TWI876626B - Negative type photosensitive resin composition and electronic device comprising same - Google Patents

Abstract

The present invention relates to a polyimide resin, a negative-type photosensitive resin composition including the same, and an electronic device including an organic insulating film or photosensitive pattern formed from the negative-type photosensitive resin composition.

Description

Negative photosensitive resin composition and electronic device containing the same

The present invention relates to a photosensitive resin composition, and more particularly, to a negative closed-ring polyimide resin having excellent solubility and not expanding during development, a negative photosensitive resin composition comprising the same, and an electronic device.

This application claims priority and benefits to Korean Patent Application No. 10-2022-0141533 filed on October 18, 2022 with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

Photosensitive resins are typical functional polymer materials that have been put into practical use in the production of various precision electronics and information industry products, and are currently used in cutting-edge technology industries, especially in the production of semiconductors and displays. Generally speaking, a photosensitive resin means a polymer compound whose molecular structure undergoes chemical changes in a short time when irradiated with light, resulting in changes in physical properties such as solubility in specific solvents, coloring, and curing. Because photosensitive resins enable micro-precision processing, significantly reduce energy and raw materials compared to thermal reaction processes, and allow fast and accurate work in smaller installation spaces, photosensitive resins have been widely used in various precision electronics and information industries, such as advanced printing, semiconductor production, display production, and light-curing surface coating materials.

Such photosensitive resins can be broadly divided into negative-type photosensitive resins, which are types in which the portion irradiated with light becomes insoluble in a developer, and positive-type photosensitive resins, which are types in which the portion irradiated with light becomes soluble in a developer.

After selective exposure, the polymer used in the negative photosensitive resin needs to meet the requirements that the exposed part needs to have a higher solubility in the developer, while the unexposed area needs to have a lower solubility or no solubility in the developer. Such requirements are increasingly needed so that extremely fine patterns can be formed in the precision electronics and information industries.

The present invention has been devoted to providing a polyimide having a closed ring structure, which does not cause expansion during the development process during the formation of a pattern using a negative photosensitive composition and has excellent solubility, and a negative photosensitive resin composition comprising the same.

In addition, the object of the present invention is to provide an electronic device including an organic insulating film or a photosensitive pattern formed by a negative photosensitive resin composition.

The exemplary embodiment of this specification provides a polyimide resin having a structure including the following chemical formula 1.

[Chemical formula 1]

意謂鍵結至另一取代基的部分或重複單元，X1及X2彼此相同或不同，且各自獨立地為四價有機基團，Y為二價至四價有機基團，R₃至R₆彼此相同或不同，且各自獨立地為氫；或由以下化學式2表示，其限制條件為相對於所述聚醯亞胺樹脂中所包括的OH基團的總莫耳數，由以下化學式2表示的結構的比率為1莫耳%或大於1莫耳%，m1、m2、k1以及k2各自為0或1，且1

m1+m2+k1+k2

2，Z為直接鍵或二價有機基團，當Y及Z的莫耳(mol)比的總和為1且Z為二價有機基團時，Z的莫耳比為0.05

Z

0.3，n為1至50的實數，以及m為0至50的實數，

means a part or repeating unit bonded to another substituent, X1 and X2 are the same or different from each other and are each independently a tetravalent organic group, Y is a divalent to tetravalent organic group, _R3 to _R6 are the same or different from each other and are each independently hydrogen; or represented by the following chemical formula 2, with the restriction that the ratio of the structure represented by the following chemical formula 2 is 1 mol% or greater relative to the total molar number of OH groups included in the polyimide resin, m1, m2, k1 and k2 are each 0 or 1, and 1

m1+m2+k1+k2

2. Z is a direct bond or a divalent organic group. When the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05.

Z

0.3, n is a real number from 1 to 50, and m is a real number from 0 to 50,

In Chemical Formula 2, * is a portion bonded to Chemical Formula 1, R7 is hydrogen; or a substituted or unsubstituted alkyl group, and p is an integer from 1 to 10.

Another exemplary embodiment of the present invention provides a negative photosensitive resin composition, comprising: a polyimide resin; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

In addition, another exemplary embodiment of the present invention provides an electronic device including an organic insulating film or a photosensitive pattern formed by a negative photosensitive resin composition.

Even in the development process after selective exposure during pattern formation using the negative photosensitive resin composition according to the present specification, the polyimide resin has excellent solubility without swelling. In addition, it is possible to provide an electronic device including an organic insulating film or photosensitive pattern having excellent performance, the organic insulating film or photosensitive pattern being formed by the negative photosensitive resin composition according to the present specification.

1: Silicon wafer (Si wafer)

2: First photosensitive pattern (PID1)

3: Pad

4: Solder balls

5: Second photosensitive pattern (PID2)

6: Substrate

7: First photosensitive pattern (RDL)

8: Pad

9: Second photosensitive pattern (PDL)

10: OLED layer

FIG. 1 shows an example of an organic insulating film for a semiconductor, including a photosensitive resin composition according to an exemplary embodiment of the present invention.

FIG. 2 shows an example of an organic insulating film for an organic light-emitting device, including a photosensitive resin composition according to an exemplary embodiment of the present invention.

Figures 3 and 4 are photographs of photosensitive patterns according to exemplary embodiments of the present invention.

[Best Mode]

Hereinafter, the polyimide resin, the negative photosensitive resin composition, and the electronic device according to specific exemplary embodiments of the present invention will be described in detail.

When a component "includes" a constituent element in this specification, unless otherwise specifically described, this does not mean to exclude another constituent element, but means that it may further include another constituent element.

An exemplary embodiment of the present invention provides a polyimide resin having a structure of the following chemical formula 1.

意謂鍵結至另一取代基的部分或重複單元，X1及X2彼此相同或不同，且各自獨立地為四價有機基團，Y為二價至四價有機基團，R₃至R₆彼此相同或不同，且各自獨立地為氫；或由以下化學式2表示，其限制條件為相對於所述聚醯亞胺樹脂中所包括的OH基團的總莫耳數，由以下化學式2表示的結構的比率為1莫耳%或大於1莫耳%，m1、m2、k1以及k2各自為0或1，且1

m1+m2+k1+k2

2，Z為直接鍵或二價有機基團，當Y及Z的莫耳(mol)比的總和為1且Z為二價有機基團時，Z的莫耳比為0.05

Z

0.3， n為1至50的實數，以及m為0至50的實數，

means a part or repeating unit bonded to another substituent, X1 and X2 are the same or different from each other and are each independently a tetravalent organic group, Y is a divalent to tetravalent organic group, _R3 to _R6 are the same or different from each other and are each independently hydrogen; or represented by the following chemical formula 2, with the restriction that the ratio of the structure represented by the following chemical formula 2 is 1 mol% or greater relative to the total molar number of OH groups included in the polyimide resin, m1, m2, k1 and k2 are each 0 or 1, and 1

m1+m2+k1+k2

2. Z is a direct bond or a divalent organic group. When the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05.

Z

0.3, n is a real number from 1 to 50, and m is a real number from 0 to 50,

In Chemical Formula 2, * is a portion bonded to Chemical Formula 1, R7 is hydrogen; or a substituted or unsubstituted alkyl group, and p is an integer from 1 to 10.

The inventors have experimentally confirmed that a photosensitive resin including a polyimide resin having the aforementioned specific structure can have higher adhesion and adhesion to substrates used in semiconductor devices or display devices, such as metal substrates (such as Au, Cu, Ni and Ti) or inorganic substrates (such as _SiO2 and SiNx), has improved mechanical properties such as excellent heat resistance or chemical resistance, and can easily form ultra-fine patterns, thereby completing the present invention.

In addition, the inventors were able to ensure fine patterns and excellent physical properties by imparting acrylate groups (-COO-) to polyimide resins including the structure of the above chemical formula 1.

Specifically, for a negative photosensitive resin composition, a high-temperature imidization process can be omitted by using a polyimide resin that can be subjected to a solution process at a low temperature without using a polyimide precursor that requires a high-temperature thermosetting process (imidization process).

The inventors have disclosed that when a polyimide having a structure in which a photopolymerizable unsaturated group is bonded to a side chain of the polyimide using a closed ring structure is used as the existing polyimide, the solubility is reduced during development, thereby resulting in a reduction in the swelling phenomenon. In addition, the inventors have disclosed that there is a problem that when a closed ring polyimide and a monomer having a photopolymerizable multifunctional group are used together, high energy is generated by exposure during the curing process, making it difficult to achieve precise patterning and increasing the process cost because the polymer itself does not have a photopolymerizable group. In addition, although attempts have been made to introduce a polyamide structure (polyamide type) by attaching a photopolymerizable group (R) to the ring-opening position after the anhydride-closed ring structure of the closed ring polyimide is opened, the inventors have revealed that there is a problem that the photopolymerizable group (R) is desorbed during the ring closure, resulting in poor dimensional stability and gas generation.

However, the polyimide resin according to the above exemplary embodiment of the present invention is characterized in that the terminal group does not generate a closed ring reaction with the main chain or the side chain bonded to the main chain even during development, and does not expand during development by including a photopolymerizable unsaturated group (represented by Chemical Formula 2) at a portion of the main chain and the terminal group.

In addition, the polyimide resin according to the exemplary embodiment of the present invention may further include an unreacted hydroxyl group (OH), carboxylic acid (COOH), thiol group or sulfonic acid group at the terminal group, and such groups can provide excellent solubility.

According to the exemplary embodiments of this specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group.

According to the exemplary embodiments of the present specification, X1 and X2 are the same or different from each other, and can be independently selected from the group consisting of a tetravalent aromatic organic group, a tetravalent aliphatic organic group, and a tetravalent organic group in which an aromatic group and an aliphatic group are bonded to each other.

According to the exemplary embodiments of the present specification, X1 and X2 are divalent hydrocarbons, or at least one carbon in the hydrocarbon is replaced by C(=O), SO ₂ , NR′, S or O, and R′ can be an alkyl group or an aryl group.

According to the exemplary embodiments of this specification, X1 and X2 are the same or different from each other, and can be independently selected from the group consisting of the following structures.

表示四價有機基團，且為與化學式1的羰基(C(=O))的 鍵聯部分。 In the structure,

represents a tetravalent organic group and is a bonding portion to the carbonyl group (C(=O)) of Chemical Formula 1.

According to the exemplary embodiment of this specification, X1 and X2 are

When the polyimide resin includes the above structure, the mechanical properties of the polyimide resin are increased, and the penetration effect of the developer during development is increased, which is effective for forming ultra-fine patterns.

According to the exemplary embodiments of the present specification, Y can be selected from the group consisting of: divalent to tetravalent aromatic organic groups, divalent to tetravalent aliphatic organic groups, and divalent to tetravalent organic groups in which aromatic groups and aliphatic groups are bonded to each other.

According to exemplary embodiments of the present specification, Y is a divalent hydrocarbon, or at least one carbon in the hydrocarbon is replaced by C(=O), SO ₂ , NR", S or O, and R" may be an alkyl group or an aryl group.

According to the exemplary embodiments of this specification, Y can be selected from the group consisting of the following structures.

可為與化學式1 的N的鍵聯部分。 In the structure, A is a divalent organic group, and

It may be a bonding portion with N of Chemical Formula 1.

表示最小二價四價 有機基團至最大四價有機基團。 According to the exemplary embodiments of this specification,

Represents the smallest divalent tetravalent organic group to the largest tetravalent organic group.

According to exemplary embodiments of the present specification, A may be a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C (=O) or SO ₂ .

According to exemplary embodiments of the present specification, A may be a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or _SO2 .

According to the exemplary embodiments of this specification, A can be selected from the group consisting of the following structures.

的各酚基的鍵聯部分。 In the structure, * is

The bonding portion of each phenolic group.

，此 處，A為

。 According to the exemplary embodiment of this specification, Y is

, where A is

.

According to the exemplary embodiments of the present specification, Z may be a direct bond or a divalent organic group of any of the following structures.

可為與化學式1 的N的鍵聯部分。 In the structure, B is a divalent organic group, and

It may be a bonding portion with N of Chemical Formula 1.

表示最小二價四價 有機基團至最大四價有機基團。 According to the exemplary embodiments of this specification,

Represents the smallest divalent tetravalent organic group to the largest tetravalent organic group.

According to exemplary embodiments of the present specification, B may be a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C (=O) or SO ₂ .

According to exemplary embodiments of the present specification, B may be a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C (=O) or SO ₂ .

According to the exemplary embodiments of this specification, B can be selected from the group consisting of the following structures.

的各苯基的鍵聯 部分。 In the structure, * is used for

The bonding portion of each phenyl group.

According to the exemplary embodiment of this specification, Z is a direct key.

The polyimide resin has the function of forming ultra-fine patterns by controlling the developing properties by including the above-mentioned structure.

According to the exemplary embodiments of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

According to the exemplary embodiments of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

According to the exemplary embodiments of the present specification, R7 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

According to the exemplary embodiment of this specification, R7 is hydrogen.

According to the exemplary embodiment of this specification, n is a real number from 1 to 50, and m is 0.

According to the exemplary embodiment of this specification, n is a real number from 1 to 50, and m is a real number from 1 to 50.

In this specification, the aromatic (organic) group may be a C6 to C20 aryl group, and the aliphatic group may be a C1 to C20 alkylene group or a C3 to C20 cycloalkylene group. Examples of aryl groups include phenylene groups and the like. Examples of halogen groups include F, Cl and the like.

In this specification, the term "substituted or unsubstituted" means substituted by one or more substituents selected from the group consisting of: deuterium; halogen group; hydroxyl group; -COOH; alkyl group; cycloalkyl group; aryl group; and heteroaryl group, or having no substituent.

In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 30. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to yet another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like, but are not limited thereto.

In this specification, an alkylene group means a divalent alkyl group, and the above description can be applied to an alkyl group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to yet another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 20. Examples of monocyclic aryl groups as aryl groups include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Examples of polycyclic aryl groups include naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl, and the like, but are not limited thereto.

In the present specification, a heterocyclic group is a heterocyclic group including O, N or S as a hetero atom, and the number of carbon atoms thereof is not particularly limited, but is 2 to 30, specifically 2 to 20. Examples of heterocyclic groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, dipyridyl, triazinyl, acridyl, pyridazinyl, quinolyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl and the like, but are not limited thereto.

In this specification, a heterocyclic group may be an aliphatic or aromatic cyclic group.

In this specification, the above description about heterocyclic groups can be applied to heteroaryl groups other than aromatic heteroaryl groups.

The other end of the polyimide resin may also have a terminal represented by Chemical Formula 2, or may also have a diamine or dianhydride used during the preparation of the polyimide as an end group.

In the exemplary embodiment of the present specification, _R3 to _R6 are the same as or different from each other, and at least one of them is represented by Chemical Formula 2, and the others are hydrogen, with the restriction that the ratio of the structure represented by Chemical Formula 2 is 1 mol% or more relative to the total molar number of OH groups included in the polyimide resin. Even in the development process after selective exposure during pattern formation using the negative photosensitive resin composition according to the exemplary embodiment, the polyimide resin has excellent solubility in the developer without swelling.

In the exemplary embodiment of the present specification, the ratio of the structure represented by Chemical Formula 2 is 10 mol% to 70 mol% relative to the total molar number of OH groups included in the polyimide resin.

When the ratio of the structure represented by Chemical Formula 2 is less than 10 mol% relative to the total molar number of OH groups included in the polyimide resin, the number of OH groups protected by the protecting group is small, and the number of OH groups not protected by the protecting group is relatively large, so that the residual film rate can be reduced. In addition, when the ratio of the structure represented by Chemical Formula 2 is greater than 70 mol% relative to the total molar number of OH groups included in the polyimide resin, the number of OH groups protected by the protecting group is large and the number of OH groups not protected by the protecting group is relatively small, so that it may be difficult to achieve ultra-fine patterns due to reduced solubility in alkaline aqueous solutions.

Preferably, the ratio of the structure represented by Chemical Formula 2 is 15 mol% to 45 mol% relative to the total molar number of OH groups included in the polyimide resin.

Polyimide resins falling within the above range can improve overall physical properties such as developing properties, residual film rate, and sensitivity.

In the exemplary embodiment of the present specification, when _m1 + _m2 + _k1 + _k2 is 1 or 2 and includes an OH or COOH group as in the above structure, the structure of Chemical Formula 2 exists not only at the end of the polyimide resin but also on its side chain, thereby advantageously improving the surface condition during formation of a photosensitive film.

莫耳比(X1+X2)

0.3。 According to the exemplary embodiment of the present specification, assuming that the sum of the molar ratios of Y and Z is 1 as the input ratio of the diamine in the polyimide resin of Chemical Formula 1, the sum of the molar ratios of Z may be 0.05.

Moiré ratio (X1+X2)

0.3.

In the exemplary embodiment of the present specification, the polyimide resin may further include a structure represented by the following chemical formula 3 as an end group.

In Chemical Formula 3, * is a part bonded to Chemical Formula 1, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is a real number from 0 to 4, and when re1 is 2 or greater than 2, Re1 are the same or different from each other, and Re is hydrogen; or a structure represented by Chemical Formula 2.

In the exemplary embodiments of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In the exemplary embodiments of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In the exemplary embodiments of the present specification, Re1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In the exemplary embodiments of this specification, Re1 is hydrogen.

In the exemplary embodiments of this specification, Re is hydrogen.

In the exemplary embodiments of this specification, Re is a structure represented by chemical formula 2.

According to the exemplary embodiments of the present specification, the weight average molecular weight of the polyimide resin is 5,000 g/mol to 200,000 g/mol.

When the weight average molecular weight is less than 5,000, it may be difficult to achieve the desired coating characteristics and mechanical characteristics during coating of the polyimide copolymer, and when the weight average molecular weight exceeds 200,000, the solubility in the developer is reduced, making it difficult to coat the polyimide copolymer as a photosensitive material.

The weight average molecular weight is one of the average molecular weights in which the molecular weight is not uniform and the molecular weight of any polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight may be a value measured by gel permeation chromatography (ie, GPC).

For the polyimide resin, a type of polyimide (an example of a polyimide of Chemical Formula 1) can be prepared using a dianhydride compound and a diamine compound as exemplified below. In addition, in order to prepare other types of polyimide, as materials and polymerization methods constituting polyimide, materials and polymerization methods known in the art can be used.

In addition, in order to make the polyimide of Chemical Formula 1 have terminal groups, the polyimide having at least one group selected from hydroxyl, carboxyl, thiol and sulfonic acid groups can be prepared using a compound having at least one group selected from hydroxyl, carboxyl, thiol and sulfonic acid groups and having an anhydride group or an amine group during the polymerization of the polyimide, and the terminal groups of Chemical Formula 1 can be prepared by reacting an isocyanate compound with the polyimide. The following process involves introducing the side chain of Chemical Formula 2 into the main chain of Chemical Formula 1 by reacting an isocyanate compound with Chemical Formula 1.

Another exemplary embodiment of the present invention provides a negative photosensitive resin composition, comprising: a polyimide resin; a photosensitizer; a crosslinking agent; a surfactant; and a solvent.

Examples of photosensitive agents include a combination of a photopolymerization initiator and a compound having two or more olefinic unsaturated bonds. By containing a photopolymerization initiator and a compound having two or more olefinic unsaturated bonds, active radicals generated in the light-irradiated area promote radical polymerization of the olefinic unsaturated bonds, making it possible to obtain a negative relief pattern in which the light-irradiated area is insoluble.

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the entire polyimide resin. When the content is 0.1 parts by weight or more, sufficient free radicals are generated by light irradiation, and the sensitivity is improved. In addition, when the content exceeds 20 parts by weight, the non-irradiated area is cured by generating excessive free radicals, making it difficult to form ultra-fine patterns. The content of the compound having two or more olefinic unsaturated bonds is preferably 5 to 50 parts by weight based on 100 parts by weight of the entire polyimide resin. When the content is 5 parts by weight or more, it is preferred because a cured resin film having high mechanical properties can be obtained by crosslinking. When the content is 50 parts by weight or less, it is preferable because the sensitivity is not impaired.

In addition, as a crosslinking agent, poly(ethylene glycol) diacrylate, dipentatriol hexaacrylate, and the like can be used.

According to the exemplary embodiment of the present specification, the crosslinking agent includes two or more types of structures represented by the following chemical formula 4.

In Chemical Formula 4, R8 and R9 are hydrogen; or substituted or unsubstituted alkyl, n' is an integer from 1 to 100, and the acrylate group (-COO-) of Chemical Formula 4 is bonded to the acrylate group of Chemical Formula 2.

According to the exemplary embodiments of the present specification, two or more types of structures represented by Chemical Formula 4 are included, and the crosslinking agent having these two types of structures may have different molecular weights.

According to the exemplary embodiments of the present specification, R8 and R9 are the same or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

According to the exemplary embodiments of the present specification, R8 and R9 are the same or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

According to the exemplary embodiments of the present specification, R8 and R9 are the same or different from each other, and are each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.

In the above configuration, ultra-fine patterns, excellent mechanical properties, heat resistance properties, and the like are ensured.

Based on 100 parts by weight of the entire polyimide resin, the content of the crosslinking agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 10 parts by weight or more, and from the perspective of maintaining mechanical properties such as elongation, it is preferably 100 parts by weight or less, and more preferably 50 parts by weight or less.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, as the silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK- BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 and the like, and As a fluorine-based surfactant, it is possible to use a product manufactured by Dai Nippon Ink & Chemicals Co., Ltd. Chemicals, Inc.) (DIC) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445 , F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442 and the like, but the surfactant is not limited thereto.

As a solvent, it is possible to use a compound known to form a photosensitive resin composition in the field to which the present invention belongs, without particular limitation. As a non-limiting example, the solvent may be one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

The ester solvent may be, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like)), alkyl 3-oxypropionates (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3- ethyl ethoxypropionate and the like)), alkyl 2-oxypropionates (e.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate and the like (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2- oxy-2-methylpropionate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate or the like.

The ether solvent may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl glycol ethyl acetate, ethyl glycol ethyl acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate or the like.

The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone or the like.

The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene or the like.

The sulfoxide solvent may be dimethyl sulfoxide or a similar substance.

In addition, the negative photosensitive resin composition may further include additives known in the art depending on its use. For example, the negative photosensitive resin composition may further include an adhesion promoter, a defoaming agent, a leveling agent, an anti-gelling agent, a mixture thereof, and the like.

As the adhesion promoter, a silane coupling agent having a functional group such as an epoxy group, a carboxyl group or an isocyanate group can be used, and specific examples thereof include trimethoxysilylbenzoic acid, triethoxysilylbenzoic acid, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, a mixture thereof, or the like. Such an adhesion promoter can be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

As the surfactant, any surfactant known to be usable in a photosensitive resin composition may be used without any particular limitation, but a fluorine-based surfactant or a silicon-based surfactant is preferably used. Such a surfactant may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyimide resin.

According to the exemplary embodiments of the present specification, the polyimide resin may include one or two or more polyimide resins.

According to the exemplary embodiments of the present specification, the electronic device may be an electronic device including an organic insulating film or a photosensitive pattern formed by a negative photosensitive resin composition.

The organic insulating film or photosensitive pattern includes a polyimide having a specific structure and an acrylic compound including one or more photocurable acrylic functional groups, and thus can have improved mechanical properties, such as excellent heat resistance, insulation or chemical resistance, while achieving higher adhesion to substrates used in semiconductor devices, such as metal substrates (such as Au, Cu, Ni and Ti) or inorganic substrates (such as _SiO2 and SiNx).

The electronic device may be any of the following: plasma display panel (PDP), touch panel, light emitting diode (LED), organic light emitting diode (OLED), liquid crystal display (LCD), thin film transistor liquid-crystal display (LCD-TFT), cathode ray tube (CRT) and semiconductor, but is not limited thereto.

Therefore, an electronic device including an organic insulating film or a photosensitive pattern formed of a negative photosensitive resin composition can achieve excellent performance such as high resolution and high sensitivity, and can exhibit not only excellent film properties and high mechanical properties, but also excellent heat resistance properties, such as the characteristic that the adhesion of the organic insulating film or the photosensitive pattern can be firmly maintained without any degradation, even if the electronic device is used for a long period of time or exposed for a long period of time under high temperature conditions.

FIG. 1 shows an example of an organic insulating film for a semiconductor, including a photosensitive resin composition according to an exemplary embodiment of the present invention. Specifically, a silicon wafer 1 is coated with a positive photosensitive resin composition, and then exposed to form a first photosensitive pattern (referred to as PID1) 2, and a pad 3 (e.g., Cu pad) is provided in contact with this pattern, and a solder ball 4 is partially provided on the top of the pad. In order to fill the bottom filler area formed in this case, a second photosensitive pattern (referred to as PID2) 5 is formed using a negative photosensitive resin composition according to an exemplary embodiment of the present invention. This PID2 5 can be used as an organic insulating film corresponding to the outermost layer of the semiconductor packaging material.

FIG. 2 shows an example of an organic insulating film for an organic light-emitting device, including a photosensitive resin composition according to an exemplary embodiment of the present invention. Specifically, in an OLED layer 10, a first photosensitive pattern (referred to as a redistributed layer (RDL)) 7 formed of a positive photosensitive resin composition is provided on a substrate 6 (e.g., TFT glass or TFT plastic (here, TFT means thin film transistor)), and a pad 8 (e.g., Ag pad) is provided to contact the pattern. In this case, in order to leave a portion of the organic light-emitting material to enter the OLED, a second photosensitive pattern (referred to as a pixel define layer (PDL)) 9 is formed using a negative photosensitive resin composition according to an exemplary embodiment of the present invention. This PDL 9 can be used as an organic insulating film for an organic light-emitting device.

FIG. 3 and FIG. 4 are photographs of photosensitive patterns according to an exemplary embodiment of the present invention. Specifically, FIG. 3 shows a 15-micrometer square pattern with a thickness of 10 micrometers (μm), and FIG. 4 shows a 5-micrometer hole pattern with a thickness of 8 micrometers.

According to the exemplary embodiments of this specification, the organic insulating film may include an interlayer insulating film and a surface protective film.

According to the exemplary embodiment of this specification, the electronic device may further include a memory component.

The organic insulating film may include various insulating films of semiconductor devices, such as interlayer insulating films, surface protective films, substrate electrode protective layers, buffer coating films, passivation films, and the like. In addition, the electronic device may include various components of the semiconductor device.

The interlayer insulating film and the surface protective film are not particularly limited, and the interlayer insulating film and the surface protective film commonly used in this field can be used.

The memory component is not particularly limited, and a memory component commonly used in the art may be adopted.

At the same time, an organic insulating film or a photosensitive pattern can be formed by coating a negative photosensitive resin composition onto a supporting substrate, drying the negative photosensitive resin composition to form a resin film; exposing the resin film; developing the exposed resin film with a developer; and heat-treating the developed photosensitive resin film.

The patterned photosensitive resin film can be easily formed on a substrate such as glass or a silicon wafer using a negative photosensitive resin composition, and in this case, as a method of coating the negative photosensitive resin composition, spin coating, rod coating, screen printing, or the like can be used.

A supporting substrate that can be used in a process for forming a photosensitive resin film can be used without any particular limitation as long as it is known that the supporting substrate is generally used in the electronic communication field or the semiconductor field, but specific examples thereof include silicon wafers, glass substrates, metal substrates, ceramic substrates, polymer substrates, and the like.

In the drying process after coating, a pre-baked film may be formed by pre-baking at 50°C to 150°C for about 1 minute to 20 minutes to evaporate the solvent. When the drying temperature is too low, the amount of residual solvent is so large that film loss may occur in the exposed area during development, resulting in a lower residual film, and when the drying temperature is too high, the curing reaction is accelerated, so that the non-exposed area may not be developed.

When exposing the resin film, the mask on which the pattern to be processed is formed can be used to irradiate the mask with UV or visible light having a wavelength of 200 nm to 500 nm, and the exposure amount during the irradiation is preferably 10 mJ/ ^cm2 to 4,000 mJ/cm2. The exposure time is not particularly limited and can be appropriately changed depending on the exposure device used, the wavelength of the irradiation light, or the exposure amount, and specifically, the exposure time can be changed within the range of 1 second to 150 seconds.

In forming the photosensitive resin film, an alkaline aqueous developer generally known to be used in producing semiconductors or displays can be used without any particular limitation.

[Mode of the invention]

Hereinafter, the present specification will be described in detail with reference to examples used to specifically describe the present specification. However, the examples according to the present specification may be modified in various forms, and it should not be interpreted that the scope of the present specification is limited to the examples described below. The examples of the present specification are provided to more completely explain the present specification to a person having ordinary knowledge in the art.

<Synthesis Example 1>

After 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.1 equivalents of 4,4'-oxydiphthalic anhydride, and 0.13 equivalents of 3-aminophenol were dissolved in PMGEA under _N2 atmosphere, toluene was added to the reactant at 140°C, and the resulting mixture was connected to a Dean-Stark apparatus to perform a reaction at 150°C overnight. After the reaction, toluene from the Dean-Stark apparatus was removed, and then PGMEA substitution was performed several times to remove residual toluene. The residual monomer was confirmed by NMR to terminate the reaction, thereby preparing Polymer 1. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was 15,000 g/mol. The structure of polymer 1 is as follows.

[Polymer 1]

In polymer 1, q is a value where the weight average molecular weight of the polymer is 15,000 g/mol, and is a real number between 20 and 40.

<Synthesis Example 2>

After 1 equivalent of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 0.25 equivalent of 4,4'-oxydiphthalic acid diamine, 1.35 equivalent of 4,4'-oxydiphthalic anhydride, and 0.16 equivalent of 3-aminophenol were dissolved in propylene glycol methyl ether acetate (PGMEA) under _N2 atmosphere, toluene was added to the reactant at 150°C, and the resulting mixture was connected to a Dean-Stark apparatus to perform a reaction at 180°C overnight. After the reaction, toluene from the Dean-Stark apparatus was removed, and then PGMEA substitution was performed several times to remove residual toluene. The residual monomer was confirmed by NMR to terminate the reaction, thereby preparing a polymer 2 having the following structural formula. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 20,000 g/mol. The structure of polymer 2 is as follows.

[Polymer 2]

In polymer 2, p and q are values where the weight average molecular weight of the polymer is 17,000 g/mol, p is a real number from 5 to 40, and q is a real number from 2 to 15.

<Synthesis Example 3>

0.016 equivalents of triethylamine and 0.1 equivalents of 2-acryloyloxyethyl isocyanate were added to the polymer 1 prepared in the above-mentioned Synthesis Example 1, and placed in an oil bath, and then reacted at 80°C overnight. When the 2H peak at 4.25 parts per million (ppm) of 2-acryloyloxyethyl isocyanate (AOI) disappeared using NMR, the reaction was terminated.

The total OH of polymer 1 was calculated by comparing the input amount with the total area of the aromatic ring of the polymer appearing at 7 ppm or more on NMR, and the substitution ratio of AOI was confirmed by comparing the area of the peak (peak value, 3H) appearing around 6 ppm relative to the total OH. The polymer was confirmed to be substituted with 10 mol% AOI. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 18,000 g/mol. The structure of polymer 3 is as follows.

[Polymer 3]

In the polymer of Synthesis Example 3, q is a value where the weight average molecular weight of the polymer is 18,000 g/mol, and q is a real number of 20 to 40.

<Synthesis Example 4>

The procedure was performed in the same manner as in Synthesis Example 3 except that the polymer 2 prepared in Synthesis Example 2 was used. When the molecular weight was measured using gel permeation chromatography (GPC), the weight average molecular weight was confirmed to be 20,000 g/mol. The total OH of polymer 1 was calculated by comparing the input amount with the total area of the aromatic ring of the polymer appearing at 7 ppm or more on NMR, and the substitution ratio of AOI was confirmed by comparing the area of the peak (peak value, 3H) appearing around 6 ppm with the total OH. It was confirmed that the polymer was substituted with 15 mol% AOI. The structure of polymer 4 is as follows.

[Polymer 4]

In the polymer, p and q are values where the weight average molecular weight of the polymer is 20,000 g/mol, p is a real number from 5 to 40, and q is a real number from 2 to 15.

<Example 1 to Example 8 and Comparative Example 1 to Comparative Example 3>

A photosensitive resin composition is prepared using the components described in Table 1 below. Specifically, a photosensitive resin composition including the prepared polyimide resin and the components shown in Table 1 below is prepared. In the following table, 100 parts by weight of a resin composition including a polyimide resin (first and/or second polyimide resin), a photosensitizer, a crosslinking agent, a surfactant, and a solvent is used as a reference.

A: OXE-01 (BASF)

B: OXE-03 (BASF)

C: Poly(ethylene glycol) (200) diacrylate (Miramer M282, Miwon)

D: Poly(ethylene glycol) (600) diacrylate (Miramer M286, Miramer)

E: BYK-307 (BYK Chemical Co., Ltd.)

F: Propylene glycol monomethyl ether acetate

<Experimental Example>

The photosensitive resin compositions of the examples and comparative examples were evaluated under the following process conditions, and the results are shown in Table 2 below. Specifically, the prepared photosensitive resin composition was coated on a Cu/Si wafer by spin coating. After performing a soft bake at 120° C. for 120 seconds, the wafer was exposed to a suitable exposure (i-line (365 nm)), and then a development process was performed using a developer (2.38 wt % TMAH solution). The pattern characteristics were confirmed by performing a post-bake at 200° C. for 1 hour each. In addition, in order to additionally measure the temperature and mechanical properties of the cured film, the Si wafer was additionally coated with the respective prepared photoresist composition to expose the entire surface, and then soft-baked and post-baked at 200°C for 1 hour.

Anti-corrosion agent evaluation conditions: PrB 120℃/120 seconds, thickness 10 microns

Exposure: 400 mJ/cm2 to 500 mJ/cm2 i-line stepper

Development: 23°C, 2.38 wt% tetramethylammonium hydroxide (TMAH) solution, immersion, rinse with deionized water

[Image resolution]

The minimum size of the pattern was measured using a scanning electron microscope (SEM) on samples obtained by post-baking the prepared photosensitive resin compositions at the same exposure dose.

[Adhesion to substrate]

A 10-row x 10-row grid shape was cut at 2 mm intervals using a blade and aligned onto a fully exposed cured film on a prefabricated substrate, and the adhesion characteristics between the cured film and the substrate were evaluated by attaching the grid shape to a cellophane tape and detaching the cellophane tape to count the number of peeled pieces among a total of 100 grid shapes.

○: Less than 15 peeled off

△: Peel off 15 or more than 15 and less than 30

X: Remove 30 or more

[Measurement of glass transition temperature (Tg) and elongation at break of cured film]

The cured film was produced by peeling off the fully exposed cured film on the prefabricated substrate from the substrate using an aqueous hydrogen fluoride solution. For the insulating film with a thickness of 10 microns dried in an oven, the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the cured film were measured by thermomechanical analysis (TMA), and the elongation at break was measured at room temperature using a universal testing machine (UTM) at a speed of 5 cm/min.

Z

0.3的範圍，具有相對較高斷裂伸長率，同時維持良好玻璃轉化溫度(Tg)及熱膨脹係數(CTE)，可確認有可能確保極佳耐熱性及極佳機械特性，且同時有可能形成精細圖案。相比之下，在比較例1至比較例3中，僅使用合成實例1及/或合成實例2的聚合物，使得固化物理特性極差，CTE極低，且由於不包括化學式2的不飽和基團或Z的莫耳比不滿足上述範圍，因此斷裂伸長率相較於實例群組較低。 As shown in the results in Table 2 above, the polyimide resin and the photosensitive resin composition including the same according to the present specification have high-resolution pattern characteristics, and the cured film has excellent adhesion to the substrate. Since the cured films using the photosensitive resin compositions of Examples 1 to 7 include the unsaturated group of Chemical Formula 2 using the polymer in Synthesis Example 1 and/or Synthesis Example 4, and by allowing the molar ratio of Z to meet 0.05 when the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group,

Z

0.3, having a relatively high elongation at break, while maintaining a good glass transition temperature (Tg) and coefficient of thermal expansion (CTE), it can be confirmed that it is possible to ensure excellent heat resistance and excellent mechanical properties, and at the same time it is possible to form fine patterns. In contrast, in Comparative Examples 1 to 3, only the polymers of Synthesis Example 1 and/or Synthesis Example 2 are used, so that the curing physical properties are extremely poor, the CTE is extremely low, and because the unsaturated group of Chemical Formula 2 is not included or the molar ratio of Z does not meet the above range, the elongation at break is relatively low compared to the Example Group.

Claims (18)

A negative photosensitive resin composition comprises: a polyimide resin, wherein the polyimide resin comprises a structure of the following chemical formula 1, and the content of the polyimide resin is 50 parts by weight or more based on 100 parts by weight of the negative photosensitive resin composition:

In chemical formula 1,

means a part or repeating unit bonded to another substituent, X1 and X2 are the same or different from each other and are each independently a tetravalent organic group, Y is a divalent to tetravalent organic group, _R3 to _R6 are the same or different from each other and are each independently hydrogen; or represented by the following chemical formula 2, with the restriction that the ratio of the structure represented by the following chemical formula 2 is 1 mol% or greater than 1 mol%, m1, m2, k1 and k2 are each 0 or 1, and 1

m1+m2+k1+k2

2, Z is any divalent organic group in the following structures,

In the structure, B is a divalent organic group, and

is a bonding part with N of chemical formula 1, when the sum of the molar ratios of Y and Z is 1 and Z is a divalent organic group, the molar ratio of Z is 0.05

Z

0.3, n is a real number from 1 to 50, and m is a real number from 1 to 50,

In Chemical Formula 2, * is a moiety bonded to Chemical Formula 1, R7 is hydrogen; or a substituted or unsubstituted alkyl group, and p is an integer from 1 to 10. The negative photosensitive resin composition as described in claim 1, wherein X1 and X2 are the same or different from each other, and are independently selected from the group consisting of: a tetravalent aromatic organic group, a tetravalent aliphatic organic group, and a tetravalent organic group in which an aromatic group and an aliphatic group are bonded to each other. The negative photosensitive resin composition as described in claim 1, wherein X1 and X2 are the same or different from each other, and are each independently selected from the group consisting of the following structures:

In the structure,

It is a bonding portion to the carbonyl group (C(=O)) of Chemical Formula 1. The negative photosensitive resin composition as described in claim 1, wherein Y is selected from the group consisting of: divalent to tetravalent aromatic organic groups, divalent to tetravalent aliphatic organic groups, and divalent to tetravalent organic groups in which the aromatic group and the aliphatic group are bonded to each other. The negative photosensitive resin composition as described in claim 1, wherein Y is selected from the group consisting of the following structures:

In the structure, A is a divalent organic group, and

is a bonding portion with N of Chemical Formula 1. The negative photosensitive resin composition as described in claim 5, wherein A is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C(=O) or _SO2 . The negative photosensitive resin composition as described in claim 5, wherein A is selected from the group consisting of the following structures:

In the structure, * is

The bonding portion of each phenolic group. The negative photosensitive resin composition as described in claim 1, wherein B is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by O, S, C (=O) or _SO2 . The negative photosensitive resin composition as described in claim 8, wherein B is selected from the group consisting of the following structures:

In the structure, * is used for

The bonding portion of each phenyl group. The negative photosensitive resin composition as described in claim 1 further comprises a structure represented by the following chemical formula 3 as an end group:

Wherein in Chemical Formula 3, * is a portion bonded to Chemical Formula 1, Re1 is hydrogen; or a substituted or unsubstituted alkyl group, re1 is a real number from 0 to 4, and when re1 is 2 or greater, Re1 are the same as or different from each other, and Re is hydrogen; or a structure represented by Chemical Formula 2. A negative photosensitive resin composition as described in claim 1, wherein the ratio of the structure represented by chemical formula 2 is 10 mol% to 70 mol% relative to the total molar number of OH groups contained in the polyimide resin. A negative photosensitive resin composition as described in claim 1, wherein the weight average molecular weight of the polyimide resin is 5,000 g/mol to 200,000 g/mol. The negative photosensitive resin composition as described in claim 1 further comprises: a photosensitizer; a crosslinking agent; a surfactant; and a solvent. The negative photosensitive resin composition of claim 13, wherein the crosslinking agent comprises two or more types of structures represented by the following chemical formula 4:

In Chemical Formula 4, R8 and R9 are the same as or different from each other and are each independently hydrogen; or a substituted or unsubstituted alkyl group, n' is an integer from 1 to 100, and the acrylate group (-COO-) of Chemical Formula 4 is bonded to the acrylate group of Chemical Formula 2 during exposure. A negative photosensitive resin composition as described in claim 13, wherein the polyimide resin comprises one or two or more polyimide resins. An electronic device comprising an organic insulating film or photosensitive pattern formed by the negative photosensitive resin composition as described in any one of claims 1 to 15. An electronic device as described in claim 16, wherein the organic insulating film comprises an interlayer insulating film and a surface protective film. The electronic device as described in claim 16 further includes a memory component.