)₆H₄-O-C₆H₄)_s(1. ltoreq. s.ltoreq.10), wherein R₅～R₁₂Are identical or different monovalent organic radicals selected from H, CH₃Or CF₃。

The foregoing polyamide sulfonamide polymers have a weight average molecular weight in the range of 5,000 to 300,000.

The object of the present invention and the technical problem to be solved are also achieved by the following technical means. A negative-type photosensitive composition containing a polyamide sulfonamide polymer according to the present invention includes:

(A) aromatic polyamide sulfonamide polymers;

(B) photoacid generators: the content thereof in the composition is preferably 0.1 to 15 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the component (A);

(C) a crosslinking agent: the content thereof in the composition is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A); and

(D) solvent: the content thereof in the composition is preferably 50 to 600 parts by mass, more preferably 60 to 500 parts by mass, and still more preferably 80 to 300 parts by mass, per 100 parts by mass of the component (A).

The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.

The aforementioned negative-type photosensitive composition containing an aromatic polyamide sulfonamide polymer, wherein the component (B) is at least one photoacid generator selected from, but not limited to, ionic compounds including sulfonium, phosphonium or iodonium salts; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable;

wherein the component (C) comprises at least one alkoxy compound, hydroxyl compound, epoxy compound, oxetane compound or vinyl ether group compound, preferably a compound having a hydroxymethyl group or an alkoxymethyl group;

wherein the ingredients of said composition are dissolved in a solvent (D) comprising at least one compound selected from the group consisting of: esters, ethers, ether-esters, ketones, ketone-ester hydrocarbons, aromatics, and/or halogenated hydrocarbons.

The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The negative-type photosensitive composition containing the aromatic polyamide sulfonamide polymer according to the present invention is a cured product having a relief pattern, which is prepared by a method comprising the steps of:

(a) coating the composition on a substrate and heating to remove the solvent to form a photosensitive resin film;

(b) a step of pattern-exposing the photosensitive resin film by using a mask;

(c) a step of removing the unexposed region of the coating layer to obtain a resin cured film having a relief pattern, and

(d) and a step of subjecting the relief pattern resin film to a heat curing treatment.

The cured product having a relief pattern described above, wherein the temperature of the heat treatment is 250 ℃ or less.

The cured product having a relief pattern is a cured product film having a microstructured relief pattern.

The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The cured product having a relief pattern according to the present invention is applied to a redistribution layer, an interlayer insulating buffer film, a cap coat or a surface protective film.

The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the invention, the electronic device comprises the redistribution layer, the interlayer insulating buffer film, the cover coat or the surface protection film.

As can be seen from the above, the present invention discloses an aromatic polymer having both an amide bond and a sulfonamide bond in the main chain, a negative-type photosensitive composition containing the aromatic polyamide sulfonamide polymer, and applications thereof. The negative photosensitive composition comprises the following raw materials in percentage by weight: an aromatic polyamide sulfonamide polymer, a photoacid generator, a crosslinking agent, and a solvent. The composition is used for preparing a polyamide sulfamide cured film under the condition of lower curing temperature (less than or equal to 250 ℃), and the cured film can be used as a redistribution layer, an interlayer insulating buffer film, a cover coat or a surface protection film material in an electronic device.

Compared with the prior art, the invention has obvious advantages and beneficial effects. As can be seen from the above technical solutions, in order to achieve the above object, the main technical contents of the present invention are as follows:

a polysulfonamide polymer, a negative-type photosensitive composition containing the polysulfonamide polymer, a cured product prepared from the same and application thereof in semiconductor encapsulation.

By the technical scheme, the negative photosensitive composition containing the polyamide sulfonamide polymer, the cured product prepared from the negative photosensitive composition and the application of the negative photosensitive composition in semiconductor packaging have at least the following advantages:

in view of the relatively high cure temperatures required for conventional photosensitive dielectric materials, novel polyamide sulfonamide compositions are used in the present invention. As a result, it was found that such films can be prepared with films having a relief microstructure under relatively low temperature (250 ℃ C. or lower) heat treatment conditions. Because the amido and the sulfonamide are simultaneously introduced in the polymerization reaction, the product has the advantages of two materials of polyamide and polysulfonamide; and the introduction of the sulfonamide greatly improves the solubility of the material in an alkaline developer, and the negative material has the advantage of small film thickness loss in the developing process by utilizing a crosslinking reaction, so that the preparation of the high-performance photosensitive polymerization dielectric material with good developing property, small film thickness loss and high resolution is facilitated. In addition, the resin composition has excellent adhesion to various substrates even under conditions of curing at low temperatures. Finally, by using fluorine atom-containing diamine precursors during polymer synthesis, these new materials would have a significant improvement in performance in reducing the water absorption of the material, thereby making the cured films prepared from the present compositions more suitable for current advanced packaging process requirements.

In conclusion, the technical scheme of the invention has the advantages and practical values, and similar designs are not published or used in similar products, so that the technical scheme is truly innovative; it has great improvement on the formula or the function, and produces good use and practical effect; and has a plurality of enhanced effects compared with the existing products, thereby being more suitable for practical use, having the value of wide industrial utilization, and being a novel, advanced and practical new design.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.

Detailed Description

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed descriptions of the embodiments of the polyamide sulfonamide polymer, the negative photosensitive composition containing the polyamide sulfonamide polymer, the cured product prepared therefrom, and the use thereof in semiconductor packaging according to the present invention are provided.

The present invention will be further specifically described below by way of examples of synthesis of polyamide sulfonamide polymers. The present invention is not limited to these polymer synthesis examples, and those having ordinary knowledge in the art can make various modifications within the technical spirit of the present invention.

One, (A) component: polyamide sulfonamide polymers

The properties of the polysulfonamide polymers prepared in Synthesis examples 1 to 6 are described below.

The aromatic polyamide sulfonamide polymer having the above formulas (1) to (3) is characterized in that the structure contains an amide bond repeating unit represented by the above general formula (1), a sulfonamide bond repeating unit represented by the general formula (2), and an amide bond and sulfonamide bond mixed repeating unit represented by the general formula (3) at the same time:

wherein m, n and p represent the number of structural units in the polymer and are integers of 1-99; the ratio between m, n and p satisfies 1:1: 2. The three structural units are randomly and randomly arranged in the polymer.

The polyamide sulfonamide polymer according to claim 1, wherein W in the general formula (1) (2) (3) is a divalent aromatic linking group which may be any one selected from the following general formulae (4), (5), or (6);

wherein R is₁，R₂，R₃，R₄Each represents a hydrogen atom or a monovalent organic group;

The method for synthesizing the polyamide sulfonamide polymer is not particularly limited, and a method of mixing a dihalide derivative with a diamine compound and carrying out a polycondensation reaction under an appropriate temperature condition is generally used. The dihalogenated derivatives here are preferably dichloroderivatives, such as m-chlorosulfonylbenzoyl chloride. One common synthetic method is as follows: in an inert gas atmosphere, dissolving a diamine precursor and 2-methylpyridine in N-methylpyrrolidone, then dropwise adding m-chlorosulfonyl benzoyl chloride (dissolved in N-methylpyrrolidone) in an equimolar amount or slightly excessive amount with a diamine monomer for reaction, settling the obtained polymer solution in a deionized water medium, filtering, and carrying out vacuum drying at 50-100 ℃ to obtain the polyamide sulfonamide polymer.

The polyamide sulfonamide polymers of the invention generally have a weight average molecular weight of between 5,000 and 300,000. Preferably a molecular weight of 10,000 to 150,000. Here, the molecular weight is measured by a Gel Permeation Chromatography (GPC) method and calculated from a standard polystyrene standard curve.

In order to improve the stability of the polyamide sulfonamide composition, the main chain end of the polyamide sulfonamide polymer may be terminated with a capping agent such as a monoacid chloride compound. The introduction ratio of the monoacid chloride compound used as the end-capping agent is preferably 0.5 to 30 mol% based on the entire amine component. As the monoacyl chloride compound: monocarboxylic acids such as 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid and monoacid chloride compounds obtained by acid chlorination of their carboxyl groups may be selected, and monocarboxylic acid chloride compounds obtained by acid chlorination of only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1, 5-dicarboxylnaphthalene, 1, 6-dicarboxylnaphthalene, 1, 7-dicarboxylnaphthalene and 2, 6-dicarboxylnaphthalene may also be selected; and active ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2, 3-dicarboximide. The blocking agent may be one or more of the aforementioned compounds.

The films prepared from the above polyamide sulfonamide polymers are typically developed using an aqueous alkaline solution. Therefore, polyamide sulfonamide polymers having high solubility in alkaline solvents are preferred. Preparing polyamide sulfonamide polymer into solution, spin-coating on a substrate such as silicon wafer, heating, drying, and removing solvent to form resin film with thickness of about 10 μm; then soaking the mixture in a tetramethylammonium hydroxide aqueous solution at the temperature of 20-25 ℃; the ease with which component (a) dissolves in the alkaline aqueous solution is judged by the time required for the film to dissolve completely.

In addition, the transmittance of the i-line directly affects the resolution of the photosensitive composition during processing. In order to obtain the optimal microstructure relief pattern under the same film thickness condition, the polyamide sulfonamide polymer preferably has a monomer structure with better light transmittance. The sulfonamide segment in the polyamide sulfonamide polymer increases i-line transmittance, and a diamine precursor containing fluorine may be selected. These fluorine-containing diamine monomers are also advantageous in reducing the effect of solution impregnation swelling on the film during development to suppress bleeding from the surface and also in reducing water absorption after curing of the composition. Therefore, in the polyamide sulfonamide polymer, W in the general formulae (1) to (3) is a divalent aromatic linking group, and it is preferable that W contains a structural unit represented by the following general formula (7) containing a trifluoromethyl group, from the viewpoint of light transmittance and water absorption.

In the polyamide sulfonamide polymer, W in the general formulae (1) to (3) is a divalent aromatic linking group, and may preferably contain a structural unit represented by the following general formula (8) from the viewpoint of reducing material stress.

In the polyamide sulfonamide polymer, W in the general formulae (1) to (3) is a divalent aromatic linking group, and may preferably contain a structural unit represented by the following general formula (9) from the viewpoints of lowering the thermal expansion coefficient of the material and increasing the glass transition temperature point.

Hereinafter, the component A (polyamide sulfonamide polymer) in the composition will be further specifically described with reference to the synthetic examples.

Synthesis example 1: synthesis of m-chlorosulfonyl benzoyl chloride

The acid chloride precursor (m-chlorosulfonyl benzoyl chloride, formula 10) for synthesizing the polyamide sulfonamide polymer, which is mentioned in the present invention, can be obtained by reacting trichloromethylbenzene (formula 11-1) with chlorosulfonic acid (formula 11-2) under mechanical stirring and heating at normal pressure. One synthetic method for the preparation of m-chlorosulfonyl benzoyl chloride is as follows: 6 parts (molar weight) of chlorosulfonic acid is placed in a three-neck flask, heated and stirred to 110-130 ℃, then 1-6 parts (molar weight) of trichloromethyl benzene is slowly dripped, and the dripping is finished within about 1.5-2 hours, and then the temperature is maintained for reaction for 3 hours. After the reaction is finished, reduced pressure distillation is carried out, and the fraction at 146 ℃ is collected under the condition of the pressure of 9mm Hg, so that the m-chlorosulfonyl benzoyl chloride is obtained.

The following synthetic examples 2 to 6 are preferable synthetic examples of polyamide sulfonamide polymers in the present invention.

Synthesis example 2: synthesis of Polymer-1

In a four-necked flask with a mechanical stirrer, a thermometer and a high purity nitrogen atmosphere, 2' -bis (trifluoromethyl) diaminobiphenyl (100mmol), 2-methylpyridine (300mmol) and anhydrous N-methyl-2-pyrrolidone (NMP) (47.25 g) were charged, stirred to be completely dissolved (the solution became clear), and cooled to-10 ℃. The solution was kept at a temperature ranging from-10 to-5 ℃ and a mixture of dissolved m-chlorosulfonylbenzoyl chloride (100mmol) (obtained from Synthesis example 1) and anhydrous N-methyl-2-pyrrolidone (42.00 g) was added dropwise thereto over a period of about half an hour, followed by stirring for 1 hour while keeping the solution at a temperature ranging from 0 to 5 ℃. The resulting reaction solution was slowly dripped into about 8 kg of water, and after settling and recovering precipitates by filtration and repeating the same process, washing with pure water was repeated 3 times, to obtain a wet product. And dried in a vacuum oven at 80 ℃ for more than 24h to obtain the final product. The resulting random copolymer was named Polymer-1, and the three structural segments of Polymer-1 were constructed as shown in the following formula (Polymer-1). The ratio between m, n and p satisfies 1:1: 2. The weight average molecular weight of polymer-1 was 55, 147, and the degree of dispersion was 1.85.

(Polymer-1)

Synthesis example 3: synthesis of Polymer-2

The synthesis of Polymer-2 was identical to that of Polymer-1 except that the diamine precursor 2,2' -bis (trifluoromethyl) diaminobiphenyl (100mmol) was completely replaced by 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (100mmol) in the synthesis of Polymer-2. Thus, the three structural segments of Polymer-2 constitute the following formula (Polymer-2). Wherein the ratio between m, n and p satisfies 1:1: 2. The weight average molecular weight of polymer-2 was 58, 765, and the dispersity was 1.74.

(Polymer-2)

Synthesis example 4: synthesis of Polymer-3

The synthesis of Polymer-3 was identical to that of Polymer-1 except that the diamine precursor 2,2' -bis (trifluoromethyl) diaminobiphenyl (100mmol) was completely replaced by 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane (100mmol) in the synthesis of Polymer-3. Thus, three structural fragments of Polymer-3 are represented by the following formula (Polymer-3). Wherein the ratio between m, n and p satisfies 1:1: 2. The weight average molecular weight of polymer-3 was 62, 149, and the dispersity was 1.80.

(Polymer-3)

Synthesis example 5: synthesis of Polymer-4

The synthesis of Polymer-4 was exactly the same as that of Polymer-1, except that the diamine precursor 2,2 '-bis (trifluoromethyl) diaminobiphenyl (100mmol) was completely replaced with 4,4' -diaminodiphenyl ether (100mmol) in the synthesis of Polymer-4. Thus, three structural fragments of Polymer-4 are represented by the following formula (Polymer-4). Wherein the ratio between m, n and p satisfies 1:1: 2. The weight average molecular weight of polymer-4 was 51, 327, and the dispersity was 1.65.

(Polymer-4)

Synthesis example 6: synthesis of Polymer-5

The synthesis of Polymer-5 was identical to that of Polymer-1 except that the diamine precursor 2,2' -bis (trifluoromethyl) diaminobiphenyl (100mmol) was completely replaced by 2, 2-dimethylbenzidine (100mmol) in the synthesis of Polymer-5. Thus, three structural fragments of Polymer-5 are represented by the following formula (Polymer-5). Wherein the ratio between m, n and p satisfies 1:1: 2. The weight average molecular weight of Polymer-5 was 52, 360, and the dispersity was 1.67.

(Polymer-5)

The above-mentioned polymer and some of the above-mentioned other components are mixed and dissolved in a solvent to prepare a photosensitive resin composition (also called varnish). The negative-type photosensitive composition of the present invention contains at least (a) one polyamide sulfonamide polymer, (B) a photoacid generator, (C) a crosslinking agent, and (D) a solvent. Wherein, the structure, the performance and the synthesis of the A component polyamide sulfonamide polymer are described in the first part. Filtration was performed using a filter membrane made of polytetrafluoroethylene with a pore size of 0.45 to 3 μm depending on the polymer concentration and varnish viscosity. The following will explain in detail the respective other components used in the composition of the present invention with reference to the examples of the photosensitive polyamide sulfonamide and comparative examples.

II and (B) component: photoacid generators

The photoacid generator as the component (B) in the present invention is a compound that generates an acid upon irradiation with light. The negative-type photosensitive composition containing a polysulfonamide polymer herein, after film formation, generates photoacid by exposure through a mask plate to cause crosslinking of the polymer in the film and thus causes a significant decrease in solubility of the exposed portion. These photoacid generators do not chemically react in the unexposed portions and thus maintain good solubility in the developing solution. Thus, there is a large difference (contrast) in the dissolution rates of the exposed and non-exposed areas (dark areas), and a film having a microstructured relief pattern is obtained after the development step.

The photoacid generator is selected from, but not limited to, ionic compounds including a sulfur salt, a phosphonium salt, or an iodonium salt; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable. The use of the oxime sulfonate compound enables to obtain a photoacid generator having excellent sensitivity to i-line (wavelength: 365nm), h-line (wavelength: 405nm), and g-line (wavelength: 436nm) of a general ultraviolet mercury lamp. Many oxime sulfonate compounds are commercially available. The following formula (12) represents several oxime ester compounds which are preferred in the present invention.

The content of the oxime ester compound is preferably 0.1 to 15 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the component (A), in order to obtain an optimum resolution and to improve a pattern contrast. Within the above range, the exposed portion of the polymer is crosslinked to a good degree to give a practical relief pattern. Here, the component (B) may be used alone or in combination of two or more.

Thirdly, component (C): crosslinker component

The crosslinking agent component (C) in the photosensitive polyamide sulfonamide composition of the present invention is a crosslinking agent which undergoes a crosslinking reaction with the polyamide sulfonamide polymer of component (a) in the step of exposing and heat-curing the negative-type photosensitive composition. Therefore, compounds that do not react with the other components of the polyamide sulfonamide composition are preferred. The crosslinking agent component contains at least one of an alkoxy compound, a hydroxyl compound, an epoxy compound, an oxetane compound or a vinyl ether group compound. From the viewpoint of high mechanical properties of the cured film and high reactivity at the time of low-temperature curing, a compound having a methylol group, an alkoxymethyl group or the like, for example, a compound represented by the following formula (13) is preferable.

The content of the crosslinking agent (C) is preferably 3 to 50 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of the component (A), in order to obtain the optimum resolution and the chemical agent corrosion resistance of the cured film. If the crosslinking agent is less than 3 parts by mass, the effects of improving the resolution and the resistance to corrosion by chemical agents are not remarkably exhibited; if the crosslinking agent is more than 50 parts by mass, various mechanical properties of the material may be degraded. The component (C) may be used singly or in combination of two or more of the above crosslinking agents.

Fourthly, component (D): solvent(s)

(D) Component (C) as a solvent, and the varnish is formed by dissolving the above components (a) to (C). As the component (D), there can be used solvents such as amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like. In general, there is no particular limitation as long as other components in the negative-type photosensitive composition can be sufficiently dissolved. Some common solvents include N-methyl-2-pyrrolidone, gamma-butyrolactone, -caprolactone, N-dimethylformamide, N-dimethylacetamide, 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, cyclohexanone, tetrahydrofuran, and the like. Among these solvents, γ -butyrolactone, N-methyl-2-pyrrolidone, and cyclopentanone are preferably used from the viewpoint of excellent solubility and coatability of the resin film.

(D) The content of the component (a) is not particularly limited, but is preferably 50 to 600 parts by mass, more preferably 60 to 500 parts by mass, and still more preferably 80 to 300 parts by mass per 100 parts by mass of the component (a) in view of controlling the film thickness and coatability in the coating process.

Fifthly, other components of the composition

The resin composition of the present invention may contain, in addition to the above-mentioned components (a) to (D), other auxiliary components such as an anticorrosive agent, a thickener, a dissolution accelerator, a softener, a surfactant and the like as required. The addition of these adjuvants is on the principle that the essential physical properties of the final cured film of the present invention are not substantially impaired, and the addition of these adjuvants tends to improve the processing properties of the material or enhance certain properties of the final cured film to be more suitable for certain processes. These components and effects are described in detail below.

Corrosion inhibitor-when the photosensitive resin composition of the present invention is applied to copper or a copper alloy substrate, at least one of a triazole ring, an imidazole ring and a thiazole ring represented by the general formula (14) containing a carbon atom and a nitrogen atom may be added to the composition in order to suppress discoloration and decrease in stability due to corrosion of copper. Examples of the azole compound include 1H-triazole, 1H-benzotriazole, 2- (2H-benzotriazol-2-yl) p-cresol, 1, 5-dimethyltriazole, 4, 5-diethyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-ethyl-1H-triazole, 4, 5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, p-tolyltriazole, p-, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -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-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, p-tolyltriazole, p-tolyl, Tetrazole, 5-amino-tetrazole, 1-methyl-1H-tetrazole, and the like.

The content of the corrosion inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A) in order to obtain an optimum effect of inhibiting metal corrosion.

Tackifier-in order to improve the adhesion between the cured film formed from the photosensitive resin composition of the present invention and the substrate, an adhesion promoter (tackifier) component may be optionally blended in the photosensitive resin composition. The tackifier may be selected from organic silane compound or aluminum bonding auxiliary agent such as tris (ethylacetoacetato) aluminum, tris (acetylacetone) aluminum, and ethylacetoacetate diisopropylester. In order to improve the adhesion to a substrate such as copper, an organic silane compound is preferably used. The organosilane compound includes: 3- (2, 3-Epoxypropoxy) propyltrimethoxysilane, 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, n-phenyl-3-aminopropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like. These organic silane compounds may be used alone, or 2 or more kinds thereof may be used in combination.

The content of the thickener component in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, per 100 parts by mass of the component (a), from the viewpoint of improving the adhesion to the substrate.

Dissolution promoters-in the negative-type polyamide sulfonamide compositions herein, the dissolution promoters can increase the dissolution rate of the unexposed portions to enhance the contrast of the micropattern. Examples of the dissolution accelerator include compounds having a hydroxyl group or a carboxyl group. Examples of the compound having a hydroxyl group include p-cumylphenol, resorcinols, bisphenols, linear or non-linear phenolic compounds, phenolic substitutes of 2 to 5 for diphenylmethane, phenolic substitutes of 1 to 5 for 3, 3-diphenylpropane, and the like. These dissolution promoters may be used alone or in combination of two or more. The content of the dissolution promoter component in the composition is preferably 1 to 50 parts by mass per 100 parts by mass of the component (a).

Softeners-in the negative-type polysulfonamide compositions herein, the softeners may increase the flexibility of the cured film made therefrom to increase the elongation parameter at break of the material. As the softener, compounds such as polyols, polyesters, polyhydroxy esters, etc. having different molecular weights can be selected. These softeners may be used alone or in combination of two or more. If a softener component is selected, the content thereof in the composition is preferably 1 to 40 parts by mass per 100 parts by mass of the component (A).

Surfactant-in order to improve coatability and surface smoothness during spin coating film formation, a surfactant may be added to the composition as a leveling agent, and examples of the film-forming agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Some examples are available directly from the market, including MegafacF171, F173 (manufactured by japan ink chemical industries, ltd.); KP341, KBM303, and KBM803 of organosiloxane (manufactured by shin-Etsu chemical Co., Ltd.); there are also 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, per 100 parts by mass of the component (A).

The following are preferred embodiments of the negative-working photosensitive compositions of the present invention containing polyamide sulfonamide polymers.

Example 1: the negative photosensitive resin composition of the present invention was obtained by adding E-1(1 part by mass) as an anticorrosive, F-1(1.6 parts by mass) as a thickener, G-1(15 parts by mass) as a softener, and H-1(0.05 part by mass) as a leveling agent to polymer-1 (100 parts by mass) obtained in synthesis example 2, B-1(3 parts by mass, relative to polymer-1) as a photoacid, C-1(20 parts by mass) as a crosslinking agent, and a mixed solvent (D-1, 180 parts) of cyclopentanone + 10% 2-heptanone dissolved in the solvent. The information on the other components than the polymer component (A) is referred to below:

(D-1) 90% cyclopentanone + 10% 2-heptanone

(D-2) cyclopentanone

(E-1) tetrazole

(E-2) 5-amino-tetrazole

(E-3) 1H-benzotriazole

(F-1) 3- (2, 3-glycidoxy) propyltrimethoxysilane

(F-2) 3- [ bis (2-hydroxyethyl) amino ] propane-triethoxysilane

(F-3) gamma-ureidopropyltriethoxysilane

(G-1):K-PURE CDR-3314(King Industries，Inc)

(H-1):PolyFox PF-6320(OMNOVA Solutions Inc.)

Examples 2 to 10 and comparative examples 1 to 5 were prepared in exactly the same manner as in example 1 except that the respective components or contents used therein were different. The details of the varnish components described in these examples/comparative examples and the parts by mass (shown in parentheses) thereof relative to the polymer (A) (100 parts by mass) are shown in Table-1 below.

TABLE-1

NA: representing compositions without such components.

The photosensitive resin compositions (also called varnishes) obtained in the above examples/comparative examples were filtered through a polytetrafluoroethylene filter membrane to obtain final negative photosensitive resin compositions. The polytetrafluoroethylene filter membrane can be selected to have a pore size of 0.45-3 microns, depending on the polymer concentration in the composition and the viscosity of the varnish. The varnish obtained in the above examples/comparative examples was formed into a cured film of polyamide sulfonamide coated on a copper wafer by the method described in claim 6.

Embodiments of the method for producing a patterned cured product, the redistribution layer, the interlayer insulating buffer film, the coverlay or surface protective film, and the electronic device according to the present invention will be described in detail below. The present invention is not limited to the following embodiments.

The method for preparing a pattern cured product by using the polyamide sulfonamide composition comprises the following steps:

(a) resin film forming step: a step of coating the polyamide sulfonamide polymer composition according to claim 1 to 5 on a substrate, and heating and drying the coating to remove the solvent to form a photosensitive resin film. Examples of the substrate include a semiconductor substrate such as an Si substrate (silicon wafer), a ceramic substrate, a metal substrate (including a copper substrate, an aluminum substrate, a copper alloy substrate, and the like), a silicon nitride substrate, and the like. Examples of the coating method include spin coating, spray coating, and dipping, and spin coating by a spin coater is preferable from the viewpoint of controlling the film thickness. The heat drying may be performed using a hot plate, an oven, or the like. The heating and drying temperature is preferably 90-150 ℃, and more preferably 90-130 ℃.

(b) An exposure step: and pattern-exposing the photosensitive resin film using a mask. The pattern exposure is, for example, exposure to a predetermined pattern through a photomask. The active light to be irradiated includes ultraviolet rays such as i-rays, visible rays, and radiation rays, and i-rays are preferable. As the exposure apparatus, a scanner exposure machine, a projector exposure machine, a stepper exposure machine, or the like can be used.

(c) A developing step: by performing the developing step, a resin film having a microstructure relief pattern can be obtained. Generally, development is performed by a method such as a dipping method or a spin spray method. In the case of using the negative photosensitive resin composition of the present invention, the developer can remove the unexposed portion of the film to obtain a relief pattern. The developing time is generally 10 seconds to 15 minutes, and preferably 20 seconds to 5 minutes from the viewpoint of improving productivity and process control. As the developer, inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water; organic amines such as ethylamine, triethanolamine and diethylamine may also be used; an aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide may also be used. In the above-mentioned various developing solutions, a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added as necessary to enhance the effect. Among these developers, an aqueous tetramethylammonium hydroxide solution is preferable. In general, an aqueous solution of TMAH having a concentration of 2.38 mass% is preferably used. It should be noted that, depending on the dissolution rate of the component (a), the concentration of TMAH in the alkaline developer may be diluted appropriately to adjust the film dissolution rate of the exposed region and the non-exposed region so as to obtain the optimum contrast at the time of development. After the development, the developer may be removed by washing with a rinse solution, whereby a patterned thin film can be obtained. The rinse solution may be distilled water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, or the like, used alone or in combination.

(d) And a heat curing step, wherein the heat treatment step is a process of heating and curing the relief pattern resin film so as to obtain the optimal physical properties of the material. In this step, the relief pattern obtained by the above-described development is heated, thereby being converted into a cured relief pattern. A method using a hot plate or an oven may be selected, and the heating temperature is preferably 250 ℃. The time of the heat treatment is usually 30 minutes to 4 hours, and more preferably 30 minutes to 2 hours, from the viewpoint of the time required for the crosslinking reaction. The atmosphere of the heat treatment may be air or an inert gas atmosphere such as nitrogen or argon. From the viewpoint of preventing oxidation of the pattern resin film and cost, it is preferable to heat-cure the pattern resin film in a high-purity nitrogen gas (. gtoreq.99.999%) atmosphere.

The cured product of the present invention is a cured polymer resin film obtained by the above-mentioned treatment step, and such a film may be a cured film having a relief pattern as described above or a cured film having no pattern.

The cured film may be stacked in direct contact with the semiconductor element, or may be stacked with another layer interposed therebetween. They may also be used to encase other materials such as metal wires to act as an insulating medium. Examples of applications include redistribution layers, interlayer insulating buffer films, covercoat or surface protection film materials, and the like.

By using one or more materials selected from the redistribution layer, the interlayer insulating buffer film, the covercoat layer, and the surface protective film, electronic components such as semiconductor packages, multilayer wiring boards, and display circuits can be manufactured with high reliability and high stability.

Sixth, evaluation of adhesiveness

According to one standard adherence test method of the American Society for Testing and Materials (ASTM): d3359 Standard method for testing adhesive lines with Tape (Standard Test methods for Measuring Adhesion by Tape Test), the cured film obtained (cured at 250 ℃ for 1 hour under nitrogen atmosphere to obtain a film with an unrelieved pattern of about 6 to 10 μm on a copper substrate) was cut into 10 × 10 grid-like small cells (1 mm per grid area) in the vertical direction with a saw-tooth-shaped hundred-grid blade. An adhesive tape (3M production) was attached to these small pieces of the cured film according to the method described in ASTM D3359, and the adhesive tape was peeled off. The line of application of the material was judged from the number of small pieces of the cured film peeled from the substrate when the adhesive tape was peeled off. In the present invention, the following criteria a or B are used to judge the adhesiveness of the material film to the copper substrate. The detailed results are listed in table 2.

A: lattice without peeling

B, the number of the peeling lattices is at least 1

Seventh, evaluation of discoloration inhibition

The resulting cured film coated on copper metal was evaluated for appearance by optical microscope and naked eye. If the cured film can well maintain the original color of the underlying copper metal film after curing, it is evaluated as A that discoloration is suppressed; if the copper color under the cured film clearly shifts to deep red/brown, it is evaluated as B that discoloration is not suppressed. The detailed results are listed in table 2.

A: inhibit color change

B: without inhibiting discoloration

TABLE-2

Examples/comparative examples	Adhesion Property	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	Can not form a film	Can not form a film
Comparative example #2	Can not form a film	Can not form a film
			Comparative example #3	A	B
Comparative example #4	Film peeling	Film peeling
			Comparative example #5	Film peeling	Film peeling

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. An aromatic polyamide sulfonamide polymer characterized in that the structure of the polymer contains an amide bond repeating unit represented by the following general formula (1), a sulfonamide bond repeating unit represented by the general formula (2), and an amide bond and sulfonamide bond mixed repeating unit represented by the general formula (3):

wherein:

m, n and p represent the number of structural units in the polymer and are integers of 1-99; the ratio of m, n and p satisfies the relation of 1:1: 2; the three structural units represented by the general formulas (1), (2) and (3) are randomly arranged in disorder in the polymer; w in the general formulae (1), (2) and (3) is a divalent aromatic linking group.

2. The polyamide sulfonamide polymer according to claim 1, wherein W is selected from any one of the groups represented by the following general formula (4), (5), or (6);

wherein Q represents a direct bond or other 2-valent 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)₂Substituted or unsubstituted (-o, -m, -p) phenylene, phenylene ether group (C)₆H₄-O-C₆H₄)_s(1≤s≤10)；

Wherein T represents a direct bond or other 2-valent organic group selected from O, S, CO and SO₂、Si(CH₃)₂、CH(OH)、(CH₂)_x(1≤x≤10)、(CF₂)_y(1≤y≤10)、C(CH₃)₂、C(CF₃)₂Substituted or unsubstituted (-o, -m, -p) phenylene, phenylene ether group (C)₆H₄-O-C₆H₄)_s(1. ltoreq. s.ltoreq.10), wherein R₅～R₁₂Are identical or different monovalent organic radicals selected from H, CH₃Or CF₃。

3. The aromatic polyamide sulfonamide polymer of claim 1 having a weight average molecular weight in the range of 5,000 to 300,000.

4. A negative-tone photosensitive composition containing the polyamide sulfonamide polymer of any of claims 1-3, comprising:

(A) aromatic polyamide sulfonamide polymers;

(B) photoacid generators: the content thereof in the composition is preferably 0.1 to 15 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the component (A);

5. The negative-type photosensitive composition containing an aromatic polyamide sulfonamide polymer according to claim 4, wherein the ingredient of component (B) is at least one photoacid generator selected from, but not limited to, ionic compounds including a sulfonium salt, a phosphonium salt or an iodonium salt; the nonionic compound includes an oxime sulfonate, a sulfonate compound, or a quinone diazide compound; or mixtures thereof. From the viewpoint of sensitivity and imaging property, oxime sulfonate compounds are preferable; and/or

Wherein the component (C) comprises at least one alkoxy compound, hydroxyl compound, epoxy compound, oxetane compound or vinyl ether group compound, preferably having a hydroxymethyl group or an alkoxymethyl group; and/or

6. A negative-type photosensitive composition-containing aromatic polyamide sulfonamide polymer according to any one of claims 4 to 5, which is a cured product having a relief pattern, prepared by a method comprising the steps of:

(b) a step of pattern-exposing the photosensitive resin film by using a mask;

7. The cured product having a relief pattern according to claim 6, wherein the temperature of the heat treatment is 250 ℃ or less.

8. The embossed patterned cured product according to claim 6, which is a cured product film having a microstructured embossed pattern.

9. The cured product having a relief pattern according to any one of claims 6 to 8, which is applied to a redistribution layer, an interlayer insulating buffer film, a cap coat or a surface protective film.

10. An electronic device comprising the redistribution layer, the interlayer insulating buffer film, the covercoat layer, or the surface protective film of claim 9.