TW202225223A - Alkali-soluble copolymer comprising maleimide derivative as polymerized unit and photoresist composition comprising the same - Google Patents

Abstract

The present invention relates to an alkali-soluble copolymer and a photoresist composition comprising the same, and more specifically, a copolymer that comprises (meth)acrylic monomer and maleimide monomer having functional aryl substituent as polymerized units and thus shows remarkably improved alkali solubility, and a photoresist composition that comprises the same and can be removed by a water- soluble solution, and thus can be used in LED, TFT-LCD, MEMS, and semiconductor field.

Description

Alkali-soluble copolymer comprising maleimide derivative as polymerized unit and photoresist composition comprising the same

The present invention relates to an alkali-soluble copolymer and a photoresist composition comprising the copolymer, and more particularly, relates to a (meth)acrylic monomer and a maleimide having functional aryl substituents A copolymer in which the monomer acts as a polymerized unit and thus exhibits significantly improved alkali solubility, and a photoresist composition comprising the copolymer. In addition, the present invention relates to a photoresist composition, which can be patterned by a conventional lithography process and can be removed by a water-soluble solution, so that it can be used in LED, TFT-LCD, MEMS and semiconductor fields.

The photosensitive composition generally includes an alkali-soluble binder resin, a polymerizable compound having an unsaturated bond, a photopolymerization initiator, a solvent, and other additives, which can be used to form patterns by applying it to a substrate A film is formed, exposed to light using a photomask or the like to expose specific portions of the film, and treated with a developer to remove unexposed portions. Because of this feeling Since the photosensitive composition can be cured by irradiation, it can be used for photocurable ink, photosensitive printing plate, various photoresist, photoresist for LCD, transparent photosensitizer, and the like.

In these photosensitive compositions, the alkali-soluble binder resin provides adhesion to the substrate to allow coating, is dissolved in an alkali developer solution to allow fine patterns to be formed, and at the same time is the pattern obtained Provides strength to prevent pattern collapse during post-processing. As these alkali-soluble binder resins, for example, a resin having a (meth)acrylate structure including a hydroxyl group and a carboxylic acid group is known (Korean Patent Publication No. 10-2017-0141197).

In general, the photosensitive composition is formed into a film having a thickness of several micrometers (μm) to several tens of micrometers, and since most of the film needs to be developed, the binder resin used in the photosensitive resin composition should be Dissolves in alkaline developer in a short period of time, otherwise, it may cause several defects due to residues in the subsequent process. In addition, in order to be used as a non-residual structure after the required process, the photosensitive composition needs to have the characteristics of removing patterns in an environmentally friendly aqueous solution of an alkaline developer. Therefore, the photosensitive composition also needs to have good developability.

The object of the present invention is to provide a photoresist composition comprising an adhesive, and the adhesive has a significantly improved solubility in an alkaline aqueous solution.

To achieve the above object, the present invention provides an alkali-soluble copolymer comprising a (meth)acrylic monomer as a polymerized unit and a maleimide monomer substituted with a functional aryl group. The functional aryl substituted maleimide monomer system is selected from the group consisting of: maleimide derivatives having an aryl group having one or more hydroxy functional groups and which are related to maleimide the nitrogen bond of the moiety; a maleimide derivative having an aryl group having one or more carboxyl functional groups that is bonded to the nitrogen of the maleimide moiety; or a combination thereof. In the alkali-soluble copolymer, the content of the functional aryl-substituted maleimide monomer is 0.5 mol % or more based on 100 mol % of the total amount of monomers constituting the copolymer.

Another aspect of the present invention is to provide a photoresist composition comprising the alkali-soluble copolymer of the present invention as a binder resin.

The alkali-soluble copolymer according to the present invention exhibits a remarkably improved alkali solubility, and the photoresist composition including the copolymer can be removed by an alkali developer solution in a very short time without leaving a residual film, and It can be removed after the process where it is needed because of its pattern-removing properties in an environmentally friendly alkaline aqueous solution.

FIG. 1 shows photographs of the results of the presence/absence of a residual film on a substrate after exposing the photoresist coating film to an aqueous alkaline solution performed in Examples 1 and 2 of the present invention.

2 is a photograph showing the results of the presence/absence of a residual film on the substrate after exposing the photoresist coating film to an alkaline aqueous solution performed in Comparative Examples 1 and 2 of the present invention.

FIG. 3 is a photograph showing the result of patterning from a photoresist coating film performed in Examples 1 and 2 of the present invention.

4 is a photograph showing the result of patterning from a photoresist coating film performed in Comparative Examples 1 and 2 of the present invention.

FIG. 5 is a photograph showing the results of evaluation of the performance of removing the photoresist coating film by an alkaline aqueous solution in Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention.

The present invention is described in more detail below.

[Photosensitive resin composition]

The terms and expressions used in this specification and the scope of the patent application should not be construed limited by their conventional or lexical meanings, but should be based on the principle that the inventor can properly define the meanings and concepts of the terms to explain his invention in the best way , to be interpreted in terms of meanings and concepts consistent with the technical idea of the present invention.

The photosensitive resin composition of the present invention includes (a) an alkali-soluble copolymer including a maleimide derivative as the polymerized unit of the present invention, and the composition may further include at least one of the following: (b) a light Initiator, (c) photopolymerizable compound, (d) auxiliary curing agent, (e) silane coupling agent, (f) surfactant, and (g) solvent.

In this specification, the term "(meth)acryloyl" is used as a concept including "acryloyl" and "methacryloyl".

(a) Alkali-soluble copolymer comprising maleimide derivative as polymerized unit

The alkali-soluble copolymer of the present invention comprises a (meth)acrylic monomer as a polymerized unit; and a first maleimide monomer, which is substituted with a functional aryl group The maleimide monomer. The functional aryl substituted maleimide monomer system is selected from the group consisting of: maleimide derivatives having an aryl group having one or more hydroxy functional groups and which are related to maleimide the nitrogen bond of the moiety; a maleimide derivative having an aryl group having one or more carboxyl functional groups that is bonded to the nitrogen of the maleimide moiety; or a combination thereof. The content of the first maleimide monomer is 0.5 mol % or more based on 100 mol % of the total amount of monomers constituting the copolymer.

In a specific embodiment, the (meth)acrylic monomer included in the alkali-soluble copolymer of the present invention as a polymerized unit may be (meth)acrylic acid, aliphatic (meth)acrylate, aromatic (meth)acrylate, etc. C1-C18 aliphatic (meth)acrylate, C6-C20 aromatic (meth)acrylate, or a combination thereof. In addition, (meth)acrylic monomers can be unsubstituted or via one or more functional groups (eg, alkoxy, epoxy, oxetanyl, amido, hydroxyl, halo, silane) base, etc.) substitution.

In a specific embodiment, the (meth)acrylic monomer may be one or more selected from the group consisting of: methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) ) propyl acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate Octyl acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, (meth)acrylate Cetyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzene (meth)acrylate Methyl ester, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate base) acrylic acid, itaconic acid, monoalkyl itaconic acid, monoalkyl fumarate, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (methyl) ) 2,3-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyloxetan-3-methyl (meth)acrylate, ( 3-ethyloxetan-3-methyl meth)acrylate, (meth)acrylamide, N-methyl (meth)acrylamide, allyl (meth)acrylate, ( 2-hydroxyethyl meth)acrylate, 3-(meth)acryloyloxypropylmethyldimethoxysilane, tetrahydrofurfuryl (meth)acrylate, ethylene glycol dicyclopentenyl ether ( Meth)acrylate, 2-ethyl-2methyl-1,3-dioxolane methyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, 4-(methyl) base) acryloyl morpholine, phenylglycidyl ether (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-[4-(1-Methyl-1-phenylethyl)-phenoxy]ethyl (meth)acrylate, 3-butyl (meth)acrylate, 2-hexahydrophthalate (Meth)acryloyloxypropyl ester, γ-butyrolactone (meth)acrylate, propoxyethyl (meth)acrylate, N-isobutoxymethyl (meth)acrylate , 2-(meth)acryloyloxyethyl phthalate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylic acid ester, tetrafluoropropyl (meth)acrylate, heptafluorodecyl (meth)acrylate, o-hydroxyphenyl (meth)acrylate, m-hydroxyphenyl (meth)acrylate, p-hydroxyl (meth)acrylate Phenyl ester and tribromophenyl (meth)acrylate, but not limited thereto.

In a preferred embodiment, the (meth)acrylic monomer can be selected from the group consisting of: glycidyl (meth)acrylate, (meth)acrylic acid, methyl (meth)acrylate and its combination.

In the alkali-soluble copolymer of the present invention, the content of the (meth)acrylic monomer may be 20 to 99.5 mol %, 25 to 99.5 mol % based on the total amount of the monomers constituting the copolymer being 100 mol % %, 30 to 99.5 mol%, 35 to 99.5 mol%, 40 to 99.5 mol%, 41 to 99.5 mol%, 42 to 99.5 mol%, 43 to 99.5 mol%, 44 to 99.5 mol%, 45 to 99.5 mol%, 46 to 99.5 mol%, 47 to 99.5 mol%, 48 to 99.5 mol%, 49 to 99.5 mol%, 50 to 99.5 mol%, 51 to 99.5 mol%, 52 to 99.5 mol%, 53 to 99.5 mol%, 54 to 99.5 mol%, 55 to 99.5 mol%, 60 to 99.5mol%, 65 to 99.5mol%, 70 to 99.5mol%, 20 to 99mol%, 25 to 99mol%, 30 to 99mol%, 35 to 99mol% Ear%, 40 to 99 mole%, 41 to 99 mole%, 42 to 99 mole%, 43 to 99 mole%, 44 to 99 mole%, 45 to 99 mole%, 46 to 99 mole% %, 47 to 99 mol%, 48 to 99 mol%, 49 to 99 mol%, 50 to 99 mol%, 51 to 99 mol%, 52 to 99 mol%, 53 to 99 mol% , 54 to 99 mol%, 55 to 99 mol%, 60 to 99 mol%, 65 to 99 mol%, 70 to 99 mol%, 20 to 97 mol%, 25 to 97 mol%, 30 to 97 mol%, 35 to 97 mol%, 40 to 97 mol%, 41 to 97 mol%, 42 to 97 mol%, 43 to 97 mol%, 44 to 97 mol%, 45 to 97 mol%, 46 to 97 mol%, 47 to 97 mol%, 48 to 97 mol%, 49 to 97 mol%, 50 to 97 mol%, 51 to 97 mol%, 52 to 97 mol% 97 mol%, 53 to 97 mol%, 54 to 97 mol%, 55 to 97 mol%, 60 to 97 mol%, 65 to 97 mol%, 70 to 97 mol%, 20 to 95 mol% mol%, 25 to 95mol%, 30 to 95mol%, 35 to 95mol%, 40 to 95mol%, 41 to 95mol%, 42 to 95mol%, 43 to 95mol% Ear%, 44 to 95 mole%, 45 to 95 mole%, 46 to 95 mole%, 47 to 95 mole%, 48 to 95 mole%, 49 to 95 mole%, 50 to 95 mole% %, 51 to 95 mol%, 52 to 95 mol%, 53 to 95 mol%, 54 to 95 mol%, 55 to 95 mol%, 60 to 95 mol%, 65 to 95 mol% , 70 to 95 mol%, 20 to 90 mol%, 25 to 90 mol%, 30 to 90 mol%, 35 to 90 mol%, 40 to 90 mol% mol%, 41 to 90 mol%, 42 to 90 mol%, 43 to 90 mol%, 44 to 90 mol%, 45 to 90 mol%, 46 to 90 mol%, 47 to 90 mol% %, 48 to 90 mol%, 49 to 90 mol%, 50 to 90 mol%, 51 to 90 mol%, 52 to 90 mol%, 53 to 90 mol%, 54 to 90 mol% %, 55 to 90 mol%, 60 to 90 mol%, 65 to 90 mol%, 70 to 90 mol%, 20 to 80 mol%, 25 to 80 mol%, 30 to 80 mol% , 35 to 80 mol%, 40 to 80 mol%, 41 to 80 mol%, 42 to 80 mol%, 43 to 80 mol%, 44 to 80 mol%, 45 to 80 mol%, 46 to 80 mol%, 47 to 80 mol%, 48 to 80 mol%, 49 to 80 mol%, 50 to 80 mol%, 51 to 80 mol%, 52 to 80 mol%, 53 to 80 mol%, 54 to 80 mol%, 55 to 80 mol%, 60 to 80 mol%, 65 to 80 mol%, 70 to 80 mol%, 20 to 70 mol%, 25 to 70 mol%, 30 to 70 mol%, 35 to 70 mol%, 40 to 70 mol%, 41 to 70 mol%, 42 to 70 mol%, 43 to 70 mol%, 44 to 70 mol% mol%, 45 to 70mol%, 46 to 70mol%, 47 to 70mol%, 48 to 70mol%, 49 to 70mol%, 50 to 70mol%, 51 to 70mol% %, 52 to 70 mol%, 53 to 70 mol%, 54 to 70 mol%, 55% to 70 mol%, 60 to 70 mol%, 65 to 70 mol%, 20 to 60 mol% %, 25 to 60 mol%, 30 to 60 mol%, 35 to 60 mol%, 40 to 60 mol%, 41 to 60 mol%, 42 to 60 mol%, 43 to 60 mol% %, 44 to 60 mol%, 45 to 60 mol%, 46 to 60 mol%, 47 to 60 mol%, 48 to 60 mol%, 49 to 60 mol%, 50 to 60 mol% , 51 to 60 mol%, 52 to 60 mol%, 53 to 60 mol%, 54 to 60 mol%, 55 to 60 mol%, 20 to 55 mol%, 25 to 55 mol%, 30 to 55 mol%, 35 to 55 mol%, 40 to 55 mol%, 41 to 55 mol%, 42 to 55 mol%, 43 to 55 mol%, 44 to 55 mol%, 45 to 55 mol%, 46 to 55 mol%, 47 to 55 mol%, 48 to 55 mol%, 49 to 55 mol%, 50 to 55 mol%, 51 to 55 mol%, 52 to 55 mol%, 53 to 55 mol%, 54 to 55 mol%, 20 to 54 mol%, 25 to 54 mol%, 30 to 54 mol%, 35 to 54 mol%, 40 to 54 mol%, 41 to 54 mol%, 42 to 54 mol%, 43 to 54 mol%, 44 to 54 mol%, 45 to 54 mol%, 46 to 54 mol%, 47 to 54 mol%, 48 to 54 mol %, 49 to 54 mol %, 50 to 54 mol %, 51 to 54 mol %, 52 to 54 mol %, or 53 to 54 mol %.

In a specific embodiment, the first maleimide monomer included in the alkali-soluble copolymer of the present invention as a polymerized unit can be selected from: maleimide derivatives having C6-C20 aryl groups, the The aryl group has 1 to 3 hydroxyl functional groups and is bonded to the nitrogen of the maleimide moiety; the maleimide derivative with a C6-C20 aryl group, the aryl group has 1 to 3 carboxyl functional groups and is bonded to the nitrogen of the maleimide moiety; or a combination thereof. More specifically, the first maleimide monomer can be selected from: maleimide derivatives having a C6-C10 aryl group, the aryl group having 1 to 3 hydroxyl functional groups and is related to maleimide. A nitrogen bond of the maleimide moiety; a maleimide derivative having a C6-C10 aryl group having 1 to 2 carboxyl functional groups and bonded to the nitrogen of the maleimide moiety; or combinations thereof, but not limited thereto.

In a preferred embodiment, the first maleimide monomer can be one or more selected from the group consisting of the following compounds:

In an embodiment, in the first maleimide monomer according to the present invention, p-hydroxyphenylmaleimide having a functional group (hydroxyl or carboxyl group) at the para position and maleimide p-benzoate The imide compounds can be prepared by the following reaction formulas 1 and 2, respectively:

According to the above reaction formula 1, maleic anhydride is reacted with 4-aminophenol to obtain (N-hydroxyphenyl) maleamic acid (HPMAc) (1) yellow solid product, and then p-toluenesulfonic acid is used as a catalyst The hydroxyphenylmaleimide (2) can be prepared in the form of orange needle crystals by carrying out the dehydration reaction.

According to the above reaction formula 2, maleic anhydride is reacted with 4-aminobenzoic acid to obtain (N-benzoic acid) maleamic acid (BAMAc) (3) yellow solid product, and then p-toluenesulfonic acid is used As a catalyst for dehydration reaction, 4-maleido benzoic acid (4) can be prepared in the form of yellow powder.

In the alkali-soluble copolymer of the present invention, the content of the first maleimide monomer is 0.5 mol % or more based on 100 mol % of the total amount of monomers constituting the copolymer. More specifically, in the alkali-soluble copolymer, the content of the first maleimide monomer may be 0.5 to 50 mol % based on 100 mol % of the total amount of monomers constituting the copolymer, 0.5 to 45 mol %, 0.5 to 40 mol %, 0.5 to 35 mol %, 0.5 to 30 mol %, 0.5 to 20 mol %, 0.5 to 10 mol %, 0.5 to 9 mol %, 0.5 to 8 mol %, 0.5 to 7 mol %, 0.5 to 6 mol %, 0.5 to 5 mol %, 0.5 to 4 mol %, 0.5 to 3 mol %, 0.5 to 2 mol %, 0.5 to 0.5 mol % 1.5 mol %, 0.5 to 1 mol %, 0.75 to 50 mol %, (0.75 to 45 mol %, 0.75 to 40 mol %, 0.75 to 35 mol %, 0.75 to 30 mol %, 0.75 to 0.75 mol % 20 mol%, 0.75 to 10 mol%, 0.75 to 9 mol%, 0.75 to 8 mol%, 0.75 to 7 mol%, 0.75 to 6 mol%, 0.75 to 5 mol%, 0.75 to 4 mol% mol %, 0.75 to 3 mol %, 0.75 to 2 mol %, 0.75 to 1.5 mol %, 0.75 to 1 mol %, 1 to 50 mol %, 1 to 45 mol %, 1 to 40 mol % Ear%, 1 to 35 mole%, 1 to 30 mole%, 1 to 20 mole%, 1 to 10 mole%, 1 to 9 mole%, 1 to 8 mole%, 1 to 7 mole% %, 1 to 6 mol%, 1 to 5 mol%, 1 to 4 mol%, 1 to 3 mol%, 1 to 2 mol%, or 1 to 1.5 mol%. If the first horse If the content of the lyimide monomer is greater than 50 mol %, the adhesion to the substrate may be reduced during the development process, thereby possibly deteriorating the adhesion of the photoresist.

In an embodiment, the alkali-soluble copolymer of the present invention may further include a second maleimide monomer different from the first maleimide monomer as a polymerized unit.

In a specific embodiment, the second maleimide monomer can be selected from: maleimides having aliphatic hydrocarbon groups (more specifically, C1-C18 aliphatic hydrocarbon groups, such as C1-C18 alkyl groups) Amine derivatives, the aliphatic hydrocarbon group having one or more hydroxyl functional groups and bonded to the nitrogen of the maleimide moiety; or a combination thereof.

In a preferred embodiment, the second maleimide monomer may be unsubstituted maleimide.

When the alkali-soluble copolymer of the present invention further includes a second maleimide monomer as a polymerized unit, the amount may be 0.5 mol % or more based on 100 mol % of the total amount of monomers constituting the copolymer. many. More specifically, in the alkali-soluble copolymer, the content of the second maleimide monomer may be 0.5 to 30 mol % based on 100 mol % of the total amount of monomers constituting the copolymer, 0.5 to 20 mol %, 0.5 to 10 mol %, 0.5 to 9 mol %, 0.5 to 8 mol %, 0.5 to 7 mol %, 0.5 to 6 mol %, 0.5 to 5 mol %, 0.5 to 4 mol %, 0.5 to 3 mol %, 0.5 to 2 mol %, 0.5 to 1.5 mol %, 0.5 to 1 mol %, 0.75 to 30 mol %, 0.75 to 20 mol %, 0.75 to 0.75 mol % 10 mol%, 0.75 to 9 mol%, 0.75 to 8 mol%, 0.75 to 7 mol%, 0.75 to 6 mol%, 0.75 to 5 mol%, 0.75 to 4 mol%, 0.75 to 3 mol% mol %, 0.75 to 2 mol %, 0.75 to 1.5 mol %, 0.75 to 1 mol %, 1 to 30 mol %, 1 to 20 mol %, 1 to 10 mol %, 1 to 9 mol % Ear%, 1 to 8 mole%, 1 to 7 mole%, 1 to 6 mole%, 1 to 5 mole%, 1 to 4 mole%, 1 to 3 mole%, 1 to 2 mole% %, or 1 to 1.5 mol %.

In an embodiment, the alkali-soluble copolymer of the present invention may further include vinyl monomers as polymerized units.

In a specific embodiment, the vinyl monomer can be an aromatic vinyl monomer, an aliphatic vinyl monomer, or a combination thereof, more specifically, a C6-C20 aromatic vinyl monomer, C1 -C18 aliphatic vinyl monomer, or a combination thereof.

In a preferred embodiment, the vinyl monomer may be styrene.

When the alkali-soluble copolymer of the present invention further includes a vinyl monomer as a polymerized unit, the amount may be 1 mol% or more based on 100 mol% of the total amount of the monomers constituting the copolymer, more specifically can be 1 to 40 mol%, 1 to 39 mol%, 1 to 38 mol%, 1 to 37 mol%, 1 to 36 mol%, 1 to 35 mol%, 1 to 34 mol% Ear%, 1 to 33 mole%, 1 to 32 mole%, 1 to 31 mole%, 1 to 30 mole%, 10 to 40 mole%, 10 to 39 mole%, 10 to 38 mole% %, 10 to 37 mol%, 10 to 36 mol%, 10 to 35 mol%, 10 to 34 mol%, 10 to 33 mol%, 10 to 32 mol%, 10 to 31 mol% , 10 to 30 mol%, 20 to 40 mol%, 20 to 39 mol%, 20 to 38 mol%, 20 to 37 mol%, 20 to 36 mol%, 20 to 35 mol%, 20 to 34 mol%, 20 to 33 mol%, 20 to 32 mol%, 20 to 31 mol%, 20 to 30 mol%, 30 to 40 mol%, 30 to 39 mol%, 30 to 38 mol%, 30 to 37 mol%, 30 to 36 mol%, 30 to 35 mol%, 30 to 34 mol%, 30 to 33 mol%, 30 to 32 mol%, 30 to 30 mol% 31 mol%, 35 to 40 mol%, 35 to 39 mol%, 35 to 38 mol%, 35 to 37 mol%, or 35 to 36 mol%.

In a specific embodiment, the alkali-soluble copolymer of the present invention may include the structure shown in the following formula 1:

In the above formula 1,

A is hydrogen or a C1-C18 aliphatic hydrocarbon group with one or more hydroxyl functional groups,

B is a C6-C20 aryl group with one or more hydroxyl functional groups,

C is a C6-C20 aryl group with one or more carboxyl functional groups,

R ₁ is a C6-C20 aromatic group or a C1-C18 aliphatic group,

R ₂ is hydrogen or methyl,

R ₃ is hydrogen, a C1-C18 aliphatic group or a C6-C20 aromatic group,

l, m, n, o and p are each the molar ratio of the corresponding monomer repeating unit, and l+m+n+o+p is 1,

l is 0 to 0.3,

m and n are each independently 0 to 0.5, subject to the condition that m+n is 0.1 or more,

o is 0 to 0.3, and

p ranged from 0.4 to 0.99.

The alkali-soluble copolymer of the present invention may be a copolymer, a terpolymer, a tetrapolymer, a pentapolymer, or a polymer higher than the foregoing, considering the solubility control of the alkaline solution and the resistance to the substrate. Adhesion, etc., quaternary or higher polymers are suitable for photoresist applications.

The alkali-soluble copolymer of the present invention can be obtained by polymerization of several generally known polymerization methods such as radical polymerization, cationic polymerization, anionic polymerization, polycondensation and the like. It can be prepared by any method, and considering the simplicity and economy of preparing the copolymer, it is preferable to use free radical polymerization. Alternatively, it can be prepared by mixing the monomers with the polymerization solvent, heating the mixture to an appropriate temperature according to the half-life temperature of the thermal initiator used, and then removing oxygen under a nitrogen atmosphere. More preferably, it can be prepared by adding a free radical polymerization initiator and a chain transfer agent and maintaining at an appropriate temperature. The polymerization time and temperature may vary depending on the type of thermal initiator used. As a radical polymerization initiator, a known thermal initiator can be used, and more specifically, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2 can be used ,4-dimethylvaleronitrile (V-65), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), benzyl peroxide, lauryl peroxide , tert-butyl peroxypivalate, 1,1'-bis-(bis-tert-butylperoxy)cyclohexane, 1,1'-azobis(cyclohexane-1-carbonitrile) , 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 2,2'-azobis[2-methylpropionate] yl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis[2- (2-imidazolinyl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolinyl)propane], and the like.

-2,4,6-三酮(1,3,5-tris(3-mercaptobutyroethyl)-1,3,5-triazin-2,4,6-trione)、巰基乙酸、3-巰基丙基三乙氧基矽烷、2-巰基丙酸、3-巰基丙酸等。 As the chain transfer agent for controlling the weight average molecular weight (Mw) of the copolymer, commonly known chain transfer agents can be used, and more specifically, 1-dodecanethiol, octadecanethiol, neopentyltetrakis can be used Alcohol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyric acid ethyl)-1,3,5-tris

-2,4,6-trione (1,3,5-tris(3-mercaptobutyroethyl)-1,3,5-triazin-2,4,6-trione), mercaptoacetic acid, 3-mercaptopropyltriethyl Oxysilane, 2-mercaptopropionic acid, 3-mercaptopropionic acid, etc.

In a specific embodiment, the weight-average molecular weight (Mw) of the alkali-soluble copolymer of the present invention may be 1,000 to 100,000 g/mol, and the polydispersity index (PDI) thereof may be 1.0 to 10. More specifically For example, the weight average molecular weight (Mw) may be 4,000 to 50,000 g/mol and the polydispersity index (PDI) may be 1.0 to 3.0, But not limited to this. In addition, the alkali-soluble copolymer of the present invention can be a random copolymer, and the arrangement order of each polymer unit is not limited, but not limited thereto.

Since the alkali-soluble copolymer of the present invention exhibits significantly improved solubility in alkaline developer solutions (eg, tetramethylammonium hydroxide (TMAH) solution, potassium hydroxide (KOH) solution), it can be very useful in Used as a binder resin component for photoresist compositions.

Therefore, another aspect of the present invention provides a photoresist composition comprising the alkali-soluble copolymer of the present invention as a binder resin.

If necessary, the amount of the binder resin in the photoresist composition of the present invention can be appropriately adjusted. In a specific embodiment, for example, based on the total weight of the composition as 100 parts, the content of the binder resin can be 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, and 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight parts or less or 55 parts by weight or less, but not limited thereto.

In addition to the alkali-soluble copolymer of the present invention as a binder resin component, the photoresist composition of the present invention may further include one or more components conventionally used in photoresist compositions.

(b) Photoinitiator

系、安息香系、苯乙酮系、咪唑系、

酮或肟酯系化合物等。作為此等光起始劑，舉例而言，可為氧化三苯基膦、二苯基甲酮、苯基聯苯基酮、1-羥基-1-苯甲醯基環己烷、苯甲基二甲基縮酮、1-苯甲基-1-二甲基胺基-1-(4-嗎啉基(morpholino)-苯甲醯基)丙烷、2-嗎啉基-2-(4-甲基巰基)苯甲醯基丙烷(2-morpholyl-2-(4-methylmercapto)benzoylpropane)、噻 噸酮(thioxanthone)、1-氯-4-丙基噻噸酮、異丙基噻噸酮、二乙基噻噸酮、乙基蒽醚、4-苯甲醯基-4-甲基二苯基硫醚、安息香丁醚、2-羥基-2-苯甲醯基丙烷、2-羥基-2-(4-異丙基)苯甲醯基丙烷、4-丁基苯甲醯基三氯甲烷、4-苯氧基苯甲醯基二氯甲烷、苯甲醯基甲酸甲酯、1,7-雙(9-吖啶基)庚烷、9-正丁基-3,6-雙(2-嗎啉基-異丁醯基)咔唑、2-甲基-4,6-雙(三氯甲基)-s-三

、2-苯基-4,6-雙(三氯甲基)-s-三

、2-萘基-4,6-雙(三氯甲基)-s-三

、2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮、2-甲基-1-[(4-甲硫基)苯基]-2-嗎啉基丙-1-酮、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、4,4'-雙(二乙基胺基)二苯基甲酮、2-巰基苯并噻唑、Irgacure 369、Irgacure 379、Irgacur 651、Irgacure 907、Darocur TPO、Irgacure 819、OXE-01、OXE-02(汽巴精化(Ciba Specialty Chemicals))、N-1919、NCI-831(艾迪科(Adeka))、SPI-02、SPI-03、SPI-04、SPI-05、SPI-06、SPI-07(三養社(Samyang Corporation))等，其可以單獨使用，亦可將前述兩者或更多者組合使用。 As the photoinitiator contained in the photosensitive resin composition of the present invention, commonly used three can be used.

series, benzoin series, acetophenone series, imidazole series,

ketone or oxime ester compounds, etc. As these photoinitiators, for example, triphenylphosphine oxide, diphenyl ketone, phenyl biphenyl ketone, 1-hydroxy-1-benzylcyclohexane, benzyl Dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4-morpholino-benzyl)propane, 2-morpholino-2-(4- Methylmercapto) benzoylpropane (2-morpholyl-2-(4-methylmercapto)benzoylpropane), thioxanthone, 1-chloro-4-propyl thioxanthone, isopropyl thioxanthone, Diethyl thioxanthone, ethyl anthracene, 4-benzyl-4-methyldiphenyl sulfide, butyl benzoin, 2-hydroxy-2-benzyl propane, 2-hydroxy-2 -(4-Isopropyl)benzylpropane, 4-butylbenzyltrichloromethane, 4-phenoxybenzyldichloromethane, methyl benzylcarboxylate, 1,7 -Bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis(2-morpholinyl-isobutyryl)carbazole, 2-methyl-4,6-bis(trichloromethane) base)-s-three

, 2-phenyl-4,6-bis(trichloromethyl)-s-tri

, 2-naphthyl-4,6-bis(trichloromethyl)-s-tri

, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-methyl-1-[(4-methylthio)phenyl]-2 -Morpholinylpropan-1-one, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 4 ,4'-bis(diethylamino) benzophenone, 2-mercaptobenzothiazole, Irgacure 369, Irgacure 379, Irgacur 651, Irgacure 907, Darocur TPO, Irgacure 819, OXE-01, OXE-02 (Ciba Specialty Chemicals), N-1919, NCI-831 (Adeka), SPI-02, SPI-03, SPI-04, SPI-05, SPI-06, SPI- 07 (Samyang Corporation) and the like, which may be used alone or in combination of two or more of the foregoing.

The content of the photoinitiator according to the present invention is present in an amount that increases transparency and minimizes exposure, which may be 0.01 to 15% by weight, 0.01 to 10% by weight, 0.01 to 9% by weight, 0.01 to 8% by weight , 0.01 to 7% by weight, 0.01 to 6% by weight, 0.01 to 5% by weight, 0.05 to 10% by weight, 0.05 to 9% by weight, 0.05 to 8% by weight, 0.05 to 7% by weight, 0.05 to 6% by weight, 0.05 to 5 wt %, 0.1 to 10 wt %, 0.1 to 9 wt %, 0.1 to 8 wt %, 0.1 to 7 wt %, 0.1 to 6 wt %, or 0.1 to 5 wt %. If the amount of the photoinitiator is less than 0.01 wt %, the remaining rate may be deteriorated due to low sensitivity, thereby possibly causing difficulty in pattern formation. Conversely, if the light starts If the amount of the agent is more than 15% by weight, storage stability may be problematic, and foreign matter may be generated on the film surface due to reduced solubility of the photoinitiator.

(c) Multifunctional monomer (multifunctional monomer)

The multifunctional monomer of the present invention is generally a crosslinkable monomer having two or more vinylic double bonds, for example, polyethylene glycol di( meth)acrylate; ethylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; propylene glycol di(meth)acrylate; trimethylol Propane di(meth)acrylate; addition reaction product of bisphenol A and diglycidyl ether acrylic acid; ethyl isocyanuric acid tri(meth)acrylate; β-hydroxyethyl(meth)acrylic acid The phthalic acid diester; the addition reaction product of β-hydroxyethyl (meth)acrylate and toluene diisocyanate; selected from trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra (Meth)acrylate, Neotaerythritol tri(meth)acrylate, Neotaerythritol tetra(meth)acrylate, Dipivalerythritol penta(meth)acrylate, Dipivalerythritol hexa The ester compound of the group consisting of (meth)acrylate and dipivalerythritol tri(meth)acrylate; the addition reaction product of trimethylol and propane triglycidyl ether acrylic acid; The addition reaction product of oxygen resin and (meth)acrylic acid and the novolac epoxy acrylic resin generated by the reaction of phthalic anhydride, etc.

In the present invention, an isocyanurate compound can be used as the photopolymerizable compound. The trimer isocyanate compound may be a monoallyl diglycidyl trimer isocyanate compound, a diallyl monoglycidyl trimer isocyanate compound, a triallyl trimer isocyanate compound, or the like. Specifically, the monoallyl diglycidyl triisocyanate compound may be, for example, monoallyl diglycidyl triisocyanate, 1-allyl-3,5-bis(2-methylglycidyl) base) trimeric isocyanate, 1-(2-methacryl)-3,5-diglycidyl trimeric isocyanate acid ester, 1-(2-methacryl)-3,5-bis(2-methylglycidyl) isocyanate, etc. Specifically, the diallyl monoglycidyl triisocyanate compound may be, for example, diallyl monoglycidyl triisocyanate, 1,3-diallyl-5-(2-methylglycidyl base) triisocyanate, 1,3-bis(2-methacryl)-5-glycidyl triisocyanate, 1,3-bis(2-methacryl)-5-(2-methyl) glycidyl) trimeric isocyanate, etc. Specifically, the triallyl trimer isocyanate compound may be, for example, triallyl trimer isocyanate, ginseng (2-methacryl) trimer isocyanate, and the like. Any one selected from the above, or a mixture of two or more may be used.

In the present invention, based on the total weight of the photoresist resin composition, the content of the multifunctional monomer may be 2 to 70 wt %, more specifically, 2 to 70 wt %, 2 to 60 wt %, 2 to 70 wt %. 50 wt%, 2 to 40 wt%, 2 to 30 wt%, 2 to 20 wt%, 2 to 15 wt%, 2 to 14 wt%, 2 to 13 wt%, 2 to 12 wt%, 2 to 11 wt% %, 2 to 10% by weight, 5 to 70% by weight, 5 to 60% by weight, 5 to 50% by weight, 5 to 40% by weight, 5 to 30% by weight, 5 to 20% by weight, 5 to 15% by weight, 5 to 14% by weight, 5 to 13% by weight, 5 to 12% by weight, 5 to 11% by weight, 5 to 10% by weight, 10 to 70% by weight, 10 to 60% by weight, 10 to 50% by weight, 10 to 40 wt %, 10 to 30 wt %, 10 to 20 wt %, 10 to 15 wt %, 10 to 14 wt %, 10 to 13 wt %, 10 to 12 wt %, or 10 to 11 wt %. When the amount of the polyfunctional (meth)acrylic monomer is within the above range, the pattern shape of the exposed portion after exposure and development processes can be well maintained.

According to the present invention, the composition ratio of the polyfunctional (meth)acrylic monomer and the binder resin can be appropriately adjusted, and a photoresist resin composition capable of maintaining the pattern shape and developability can be prepared.

(d) Auxiliary curing agent

唑、2,5,-二巰基-1,3,4-噻二唑及2-巰基-4,6-二甲基胺基吡啶，且可使用上述任一者或兩者或更多者之組合。基於光阻組成物之總重量，輔助固化劑的量較佳可為0.1至10重量%。 The role of the auxiliary curing agent is to promote the free radical generation of the photoinitiator and increase the curing speed of the film. Examples of the auxiliary curing agent can be selected from the following groups: dioctyl phthalate, phthalic acid Diisononyl, dioctyl adipate, tricresyl phosphate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2-mercaptobenzimidazole, 2-mercapto benzothiazole, 2-mercaptobenzo

azole, 2,5,-dimercapto-1,3,4-thiadiazole, and 2-mercapto-4,6-dimethylaminopyridine, and any one or two or more of the above may be used combination. The amount of the auxiliary curing agent may preferably be 0.1 to 10 wt % based on the total weight of the photoresist composition.

(e) Adhesion aid

The function of the adhesive agent is to improve the adhesion to the substrate, and in order to improve the contact adhesion to the substrate, it can have reactive substituents such as vinyl, carboxyl, methacryloyloxy, isocyanate, epoxy, etc. . Examples of adhesion aids may be trimethoxysilylbenzoic acid, gamma-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyl triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. These adhesion aids may be used alone or in combination of two or more thereof. The amount of the adhesion aid may preferably be 0.1 to 10 wt % based on the total weight of the photoresist composition.

(f) Surfactant

If necessary, a surfactant may be further included, the function of which is to improve the coatability or developability of the photosensitive resin composition. The type of the surfactant is not particularly limited, for example, it can be a fluorine-based surfactant or a silicone surfactant. As commercial products of fluorine-based surfactants, BM-1000, BM-1100 (BM Chemie), Fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M), SH-28PA/-190/SZ-6032 (Toray Silicone), etc. As a commercial product of polysiloxane surfactants, BYK-310, BYK-313, BYK-320, BYK-333 (BYK), etc. can be used. Considering the dispersibility, BYK-307 can be preferably used.

Based on the total weight of the photoresist composition of the present invention, the content of the surfactant may be 0.01 to 5% by weight, 0.01 to 4% by weight, 0.01 to 3% by weight, 0.01 to 2% by weight, 0.01 to 1% by weight, 0.01% by weight to 0.5 wt%, 0.01 to 0.4 wt%, 0.01 to 0.3 wt%, 0.01 to 0.2 wt%, 0.01 to 0.1 wt%, 0.05 to 4 wt%, 0.05 to 3 wt%, 0.05 to 2 wt%, 0.05 to 1 % by weight, 0.05 to 0.5% by weight, 0.05 to 0.4% by weight, 0.05 to 0.3% by weight, 0.05 to 0.2% by weight, 0.05 to 0.1% by weight, 0.075 to 4% by weight, 0.075 to 3% by weight, 0.075 to 2% by weight , 0.075 to 1% by weight, 0.075 to 0.5% by weight, 0.075 to 0.4% by weight, 0.075 to 0.3% by weight, 0.075 to 0.2% by weight, 0.075 to 0.1% by weight, 0.1 to 4% by weight, 0.1 to 3% by weight, 0.1 to 2 wt %, 0.1 to 1 wt %, 0.1 to 0.5 wt %, 0.1 to 0.4 wt %, 0.1 to 0.3 wt %, or 0.1 to 0.2 wt %. When the amount of the surfactant is within the above range, it is beneficial to improve the coatability or developability of the photoresist composition.

(g) Solvent

As the solvent, an appropriate solvent can be used in consideration of compatibility with the binder resin, multifunctional monomer and other additives. For example, the solvent may be alcohols, such as methanol, ethanol, etc.; ethers, such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers, such as ethylene glycol Alcohol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Diethyl Glycol diethyl ether, etc.; cellosolve acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; carbitols ), such as methyl ethyl carbitol, diethyl carbitol, etc.; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene , xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentanone base ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; Alkyl oxyacetates, such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetates, such as methyl methoxyacetate, ethyl methoxyacetate esters, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; alkyl 3-oxypropionate, such as methyl 3-oxypropionate, 3-oxypropionate 3-alkoxypropionate alkyl esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3- Methyl ethoxypropionate, etc.; alkyl 2-oxypropionate, such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; - Alkoxypropionate alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate Esters, etc.; 2-Oxy-2-methylpropionic acid alkyl esters, such as 2-oxy-2-methylpropionic acid methyl ester, 2-oxy-2-methylpropionic acid ethyl ester, etc.; 2 -Alkoxy-2-methylpropionic acid alkyl esters, such as 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methyl propionic acid ethyl ester, etc.; esters , such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, etc.; ketoesters, such as pyruvic acid ethyl ester, etc.; and the solvent may be a single solvent selected from the following or a mixed solvent of two or more: N-methylformamide, N,N-dimethylformamide, N-methylformamide Toluidine, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzene Methyl ethyl ether, dihexyl ether, acetone acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, Diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

The photoresist composition of the present invention exhibits excellent developability in the alkaline developer solution 2.38% TMAH solution used in the photoresist process, and can be easily removed even if an environmentally friendly alkaline aqueous solution is used, so it is very suitable for use as a Photoresist to be retained and photoresist to be removed.

[Example]

<Monomer synthesis>

1: Synthesis of 4-hydroxyphenylmaleimide

In a 500-mL three-necked round-bottomed flask equipped with a reflux cooling device, maleic anhydride (50.99 g, 0.52 mol) was dissolved in acetone, and the acetone dispersed in acetone was added slowly over a period of about 30 minutes. 4-Aminophenol (52.38 g, 0.48 mol). After the reaction at room temperature, the resulting yellow solid was filtered, washed with acetone and distilled water for 3 to 4 times, and then vacuum-dried at 60° C. to obtain 76.49 g (yield: 72%) of (N-hydroxyphenyl)methylene lysine (HPMAc) (1).

¹ H-NMR (400 MHz, acetone- d6 ): δ 10.45(br,1H), 8.7(br,1H), 7.52(d,2H), 6.9(d,2H), 6.72(d,1H), 6.35( d,1H)

Next, the resulting HPMAc(1) (76.49 g, 0.37 mol) was put into a 1-liter three-neck round-bottomed flask equipped with a reflux cooling device, and p-toluenesulfonic acid (7 g, 0.04 mol) was added therein. ), toluene (500 mL) and dimethylformamide (DMF) (40 mL) were reacted at 150°C under reflux under nitrogen atmosphere. When the toluene solvent began to reflux with the increase of the temperature in the flask, a dean-stark apparatus was set up to remove the water produced by the side reaction by azeotropic distillation with the toluene solvent. The reaction was carried out for 6 hours, after the reaction was completed, the toluene solvent was removed under reduced pressure, the product was precipitated in cold water, filtered, washed with 5% sodium bicarbonate (NaHCO ₃ ) solution and excess water, and then in isopropanol/water (1 : 1) Recrystallization in solution. The bright orange crystalline product of 4-hydroxyphenylmaleimide (2) was obtained in 70% yield.

¹ H-NMR (400 MHz, acetone- d6 ): δ 8.91(br,1H), 7.16(d,2H), 6.95(s,2H), 6.8(d,2H)

2: Synthesis of 4-maleiminobenzoic acid

As in the synthesis of the hydroxyphenylmaleimide (2) monomer, maleic anhydride (50.99 g, 0.52 mol) was dissolved in acetone in a 500 mL three-neck round bottom flask equipped with reflux cooling. , into which 4-aminobenzoic acid (65.83 g, 0.48 moles) dispersed in acetone was slowly added over a period of about 30 minutes. The reaction was carried out at room temperature for about 1 hour and 30 minutes. The yellow solid formed after the reaction was filtered, washed with acetone and distilled water for 3 to 4 times, and vacuum-dried at 60° C. to obtain 88.94 g (yield: 83%) of (N-benzoic acid) maleamic acid (BAMAc). )(3). Next, the resulting (BAMAc)(3) (88.94 g, 0.43 mol) was put into a 1-liter three-neck round bottom flask equipped with a reflux cooling device, and p-toluenesulfonic acid (7 g, 0.04 mol) was added therein. molar), toluene (500 mL) and DMF (40 mL), and the reaction was carried out at reflux at 150°C under nitrogen atmosphere. When the toluene solvent began to reflux with the increase of the temperature in the flask, a Dean-Stark apparatus was set up to remove the water produced by the side reaction by azeotropic distillation with the toluene solvent. The reaction was carried out for 6 hours, the toluene solvent was removed under reduced pressure after the reaction, the product was precipitated in cold water, filtered, washed with 5% sodium bicarbonate (NaHCO ₃ ) solution and excess water, and then washed in isopropanol/water (1:1) recrystallized in solution. 4-Maleiminobenzoic acid (4) was obtained as a bright yellow powder in 75% yield.

¹ H-NMR (400 MHz, acetone- d6 ): δ 11.3(br,1H), 8.17(d,2H), 7.6(d,2H), 7.1(s,2H)

<Preparation of Alkali-Soluble Copolymer>

Alkali-soluble copolymers were prepared by using monomer compositions having the species and molar ratios shown in Table 1 below. Additional ingredients and polymerization conditions used in the preparation of the copolymers, as well as the weight average molecular weight (Mw) and polydispersity index (PDI) of the resulting copolymers are also shown in Table 1 below.

[Table 1]

[Preparation of Copolymer A-1]

As monomers, maleimide (MI), styrene (STY), glycidyl methacrylate (GMA), methyl methacrylate (MMA) and 4-hydroxyphenylmaleimide (HPMI) ) were mixed in a molar ratio of 10:35:10:44:1, respectively. 40 parts by weight of this mixture was put into a three-necked round bottom flask, and then 1.5 parts by weight of a thermal initiator and 2.5 parts by weight of a chain transfer agent were added thereto. 60 parts by weight of methyl 3-methoxypropionate was added to the reaction flask as a polymerization solvent to dissolve the monomer, initiator and chain transfer agent, and then the temperature was maintained at 70°C under stirring to polymerize The action is carried out for about 6 hours. Then, 100 ppm of tertiary butylhydroquinone (t-BHQ) was used as A polymerization inhibitor is added to inhibit further polymerization. The prepared copolymer had a weight average molecular weight (Mw) of 10,344 and a polydispersity index (PDI) of 2.00.

[Preparation of Copolymer A-2]

Except using maleimide (MI), styrene (STY), glycidyl methacrylate (GMA), methyl methacrylate (MMA) and The method for preparing copolymer A-1 was carried out in the same manner except that a monomer mixture of 4-maleiminobenzoic acid (BAMI) was used instead of the monomer mixture used for preparing copolymer A-1 to prepare copolymer A-2. The prepared copolymer had a weight average molecular weight (Mw) of 10,954 and a polydispersity index (PDI) of 2.12.

[Preparation of Copolymer B-1]

Except using monomers of maleimide (MI), styrene (STY), glycidyl methacrylate (GMA) and methyl methacrylate (MMA) in a molar ratio of 10:35:10:45 The preparation method of the copolymer A-1 was carried out in the same manner except that the monomer mixture used for the preparation of the copolymer A-1 was replaced by the mixture to prepare the copolymer B-1. The prepared copolymer had a weight average molecular weight (Mw) of 10,212 and a polydispersity index (PDI) of 1.97.

[Preparation of Copolymer B-2]

Except for the use of maleimide (MI), styrene (STY), glycidyl methacrylate (GMA), methacrylic acid (MAA) and methyl methacrylate in a molar ratio of 10:35:10:10:25 The preparation method of the copolymer A-1 was carried out in the same manner except that the monomer mixture used for preparing the copolymer A-1 was replaced by a monomer mixture of methyl acrylate (MMA) to prepare a copolymer B-2. The prepared copolymer had a weight average molecular weight (Mw) of 12,042 and a polydispersity index (PDI) of 2.18.

<Preparation of photoresist composition, preparation of coating film, performance evaluation of coating film>

Photoresist compositions were prepared by using the types and amounts of ingredients shown in Table 2 below. A coating film is prepared on a silicon wafer using the prepared photoresist composition. The dissolution rate of the coating film on the silicon wafer in the alkaline solution was measured, and the results are shown in Table 2 below. In addition, the presence/absence of the residual film was observed after the coating film on the silicon wafer was exposed to the alkaline solution, and the results are shown in Table 2 below, Figure 1 (Examples 1 and 2) and Figure 2 (Comparative Examples 1 and 2) )middle.

[Table 2]

[Preparation of photoresist composition]

The photoresist compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared as follows. The above-prepared alkali-soluble copolymers A-1, A-2, B-1 and B-2 were respectively used as binder resins, dipivaloerythritol hexaacrylate (DPHA) as multifunctional monomer, and OXE -02 (BASF) as photoinitiator and BYK-307 as surfactant. MMP (methyl 3-methoxypropionate) was added as a solvent to adjust the solid content of the photoresist to 35%.

[Preparation of coating film using photoresist composition]

The photoresist compositions prepared in Examples and Comparative Examples were respectively coated on silicon wafers with a thickness of about 8 μm by spin coating. Then, the coating film was pre-baked on a hot plate at 100° C. for about 10 minutes to remove the solvent remaining in the coating film.

[Evaluation of pattern forming ability of photoresist composition]

The coating film on the substrate was irradiated with i-line based light of 100 millijoules (mJ) using an MA6 device (Success), and then developed by exposure to a 2.38% TMAH alkaline solution for about 60 seconds. The shape of the formed pattern was observed by using a SEM apparatus.

[Measure the dissolution rate of the coating film and observe the presence/absence of the residual film on the substrate]

The coating film on the substrate was irradiated with 100 mJ of i-line based light using an MA6 device (Success) and then developed by exposure to a 2.38% TMAH alkaline solution for about 60 seconds.

After that, in order to confirm the thickness variation of the exposed portion, the thickness was measured using a nanometer scale device.

In addition, in order to observe the presence/absence of the residual film on the substrate, the coating film was exposed to a 2.38% TMAH alkali solution for about 100 seconds, and the presence or absence of the residual film on the substrate was observed. After exposure to the alkaline solution, the unexposed surface of the substrate was cleaned with acetone, and if any residual film was removed, it was marked as "O", and if no residual film was removed, it was marked as "X".

As shown in Table 2 above, compared with the photoresist composition of the comparative example, the photoresist composition of the example, which does not use methacrylic acid which has an influence on the developability, uses the alkali-soluble copolymer of the present invention as an adhesive Agent resin - forms a better pattern, and after the exposed part is developed, the residual film shows good performance, especially when the formed pattern is further developed, it shows good developability.

Claims (11)

An alkali-soluble copolymer comprising, as one of the polymerized units (meth)acrylic monomers; and a first maleimide monomer selected from the group consisting of maleimide derivatives having an aryl group whose aryl group has one or more hydroxyl functional groups and is bonded to the nitrogen of the maleimide moiety, an aryl-bearing maleimide derivative, or a combination thereof, whose aryl group has one or more carboxyl functional groups and is bonded to the nitrogen of the maleimine moiety; Wherein, the total amount of the monomers constituting the copolymer is 100 mol %, and the content of the first maleimide monomer is 0.5 mol % or more. The alkali-soluble copolymer according to claim 1, wherein the (meth)acrylic monomer system is selected from one or more of the following groups: methyl (meth)acrylate, (methyl) Ethyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Heptyl ester, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, ten (meth)acrylate Tetraester, cetyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate , Benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid, Iconic acid, Iconic acid mono Alkyl ester, monoalkyl fumarate, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, 3,4-Epoxycyclohexylmethyl (meth)acrylate, 3-methyloxetan-3-methyl (meth)acrylate, 3-ethyloxetane (meth)acrylate Alkyl-3-methyl ester, (meth)acrylamide, N-methyl (meth)acrylamide, allyl (meth)acrylate, (meth)acrylic acid 2-Hydroxyethyl ester, 3-(meth)acrylooxypropylmethyldimethoxysilane, tetrahydrofurfuryl (meth)acrylate, ethylene glycol dicyclopentenyl ether (meth)acrylic acid ester, 2-ethyl-2-methyl-1,3-dioxolane methyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, 4-(meth)propenyl morpholine, phenylglycidyl ether (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (meth) 2-[4-(1-Methyl-1-phenylethyl)-phenoxy]ethyl acrylate, 3-butyl (meth)acrylate, 2-(methyl)hexahydrophthalate Acryloyloxypropyl, gamma-butyrolactone (meth)acrylate, propoxyethyl (meth)acrylate, N-isobutoxymethyl (meth)acrylate, phthalate 2-(meth)acryloyloxyethyl formate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, tetrafluoro Propyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, o-hydroxyphenyl (meth)acrylate, m-hydroxyphenyl (meth)acrylate, p-(methyl) ) Hydroxyphenyl acrylate and tribromophenyl (meth)acrylate. The alkali-soluble copolymer of claim 1, wherein the first maleimide monomer system is selected from one or more of the following compounds:

The alkali-soluble copolymer as claimed in claim 1 further comprises a second maleimide monomer different from the first maleimide monomer as a polymerized unit. The alkali-soluble copolymer according to claim 4, wherein the unsubstituted maleimide of the second maleimide monomer system, its aliphatic hydrocarbon group has one or more hydroxyl functional groups and is associated with A maleimide derivative having an aliphatic hydrocarbon group bonded to the nitrogen of the maleimide moiety, or a combination thereof. The alkali-soluble copolymer as claimed in claim 1 further comprises vinyl monomers as polymerized units. The alkali-soluble copolymer of claim 6, wherein the vinyl monomer is an aromatic vinyl monomer, an aliphatic vinyl monomer, or a combination thereof. The alkali-soluble copolymer according to claim 11, comprising the structure shown in the following formula 1:

Wherein, in the above formula 1: A is hydrogen or a C1-C18 aliphatic hydrocarbon group with one or more hydroxyl functional groups, B is a C6-C20 aryl group with one or more hydroxyl functional groups, C is a C6-C20 aryl group with one or more carboxyl functional groups, R ₁ is a C6-C20 aromatic group or a C1-C18 aliphatic group, R ₂ is hydrogen or methyl, R ₃ is hydrogen, a C1-C18 aliphatic group or a C6-C20 aromatic group, l, m, n, o and p are each the molar ratio of the corresponding monomer repeating unit, and l+m+n+o+p is 1, l is 0 to 0.3, m and n are each independently 0 to 0.5, subject to the condition that m+n is 0.1 or more, o is 0 to 0.3, and p ranged from 0.4 to 0.99. A photoresist composition comprising the alkali-soluble copolymer described in any one of claims 1 to 8 as a binder resin. The photoresist composition according to claim 9, further comprising at least one of the following: a photopolymerizable compound; a photoinitiator; an auxiliary curing agent; an adhesion assistant; and a surfactant. The photoresist composition according to claim 10, which is used as a photoresist for LED, TFT-LCD, MEMS or semiconductor.

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