KR20240060471A - Polyimide resin, negative type photosensitive resin composition comprising same and electronic device - Google Patents

Abstract

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

Description

Polyimide resin, negative photosensitive resin composition containing same, and electronic device {POLYIMIDE RESIN, NEGATIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION COMPRISING SAME AND ELECTRONIC DEVICE}

The present invention relates to a photosensitive resin composition, and more specifically, to a negative ring-closed polyimide resin with excellent solubility and no swelling during development, a negative photosensitive resin composition containing the same, and an electronic device.

This application claims the benefit of Korean Patent Application No. 10-2022-0141533 filed with the Korean Intellectual Property Office on October 28, 2022, the entire contents of which are incorporated herein by reference.

Photosensitive resin is a representative functional polymer material that has been used in the production of various precision electronic and information industrial products, and is currently being used importantly in the high-tech industry, especially in the production of semiconductors and displays. In general, photosensitive resin refers to a polymer compound in which a chemical change in the molecular structure occurs within a short period of time due to light irradiation, resulting in changes in physical properties such as solubility in a specific solvent, coloring, and curing. Using photosensitive resin, micro-precision processing is possible, energy and raw materials can be greatly reduced compared to thermal reaction processes, and work can be performed quickly and accurately in a small installation space, so it can be used in advanced printing fields, semiconductor production, and display production. It is widely used in various precision electronic and information industries, such as photocurable surface coating materials.

These photosensitive resins can be broadly divided into negative type and positive type. The negative type photosensitive resin is a type in which the light-irradiated portion is insoluble in the developer, and the positive type photosensitive resin is a type in which the light-irradiated portion is solubilized in the developer. am.

The polymer used in negative photosensitive resin requires that, after selective exposure, the exposed portion must have high solubility in the developer, and the unexposed portion must have low or no solubility in the developer. These requirements are for precision electronics. In the information industry, there is an increasing need to be able to form extremely fine patterns.

The present invention seeks to provide a polyimide with a closed ring structure that has excellent solubility and does not cause swelling during development when forming a pattern using a negative photosensitive composition, and a negative photosensitive resin composition containing the same.

Additionally, the present invention is to provide an electronic device including an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition.

An exemplary embodiment of the present specification provides a polyimide resin containing the structure of Formula 1 below.

[Formula 1]

In Formula 1,

는 다른 치환기 또는 반복 단위에 결합되는 부분을 의미하고,

means a portion bound to another substituent or repeating unit,

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,

R ₃ to R ₆ are the same as or different from each other, and are each independently hydrogen; or represented by the following formula (2), provided that the structure represented by the following formula (2) is 1 mol% or more relative to the total number of moles of OH groups contained 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,

m is a real number from 0 to 50,

[Formula 2]

In Formula 2,

* is a portion connected to Formula 1 above,

R7 is hydrogen; Or a substituted or unsubstituted alkyl group,

p is an integer from 1 to 10.

Another embodiment of the present invention is the polyimide resin; photosensitizer; crosslinking agent; A negative photosensitive resin composition containing a surfactant and a solvent is provided.

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

When forming a pattern using the negative photosensitive resin composition according to the present specification, the polyimide resin does not swell even during development after selective exposure and has excellent solubility. In addition, an electronic device including an organic insulating film or photosensitive pattern with excellent performance formed from the negative photosensitive resin composition according to the present specification can be provided.

Figure 1 shows an example of an organic insulating film for a semiconductor containing a photosensitive resin composition according to an exemplary embodiment of the present invention.
Figure 2 shows an example of an organic insulating film for an organic light-emitting device containing a photosensitive resin composition according to an exemplary embodiment of the present invention.
3 and 4 are photographs of a photosensitive pattern according to an exemplary embodiment of the present invention.

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

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

One embodiment of the present invention provides a polyimide resin containing the structure of Formula 1 below.

[Formula 1]

In Formula 1,

는 다른 치환기 또는 반복 단위에 결합되는 부분을 의미하고,

means a portion bound to another substituent or repeating unit,

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,

R ₃ to R ₆ are the same as or different from each other, and are each independently hydrogen; or represented by the following formula (2), provided that the structure represented by the following formula (2) is 1 mol% or more relative to the total number of moles of OH groups contained 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,

m is a real number from 0 to 50,

[Formula 2]

In Formula 2,

* is a portion connected to Formula 1 above,

R7 is hydrogen; Or a substituted or unsubstituted alkyl group,

p is an integer from 1 to 10.

The present inventors have found that the photosensitive resin containing the polyimide resin of the above-mentioned specific structure can be used as a substrate used in a semiconductor device or display device, for example, a metal substrate such as Au, Cu, Ni, Ti, or an inorganic material such as SiO ₂ or SiNx. The invention was completed after confirming through experiments that it can achieve high adhesion and adhesion to the substrate, has improved mechanical properties such as excellent heat resistance or chemical resistance, and can easily form ultra-fine patterns.

In addition, the present inventors were able to secure fine patterns and excellent physical properties by adding acrylate (-COO-) to the polyimide resin containing the structure of Chemical Formula 1.

In particular, the negative photosensitive resin composition does not use a polyimide precursor, which requires a high-temperature heat curing process (imidization process), but uses a polyimide resin that can be solution processed at low temperature, so the high-temperature imidization process can be omitted. there is.

The present inventors found that when using a structure in which a photopolymerizable unsaturated group is bonded to the side chain of a polyimide with a closed ring structure as an existing polyimide, the swelling phenomenon is reduced due to a decrease in solubility during development. In addition, when ring-closed polyimide and a monomer having a photopolymerizable multifunctional group are used together, the polymer itself does not have a photopolymerizable group, so high energy is generated during the curing process by exposure, making precise patterning difficult and process costs increasing. It was discovered that there is Additionally, attempts are being made to introduce a polyamic ester structure (poly amic ester type) by ring-opening the acid anhydride ring-closure structure of the ring-closed polyimide and attaching a photopolymerizable group (R) to the ring-opened position. It was found that there was a problem of unstable dimensional stability and gas generation due to the detachment of the synthesized group (R).

However, the polyimide resin according to the above-described embodiment of the present invention includes a photopolymerizable unsaturated group (represented by Formula 2) in some of the main chain and end groups, so that even during development, the end groups are ring-closed with the main chain or side chains bonded thereto. It does not cause a reaction and gives the characteristic that swelling does not occur during development.

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

According to an exemplary embodiment of the present specification, R7 is hydrogen; Or it is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, X1 and It can be.

_According to an exemplary embodiment of the present specification, X1 and It may be an alkyl group substituted or unsubstituted with a halogen group, or an aryl group substituted or unsubstituted with a halogen group or an alkyl group.

According to an exemplary embodiment of the present specification, X1 and X2 are the same as or different from each other, and each may be independently selected from the group consisting of the following structures.

In the above structure,

는 4가 유기기의 표시로서, 상기 화학식 1의 카보닐기(C(=O))와의 연결 부위이다.

is an indication of a tetravalent organic group and is a connection site with the carbonyl group (C(=O)) of Formula 1 above.

이다.According to an exemplary embodiment of the present specification, X1 and X2 are

am.

As the polyimide resin includes the above structure, the mechanical properties of the polyimide resin increase, and the penetration effect of the developer solution increases during development, which is effective in forming an ultrafine pattern.

According to an exemplary embodiment of the present specification, Y may be selected from the group consisting of a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are connected to each other. .

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

According to an exemplary embodiment of the present specification, Y may be selected from the group consisting of the following structures.

는 상기 화학식 1의 N과의 연결 부위일 수 있다. In the above structure, A is a divalent organic group,

may be a connection site with N of Formula 1 above.

는 최소 2가 최대 4가 유기기의 표시이다.According to one embodiment of the present specification,

is an indication of an organic group of at least 2 valence and up to 4 valence.

According to one embodiment of the present specification, A is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C (=O), or SO ₂ , or a divalent organic group of the hydrocarbon It may be a divalent organic group in which at least one hydrogen is replaced with a halogen or alkyl group.

According to one embodiment of the present specification, A is a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C (=O), or SO ₂ , or the hydrocarbon It may be a divalent organic group in which at least one hydrogen is replaced with a halogen or alkyl group.

According to an exemplary embodiment of the present specification, A may be selected from the group consisting of the following structures.

In the above structure,

의 각 페놀기에 대한 연결 부위이다.* above

This is the connection site for each phenol group.

이고, 여기서 A는

이다.According to an exemplary embodiment of the present specification, Y is

, where A is

am.

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

는 상기 화학식 1의 N과의 연결 부위일 수 있다.In the above structure, B is a divalent organic group,

may be a connection site with N of Formula 1 above.

는 최소 2가 최대 4가 유기기의 표시이다.According to one embodiment of the present specification,

is an indication of an organic group of at least 2 valence and up to 4 valence.

According to one embodiment of the present specification, B is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C (=O), or SO ₂ , or a divalent organic group of the hydrocarbon It may be a divalent organic group in which at least one hydrogen is replaced with a halogen or alkyl group.

According to an exemplary embodiment of the present specification, B is a divalent hydrocarbon, or a divalent aliphatic organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C (=O), or SO ₂ , or the hydrocarbon It may be a divalent organic group in which at least one hydrogen is replaced with a halogen or alkyl group.

According to an exemplary embodiment of the present specification, B may be selected from the group consisting of the following structures.

의 각 페닐기에 대한 연결 부위이다.In the above structure, * represents the above

This is the connection site for each phenyl group.

According to an exemplary embodiment of the present specification, Z is a direct bond.

By including the above structure, the polyimide resin has the effect of forming an ultrafine pattern through control of developability.

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

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

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

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

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

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

In the present specification, the aromatic (organic) group may be a C6 to C20 arylene group, and the aliphatic group may be a C1 to C20 alkylene group, or a C3 to C20 cycloalkylene group. The arylene group includes a phenylene group and the like.

In this specification, the halogen group includes F, Cl, etc.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; hydroxyl group; -COOH; Alkyl group; Cycloalkyl group; Aryl group; and is substituted with one or more substituents selected from the group containing heteroaryl groups or does not have any substituents.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the carbon number of the alkyl group is 1 to 30. According to another embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-oxyl group. There is a til group, etc., but it is not limited to these.

In this specification, an alkylene group refers to a divalent alkyl group, and the above description applies to the alkyl group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, it includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is 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 one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl group, but is not limited thereto. The polycyclic aryl group may include a naphthyl group, anthracenyl group, indenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but has 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridyl group, and pyridazine group. , quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuran There are others, but it is not limited to these.

In the present specification, the heterocyclic group may be an aliphatic or aromatic ring group.

In the present specification, the description regarding the heterocyclic group described above can be applied, except that the heteroaryl group is aromatic.

The other terminal of the polyimide resin may also have the terminal of Formula 2, and may have diamine or dianhydride used in producing the polyimide as the terminal group.

In an exemplary embodiment of the present specification, R ₃ to R ₆ are the same or different from each other, at least one is represented by Formula 2, and the remainder are hydrogen, provided that the structure represented by Formula 2 is the polyimide resin It is more than 1 mol% compared to the total number of moles of OH groups contained in.

When forming a pattern using the negative photosensitive resin composition according to the above embodiment, the polyimide resin does not swell even during development after selective exposure and has excellent solubility in a developer.

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

If the structure represented by Formula 2 is less than 10 mol% relative to the total number of moles of OH groups included in the polyimide resin, the number of OH protected by a protecting group is small and the number of OH not protected by a protecting group is relatively large, resulting in remaining The blocking rate may be lowered. In addition, when the structure represented by Formula 2 exceeds 70 mol% relative to the total number of moles of OH groups contained in the polyimide resin, the number of OH protected by a protecting group is large and the number of OH not protected by a protecting group is relatively large. Therefore, it may be difficult to implement ultrafine patterns due to low solubility in alkaline aqueous solutions.

Preferably, the structure represented by Formula 2 is 15 mol% to 45 mol% based on the total number of moles of OH groups included in the polyimide resin.

Polyimide resins within the above range can comprehensively improve physical properties such as developability, film retention rate, and sensitivity.

In an exemplary embodiment of the present specification, as in the above structures, when m1+m2+k1+k2 is 1 or 2 and includes an OH or COOH group, the structure of Formula 2 is applied not only to the ends of the polyimide resin but also to the side chain. It is advantageous in improving the surface condition when forming a photosensitive film.

According to an exemplary embodiment of the present specification, as the input ratio of diamine in the polyimide resin of Chemical Formula 1, assuming that the sum of the molar ratios of Y and Z is 1, if Z is a divalent organic group, The molar ratio may be 0.05 ≤ Z ≤ 0.3.

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

[Formula 3]

In Formula 3,

* is a portion connected to Formula 1 above,

Re1 is hydrogen; Or a substituted or unsubstituted alkyl group,

re1 is a real number from 0 to 4, and if re1 is 2 or more, Re1 is the same or different,

Re is hydrogen; Or it is a structure represented by Formula 2 above.

In one embodiment of the present specification, Re1 is hydrogen; Or it is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, Re1 is hydrogen; Or it is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present specification, Re1 is hydrogen; Or it is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, Re1 is hydrogen.

In one embodiment of the present specification, Re is hydrogen.

In an exemplary embodiment of the present specification, Re is a structure represented by Formula 2 above.

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

If the weight average molecular weight is less than 5,000, it may be difficult to achieve the desired coating and mechanical properties when applying the polyimide copolymer, and if it is more than 200,000, the solubility in the developer may be low, making it difficult to apply as a photosensitive material. .

The weight average molecular weight is one of the average molecular weights that are used as a standard for the molecular weight of certain polymer materials whose molecular weight is not uniform. It is a value obtained by averaging the molecular weights of the component molecular species of a polymer compound with a molecular weight distribution by weight fraction.

The weight average molecular weight may be a value measured by gel permeation chromatography, that is, GPC.

The polyimide resin can be produced as one type of polyimide (example of the polyimide of Chemical Formula 1) using a dianhydride compound and a diamine compound, as shown in Scheme 1 below. In addition, to produce other types of polyimides, materials and polymerization methods known in the art can be used.

[Scheme 1]

In addition, in order to have a terminal group for the polyimide of Formula 1, when polymerizing the polyimide, it has at least one group selected from hydroxyl group, carboxyl group, thiol group, and sulfonic acid group, and has one anhydride group or one amine group. By using the compound, a polyimide having at least one group selected from hydroxyl group, carboxyl group, thiol group, and sulfonic acid group can be prepared, and by reacting it with an isocyanate-based compound, the terminal group of Formula 1 can be prepared. In Reaction Scheme 2 below, a side chain of Chemical Formula 2 is introduced into the main chain of Chemical Formula 1 by reacting Chemical Formula 1 with an isocyanate-based compound.

[Scheme 2]

Another embodiment of the present invention is a polyimide resin; photosensitizer; crosslinking agent; A negative photosensitive resin composition containing a surfactant and a solvent is provided.

Examples of the photosensitizer include a combination of a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds. By containing a photopolymerization initiator and a compound having two or more ethylenically unsaturated bonds, active radicals generated in the light irradiated portion advance radical polymerization of the ethylenically unsaturated bonds, and a negative relief pattern in which the light irradiated portion is insolubilized can be obtained. .

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total polyimide resin. If the content is 0.1 part by weight or more, sufficient radicals are generated by light irradiation, and sensitivity is improved. In addition, when the content exceeds 20 parts by weight, the unirradiated portion is hardened due to the generation of excessive radicals, making it difficult to form an ultrafine pattern. The content of the compound having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by weight based on 100 parts by weight of the total polyimide resin. A content of 5 parts by weight or more is preferable because a cured resin film with high mechanical properties can be obtained by crosslinking. It is preferable that the content is 50 parts by weight or less because sensitivity is not impaired.

Additionally, the crosslinking agent may be poly(ethylene glycol) diacrylate, dipentaerythritol hexaacrylate, etc.

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

[Formula 4]

In Formula 4,

R8 and R9 are hydrogen; Or a substituted or unsubstituted alkyl group,

n' is an integer from 1 to 100,

The acrylate group (-COO-) of Chemical Formula 4 is connected to the acrylate group of Chemical Formula 2.

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

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

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

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

With the above configuration, ultrafine patterns, excellent mechanical properties, and heat resistance characteristics can be secured.

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, based on 100 parts by weight of the total polyimide resin, and is preferable from the viewpoint of maintaining mechanical properties such as elongation. It is preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 manufactured by BYK-Chemie. , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, 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, etc. are available. Fluorine-based surfactants include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, and F-444 from DIC (DaiNippon Ink & Chemicals). , 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, etc. can be used, but are not limited to these.

As the solvent, any compound known in the technical field to which the present invention pertains to enable the formation of a photosensitive resin composition may be used 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 solvents include 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, gamma- Butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, methoxyacetate) Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionate alkyl esters (e.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate) (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methyl Methyl propionate and 2-oxy-2-methylethylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, It may be methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.

The ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol It may be lycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

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

The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, etc.

The sulfoxide-based solvent may be dimethyl sulfoxide or the like.

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, an antifoaming agent, a leveling agent, an anti-gel agent, or a mixture thereof.

As the adhesion promoter, a silane coupling agent having a functional group such as epoxy, carboxyl, or isocyanate can be used, and specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, and gamma. -Isocyanatopropyltrimethoxysilane (γ-isocyanatopropyltrimethoxysilane), gamma-isocyanatopropyltriethoxysilane (γ-isocyanatopropyltriethoxysilane), gamma-Glycidoxypropyltrimethoxysilane (γ-Glycidoxypropyltrimethoxysilane), gamma -Glycidoxypropyltriethoxysilane (γ-Glycidoxypropyltriethoxysilane) or mixtures thereof. This adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyimide resin.

The surfactant may be used without any restrictions as long as it is known to be used in photosensitive resin compositions, but it is preferable to use a fluorine-based surfactant or a silicone-based surfactant. These surfactants 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 an exemplary embodiment of the present specification, the polyimide resin may include one or two or more types of polyimide resin.

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

The organic insulating film or photosensitive pattern includes a polyimide of a specific structure and an acrylic compound containing one or more photocurable acrylic functional groups, and can be used as a substrate used in semiconductor devices, such as Au, Cu, Ni, Ti, etc. It can achieve high adhesion to metal substrates or inorganic substrates such as SiO2 or SiNx, while also having improved mechanical properties such as excellent heat resistance, insulation, or chemical resistance.

The electronic devices include a plasma display panel (PDP), a touch panel, a light emitting diode (LED), an organic light emitting diode (OLED), and a liquid crystal display (LCD). , a thin film transistor liquid crystal display (LCD-TFT), a cathode ray tube (CRT), and a semiconductor, but is not limited thereto.

Therefore, an electronic device including an organic insulating film or photosensitive pattern formed from the negative photosensitive resin composition can realize excellent performance such as high resolution and high sensitivity, and exhibit excellent film properties and high mechanical properties, as well as excellent heat resistance properties. For example, even when used for a long time or exposed to high temperature conditions for a long time, the adhesion of the organic insulating film or photosensitive pattern is not deteriorated and can be maintained firmly.

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

Figure 2 shows an example of an organic insulating film for an organic light-emitting device containing a photosensitive resin composition according to an exemplary embodiment of the present invention. Specifically, in the OLED layer 10, a first photosensitive pattern (RDL (Redistributed DDL) formed of a positive photosensitive resin composition on a substrate 6 (e.g., TFT glass or TFT plastic (here, TFT refers to a thin film transistor) layer) (7) is provided, and a pad (e.g., Ag pad) is provided in contact with this pattern. At this time, in the OLED, in order to leave a portion for the organic light-emitting materials to enter, according to the present invention. A second photosensitive pattern (referred to as a pixel diffine layer (PDL)) 9 is formed using the negative photosensitive resin composition according to one embodiment. The PDL 9 may be used as an organic insulating film of an organic light emitting device. .

3 and 4 are photographs of a photosensitive pattern according to an exemplary embodiment of the present invention. Specifically, Figure 3 shows a 15 um square pattern and a thickness of 10 um, and Figure 4 shows a 5 um hole pattern and a thickness of 8 um.

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

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

The organic insulating film may include various insulating films of a semiconductor device, for example, an interlayer insulating film, a surface protective film, a substrate electrode protective layer, a buffer coat film, or a passivation film. Additionally, the electrical device may include various components of a semiconductor device.

The interlayer insulating film and surface protective film are not particularly limited, and those commonly used in the art may be employed.

The memory components are not particularly limited, and those commonly used in the art may be employed.

Meanwhile, the organic insulating film or photosensitive pattern includes the steps of applying the negative photosensitive resin composition on a support substrate and drying it to form a resin film; exposing the resin film to light; It may be formed through developing the exposed resin film with a developer and heat-treating the developed photosensitive resin film.

Using the negative photosensitive resin composition, a patterned photosensitive resin film can be easily formed on a substrate such as glass or silicon wafer. At this time, the method of applying the negative photosensitive resin composition is spin coating. coating, bar coating, screen printing, etc. can be used.

Support substrates that can be used in the process of forming the photosensitive resin film can be used without particular limitations as long as they are known to be commonly used in the electronic communication field or semiconductor field. Specific examples include silicon wafers, glass substrates, metal substrates, ceramic substrates, A polymer substrate, etc. can be mentioned.

In the drying process after application, a prebaked film can be formed by prebaking at 50°C to 150°C for 1 to 20 minutes to volatilize the solvent. If the drying temperature is too low, the amount of remaining solvent may become too large, which may cause film loss in the exposed area during development, lowering the remaining film. If the drying temperature is too high, the curing reaction may be accelerated and the unexposed area may not be developed. there is.

In the step of exposing the resin film, ultraviolet rays or visible light with a wavelength of 200 nm to 500 nm can be irradiated using a photomask on which the pattern to be processed is formed, and the exposure amount during irradiation is preferably 10 mJ/cm2 to 4,000 mJ/cm2. The exposure time is also not particularly limited and can be appropriately changed depending on the exposure device used, the wavelength of the irradiation light, or the exposure amount. Specifically, the exposure time can be changed within the range of 1 second to 150 seconds.

In the step of forming the photosensitive resin film, an alkaline aqueous developer known to be commonly used in the semiconductor or display production step can be used without any restrictions.

Hereinafter, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

<Synthesis Example 1>

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) 1eq, 4,4'-oxydiphthalic anhydride (4,4'-Oxydiphthalic anhydride) 1.1eq and 3-Aminophenol (3-Aminophenol) 0.13eq were dissolved in PMGEA under N ₂ atmosphere, then toluene was added to the reactant at 140°C, and Dean-Stark was connected to react at 150°C. The reaction was performed overnight at ℃. After the reaction, Dean-Stark's toluene was removed, and then PGMEA was substituted several times to remove residual toluene. Polymer 1 was prepared by confirming the residual monomer using NMR and completing the reaction. When 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 real number of 20 to 40, which indicates that the weight average molecular weight of the polymer is 15,000 g/mol.

<Synthesis Example 2>

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) 1eq, 4,4'-oxydiphthalic diamine ( 4,4'-Oxydiphthalic diamine) 0.25eq, 4,4'-Oxydiphthalic anhydride (4,4'-Oxydiphthalic anhydride) 1.35eq, 3-Aminophenol (3-Aminophenol) 0.16eq under N ₂ atmosphere. After dissolving in PGMEA (Propylene glycol methyl ether acetate), toluene was added to the reaction product at 150°C, Dean-Stark was connected, and reaction was performed overnight at 180°C. After the reaction, Dean-Stark's toluene was removed, and then PGMEA was substituted several times to remove residual toluene. Residual monomers were confirmed by NMR, the reaction was terminated, and polymer 2 of the following structural formula was prepared. When measuring molecular weight 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 having a weight average molecular weight of 17,000 g/mol, where p is a real number from 5 to 40 and q is a real number from 2 to 15.

<Synthesis Example 3>

To Polymer 1 prepared in Synthesis Example 1, 0.016 eq of triethylamine and 0.1 eq of 2-Acryloyloxyethyl isocyanate relative to the OH of polyimide were added, an oil bath was installed, and reaction was performed overnight at 80°C. The reaction was completed when the 2H peak at 4.25 ppm of AOI (2-Acryloyloxyethyl isocyanate) disappeared by NMR.

The total OH of Polymer 1 was calculated by comparing the input amount as the total area of the aromatic rings of the polymer appearing above 7ppm on NMR, and the substitution ratio of AOI was confirmed by the area of the peak (3H) appearing around 6ppm compared to the total OH. It was confirmed that the polymer was substituted with 10 mol% AOI. When measuring molecular weight 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 Polymer 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 between 20 and 40.

<Synthesis Example 4>

Polymer 1 dash was performed in the same manner as Synthesis Example 3, except that Polymer 2 prepared in Synthesis Example 2 was used. When measuring molecular weight 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 as the total area of the aromatic rings of the polymer appearing above 7ppm on NMR, and the substitution ratio of AOI was confirmed by the area of the peak (3H) appearing around 6ppm compared to 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 Polymer 4, p and q are values having a weight average molecular weight of 20,000 g/mol, p is a real number from 5 to 40, and q is a real number from 2 to 15.

<Examples 1 to 7 and Comparative Examples 1 to 3>

A photosensitive resin composition was prepared using the components listed in Table 1 below. Specifically, a photosensitive resin composition was prepared including the prepared polyimide resin and each component listed in Table 1 below. The table below is based on 100 parts by weight of the resin composition including polyimide resin (first and/or second polyimide resin), photosensitive agent, crosslinking agent, surfactant, and solvent.

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, Miwon)

E: BYK-307 (BYK-Chemie)

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 applied on a Cu/Si wafer by spin coating. After soft baking at 120°C for 120 seconds, exposure was performed at an appropriate exposure amount (i-line (365 nm)), and the development process was performed using a developer (2.38 wt% TMAH sol.). Post bake was performed at 200°C for 1 hour each to confirm pattern properties. In addition, in order to measure the temperature and mechanical properties of the cured film, each prepared photosensitive resin composition was additionally coated on the Si wafer, subjected to full-scale exposure, and then soft-baked, followed by post-bake at 200°C for 1 hour. did.

Resist evaluation conditions: PrB 120℃/120s, thickness 10㎛

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

develope: 23 ℃, 2.38 wt% TMAH (Tetramethylammonium hydroxide) solution, Dipping, DI water rinse

[Pattern resolution]

The minimum size of the pattern was measured through a SEM (Scanning Electron Microscope) of post-baked samples of each photosensitive resin composition produced at the same exposure dose.

[Adhesion to substrate]

Using a blade, cut 10 rows The adhesion characteristics were evaluated.

○: Peeled off to less than 15 pieces

△: Peeled off to more than 15 ~ less than 30 pieces

X: Peeled in more than 30 pieces

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

The cured film fully exposed on the previously prepared substrate was peeled from the substrate with an aqueous hydrogen fluoride solution, and then a cured film was manufactured. The Tg (glass transition temperature) and CTE (coefficient of thermal expansion) of the cured film were measured using TMA (Thermomechanical analysis) on an insulating film with a thickness of 10㎛ dried in an oven, and the test was performed using a UTM (Universal Testing Machine) at room temperature and a speed of 5 cm/min. Elongation at break was measured.

No. Photosensitive resin composition
Pattern resolution (um) with the substrate
adhesiveness cured film
Tg(℃) cured film
CTE
(ppm/ ℃) Breaking believer
(%) Example 1 <15 O 230 52 8 Example 2 <20 O 240 50 12 Example 3 <10 O 230 53 8 Example 4 <20 O 230 53 8 Example 5 <25 O 230 53 8 Example 6 <15 O 220 57 20 Example 7 <15 O 210 60 35 Comparative Example 1 peeling O 230 48 4 Comparative Example 2 peeling O 230 48 4 Comparative Example 3 peeling O 230 48 4

As shown in Table 2, the polyimide resin and the photosensitive resin composition containing the same according to the present specification have high-resolution pattern characteristics, and the cured film has excellent adhesion to the substrate. The cured film using the photosensitive resin composition of Examples 1 to 7 includes an unsaturated group of Formula 2 using the polymer of Synthesis Example 3 and/or 4, and the sum of the molar ratios of Y and Z is 1, and Z When it is a divalent organic group, the molar ratio of Z satisfies the range of 0.05 ≤ Z ≤ 0.3, thereby maintaining good Tg (glass transition temperature) and CTE (coefficient of thermal expansion) while maintaining relatively high elongation at break, resulting in excellent heat resistance. It was confirmed that excellent mechanical properties could be secured, and at the same time, fine patterns could be formed.

On the other hand, Comparative Examples 1 to 3 used only the polymers of Synthesis Examples 1 and/or 2, and did not contain an unsaturated group of Formula 2 or the molar ratio of Z did not satisfy the above range, so the curing properties were lower than those of the Example group. Very poor, very low CTE, or low elongation at break.

1: Silicon wafer (Si wafer)
2: First photosensitive pattern (PID1)
3, 8: Pad
4: Solder ball
5: Second photosensitive pattern (PID2)
6: substrate
7: First photosensitive pattern (RDL)
9: Second photosensitive pattern (PDL)
10: OLED layer

Claims (19)

A polyimide resin comprising the structure of Formula 1:
[Formula 1]

In Formula 1,

means a portion bound to another substituent or repeating unit,
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,
R ₃ to R ₆ are the same as or different from each other, and are each independently hydrogen; or is represented by the following formula (2), provided that the structure represented by the following formula (2) is 1 mol% or more relative to the total number of moles of -OH contained 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,
m is a real number from 0 to 50,
[Formula 2]

In Formula 2,
* is a portion connected to Formula 1 above,
R7 is hydrogen; Or a substituted or unsubstituted alkyl group,
p is an integer from 1 to 10. In claim 1,
A polyimide resin wherein X1 and In claim 1,
X1 and X2 are the same as or different from each other, and are each independently selected from the group consisting of the following structures:

In the above structure,

is a connection site with the carbonyl group (C(=O)) of Formula 1 above. In claim 1,
Y is a polyimide resin selected from the group consisting of a divalent to tetravalent aromatic organic group, a divalent to tetravalent aliphatic organic group, and a divalent to tetravalent organic group in which an aromatic group and an aliphatic group are linked to each other. In claim 1,
Y is a polyimide resin selected from the group consisting of the following structures:

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

is the connection site with N in Formula 1 above. In claim 5,
A is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C(=O), or SO ₂ , or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or alkyl group. A polyimide resin in which the substituted divalent organic group is used. In claim 5,
A is a polyimide resin selected from the group consisting of the following structures:

In the above structure,
* above

This is the connection site for each phenol group. In claim 1,
A polyimide resin in which Z is a direct bond or a divalent organic group of any of the following structures:

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

is a polyimide resin that is connected to N of Formula 1 above. In claim 8,
B is a divalent hydrocarbon, or a divalent organic group in which at least one carbon of the hydrocarbon is replaced by 0, S, C(=O), or SO ₂ , or a divalent organic group in which at least one hydrogen of the hydrocarbon is replaced by a halogen or alkyl group. A polyimide resin in which the substituted divalent organic group is used. In claim 8,
B is a polyimide resin selected from the group consisting of the following structures:

In the above structure,
* above

This is the connection site for each phenyl group. In claim 1,
The polyimide resin further includes a structure represented by the following formula (3) as an end group:
[Formula 3]

In Formula 3,
* is a portion connected to Formula 1 above,
Re1 is hydrogen; Or a substituted or unsubstituted alkyl group,
re1 is a real number from 0 to 4, and if re1 is 2 or more, Re1 is the same or different,
Re is hydrogen; Or it is the structure represented by Formula 2 above. In claim 1,
A polyimide resin in which the structure represented by Formula 2 is 10 mol% to 70 mol% relative to the total number of moles of OH groups included in the polyimide resin. In claim 1,
A polyimide resin having a weight average molecular weight of 5,000 g/mol to 200,000 g/mol. The polyimide resin according to any one of claims 1 to 13; photosensitizer; crosslinking agent; A negative photosensitive resin composition containing a surfactant and a solvent. In claim 14,
A negative photosensitive resin composition wherein the crosslinking agent includes two or more structures represented by the following formula (4):
[Formula 4]

In Formula 4,
R8 and R9 are the same 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,
The acrylate group (-COO-) of Chemical Formula 4 is connected to the acrylate group of Chemical Formula 2 upon exposure. In claim 14,
The polyimide resin is a negative photosensitive resin composition comprising one or two or more types of polyimide resin. An electronic device comprising an organic insulating film or a photosensitive pattern formed from the negative photosensitive resin composition according to claim 14. In claim 17,
An electronic device wherein the organic insulating film includes an interlayer insulating film and a surface protective film. In claim 17,
The electronic device further includes a memory component.

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