KR102262502B1 - Photosensitive resin composition and cured layer - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising two or more types of polyimide resins having a specific structure.

Description

A photosensitive resin composition and a cured film TECHNICAL FIELD

The present invention relates to a photosensitive resin composition and a cured film.

Photosensitive resin is a representative functional polymer material that has been put to practical use in the production of various precision electronic/information industry products, and is currently being used importantly in the high-tech industry, especially in the production of semiconductors and displays.

In general, a photosensitive resin refers to a polymer compound in which a change in physical properties such as solubility in a specific solvent, coloration, and curing occurs due to chemical change in molecular structure within a short time by irradiation with light. By 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, leading to advanced printing, semiconductor production, and display production. , photocurable surface coating materials, etc., are widely used in various precision electronic and information industries.

On the other hand, as electronic devices are recently highly integrated and finely patterned, a photosensitive resin capable of minimizing a defect rate and increasing processing efficiency and resolution is required. Accordingly, a method of using polyamic acid or polyamic acid as a photosensitive resin has been introduced.

However, polyamic acid is easily hydrolyzed by water in the air, so storage and stability are not sufficient. Polyamic acid has low adhesion to the applied substrate, etc., and has a problem of lowering the physical properties of electrical wiring or substrate according to high temperature application. there was. In addition, other types of photosensitive resins do not have sufficient chemical resistance, heat resistance, and electrical properties in a finally cured state, or have insufficient adhesion to a metal substrate, so that they are peeled off from the substrate during development or curing.

In particular, the development of a photosensitive resin material capable of forming an ultra-fine pattern and preventing thermal damage to a semiconductor device during a heat treatment process for curing the photosensitive resin composition is required.

The present invention provides a photosensitive resin composition that can have excellent adhesion and chemical resistance while being cured with high efficiency at a low temperature, and can also secure a high elongation while maintaining the tensile strength and modulus of the finally obtained cured film at a high level it is to do

Moreover, this invention is for providing the cured film formed from the said photosensitive resin composition.

In addition, the present invention is a cured film manufacturing method that can provide a cured material that can have excellent adhesion and chemical resistance while curing with high efficiency at low temperature and can also secure high elongation with high level of tensile strength and modulus is to provide

In the present specification, the first polyamide-imide resin comprising an imide repeating unit substituted with an epoxy group; and a second polyamide-imide resin comprising an imide repeating unit substituted with a (meth)acrylate group; A photosensitive resin composition comprising a may be provided.

In addition, in the present specification, a cured film including a cured product of the photosensitive resin composition may be provided.

In addition, in the present specification, there may be provided a method of manufacturing a cured film comprising the step of curing the photosensitive resin composition at a temperature of 250 ℃ or less.

In addition, in the present specification, using the photosensitive resin composition to form a resist film on the substrate; irradiating a pattern on the resist film using a high energy ray; A method of forming a resist pattern including; developing the resist film using an alkali developer may be provided.

Hereinafter, a photosensitive resin composition, a cured film, a method of manufacturing a cured film, and a method of forming a resist pattern according to specific embodiments of the present invention will be described in more detail.

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of “comprising” specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

In addition, in this specification, a weight average molecular weight means the weight average molecular weight (unit: g/mol) of polystyrene conversion measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature at which it is normally applied Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30° C., a chloroform solvent (Chloroform), and a flow rate of 1 mL/min.

In addition, in this specification, (meth)acrylate or (meth)acryl- means "acrylate and methacrylate" or "acryl- and methacryl-", respectively.

According to an embodiment of the invention, the first polyamide-imide resin comprising an imide repeating unit substituted with an epoxy group; and a second polyamide-imide resin comprising an imide repeating unit substituted with a (meth)acrylate group; A photosensitive resin composition comprising a may be provided.

As a result of continuous research by the present inventors, a first polyamide-imide resin comprising an imide repeating unit substituted with an epoxy group; a second polyimide resin comprising an imide repeating unit substituted with a (meth)acrylate group The photosensitive resin composition can have excellent adhesion and chemical resistance while being cured with high efficiency at low temperatures, and also can secure high elongation while maintaining the tensile strength and modulus of the finally obtained cured film at high levels. Through confirmation and confirmation, the invention was completed.

Each of the first polyamide-imide resin and the second polyamide-imide resin of the above embodiment has an imide bond in which 90% or more of the cyclization reaction is completed, so that a high curing temperature of 300° C. or more to form an imide bond Unlike PAA or PAE precursor resins that require For example, a cured product can be formed more efficiently even at a temperature of 250° C. or lower.

In addition, the photosensitive resin composition of the embodiment may include the first polyamide-imide resin including the imide repeating unit substituted with the epoxy group, and may have a feature that the epoxy group can be additionally thermally cured after photocuring, Accordingly, a cured product formed from the photosensitive resin composition may have excellent physical properties in adhesiveness and mechanical strength.

More specifically, the first polyamide-imide resin may include 30 to 80 mol%, or 40 to 70 mol% of the imide repeating unit substituted with an epoxy group. When the content of the imide repeating unit substituted with an epoxy group in the first polyamide-imide resin is too low, it may be technically disadvantageous due to insufficient adhesion to the substrate after curing or insufficient mechanical strength.

In addition, the photosensitive resin composition of the embodiment may include a second polyimide including an imide repeating unit substituted with a (meth)acrylate group, and may have a photocurable feature, and thus the photosensitive resin composition formed from the photosensitive resin composition The cargo can control the sensitivity and mechanical properties of the film after thermal curing through a photopolymerization initiator.

More specifically, the second polyamide-imide resin may include 5 to 50 wt%, or 10 to 45 mol% of the imide repeating unit substituted with a (meth)acrylate group. When the content of the imide repeating unit substituted with the meth)acrylate group in the second polyamide-imide resin is too low, the degree of curing during photocuring may be insufficient. If the content of the imide repeating unit substituted with the meth)acrylate group in the second polyamide-imide resin is too high, overcuring may occur after exposure, making it difficult to implement a fine pattern and poor developability.

On the other hand, each of the first polyamide-imide resin and the second polyamide-imide resin has a weight average molecular weight of 5,000 to 200,000 g/mol, or 7,000 to 150,000 g/mol, or 10,000 to 120,000 g/mol. It is preferable to have a cured film having excellent mechanical properties.

The structures of the first polyamide-imide resin and the second polyamide-imide resin are not particularly limited, for example, the first polyamide-imide resin and the second polyamide-imide resin. Each of the resins may include a repeating unit of Formula 1 below.

[Formula 1]

In Formula 1,

Wherein Q ₁ is an aliphatic, alicyclic or aromatic divalent functional group or a divalent organic group containing at least one heteroatom selected from the group consisting of N, O and S, and X is an aliphatic, alicyclic or aromatic tetravalent An organic group or a tetravalent organic group including any one or more heteroatoms selected from the group consisting of N, O and S, and n is an integer of 1 or more.

The first polyamide-imide resin may _{include at least one repeating unit in which Q 1} is a divalent organic group including an epoxy group.

The second polyamide-imide resin may _{include at least one repeating unit in which Q 1} is a divalent organic group including a (meth)acrylate group.

In Formula 1, X may include a tetravalent functional group selected from the group consisting of Formulas 21 to 27 below.

[Formula 21]

[Formula 22]

In Formula 22, Y ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -OCO(CH ₂ ) _n3 OCO-, wherein n1, n2 and n3 are each an integer of 1 to 10.

[Formula 23]

In Formula 23, Y ₂ and Y ₃ may be the same as or different from each other, respectively, a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -OCO(CH ₂ ) _n3 OCO-, wherein n1, n2 and n3 is an integer from 1 to 10, respectively.

[Formula 24]

In Formula 24, Y ₄ , Y ₅ and Y ₆ may be the same as or different from each other, and each may be a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - , -C(CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, or -OCO(CH ₂ ) _n3 OCO-, wherein n1 , n2 and n3 are each an integer from 1 to 10.

[Formula 25]

[Formula 26]

[Formula 27]

In Formulas 21 to 27, '*' means a bonding point.

Q1 may be a divalent functional group selected from the group consisting of the following Chemical Formulas 31 to 34.

[Formula 31]

In Formula 31, R ₁ is a functional group including an epoxy group, hydrogen, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₂ CF ₃ .

[Formula 32]

In Formula 32, L ₁ is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, -OCH ₂ -C(CH ₃ ) ₂ -CH ₂ O- or -OCO(CH ₂ ) _n3 OCO-, wherein n1, n2 and n3 are each an integer of 1 to 10, R ₁ and R ₂ may be the same as or different from each other, and hydrogen, a functional group including an epoxy group, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₂ CF ₃ .

[Formula 33]

In Formula 33, L ₂ and L ₃ may be the same as or different from each other, respectively, a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, -OCH ₂ -C(CH ₃ ) ₂ -CH ₂ O- or - OCO(CH ₂ ) _n3 OCO-, wherein n1, n2 and n3 are each an integer of 1 to 10, R _{1 ,} R ₂ and R ₃ may be the same as or different from each other, respectively hydrogen, a functional group including an epoxy group, - CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ . .

[Formula 34]

In Formula 34, L ₄ , L ₅ and L ₆ may be the same as or different from each other, each of which is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - , -C(CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _n1 -, -O(CH ₂ ) _n2 O-, -OCH ₂ -C(CH ₃ ) ₂ -CH ₂ O - or -OCO(CH ₂ ) _n3 OCO-, wherein n1, n2 and n3 are each an integer of 1 to 10, and R _{1 ,} R ₂ , R ₃ and R ₄ may be the same as or different from each other, and each hydrogen, functional group including an epoxy group, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₂ CF ₃ .

Each of the first polyamide-imide resin and the second polyamide-imide resin may include an imide group, a carboxyl group, or a derivative thereof at a terminal thereof. Since the first polyamide-imide resin and the second polyamide-imide resin each contain an imide group, a carboxyl group or a derivative thereof at the terminal, an aqueous alkaline solution, for example, potassium hydroxide or tetramethylammonium hydride It may have high solubility in tetramethylammonium hydroxide (TMAH) and the like, and thus the photosensitive resin composition may have high developability.

In the photosensitive resin composition of the embodiment, a weight ratio of the first polyamide-imide resin to the second polyamide-imide resin may be 0.5 to 5, or 1 to 4, or 1.5 to 3. In the photosensitive resin composition of the embodiment, the weight ratio of the first polyamide-imide resin to the second polyamide-imide resin is 0.5 to 5, or 1 to 4, or 1.5 to 3, The point where a fine pattern can be realized and the adhesiveness and film strength after heat curing may be high.

More specifically, in the photosensitive resin composition of the embodiment, when the weight ratio of the second polyamide-imide resin to the second polyamide-imide resin is less than 0.5, the development resistance after photocuring is reduced, and the The degree of hardening may be lowered and it may melt during development. In the photosensitive resin composition of the embodiment, if the weight ratio of the second polyamide-imide resin to the first polyamide-imide resin is greater than 5, it is technically disadvantageous

Meanwhile, the photosensitive resin composition is a negative photosensitive resin composition, and may further include a photoinitiator.

As the photoinitiator, a compound known to have a crosslinking reaction inducing effect in the art to which the present invention pertains may be applied without particular limitation.

As a non-limiting example, the photoinitiator includes 1,3,5,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione ( 1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5- d ]imidazole-2,5(1 H ,3 H )-dione), 1,3,5,6-tetrakis(butoxymethyl ) tetrahydroimidazo[4,5- d ]imidazole-2,5( 1H , 3H )-dione (1,3,4,6-tetrakis(butoxymethyl)tetrahydroimidazo[4,5- d ]imidazole- 2,5( 1H , 3H )-dione), 2,6-bis(hydroxymethyl)benzene-1,4-diol (2,6-bis(hydroxymethyl)benzene-1,4-diol), hexa Kis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine (hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine), (propane- 2,2-diylbis(2-hydroxybenzene-5,3,1-triyl))tetramethanol ((propane-2,2-diylbis(2-hydroxybenzene-5,3,1-triyl))tetramethanol) , 4,4'-(propane-2,2-diyl)bis(2,6-bis(methoxymethyl)phenol)(4,4'-(propane-2,2-diyl)bis(2,6- bis(methoxymethyl)phenol)), 3,3',5,5'-tetrakis(hydroxymethyl)-[1,1'-biphenyl]-4,4'-diol (3,3',5, 5'-tetrakis(hydroxymethyl)-[1,1'-biphenyl]-4,4'-diol), 3,3',5,5'-tetrakis(methoxymethyl)-[1,1'-bi A compound such as phenyl]-4,4'-diol (3,3',5,5'-tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol) may be applied.

The photoinitiator may be included in an amount of 0.5 to 50 parts by weight, or 1 to 40 parts by weight, based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin.

That is, for sufficient expression of the photoinitiation effect, the photoinitiator is preferably included in an amount of 0.5 parts by weight or more based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin. . However, when an excessive amount of the photoinitiator is applied to the photosensitive resin composition, the stability of the cured film may be reduced due to the remaining photoinitiator. Therefore, the photoinitiator is preferably included in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin.

In addition, the photosensitive resin composition is a negative photosensitive resin composition, and may further include a photosensitive compound including a photocurable polyfunctional acrylic compound.

A specific example of the photosensitive compound may include a photocurable polyfunctional (meth)acrylic compound (such as Tetraethyleneglycol dimethacrylate).

The photo-curable polyfunctional acrylic compound is a compound having at least two photocurable acrylic structures in its molecule, and specifically, an acrylate-based compound, a polyester acrylate-based compound, a polyurethane acrylate-based compound, and an epoxy acrylate-based compound. It may include one or more acrylic compounds selected from the group consisting of compounds and caprolactone-modified acrylate-based compounds.

For example, as the acrylate-based compound, a hydroxyl group-containing acrylate-based compound such as pentaerythritol triacrylate or dipentaerythritol pentaacrylate; and a water-soluble acrylate compound such as polyethylene glycol diacrylate or polypropylene glycol diacrylate, and examples of the polyester acrylate compound include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or di Pentaerythritol hexaacrylate etc. are mentioned. In addition, examples of the polyurethane acrylate compound include isocyanate-modified products of the hydroxyl group-containing acrylate compound. Examples of the epoxy acrylate compound include bisphenol A diglycidyl ether and hydrogenated bisphenol A diglyceride. (meth)acrylic acid adduct of cydyl ether or phenol novolak epoxy resin, etc. are mentioned, The caprolactone-modified acrylate-based compound includes caprolactone-modified ditrimethylolpropane tetraacrylate, epsilon-caprolactone-modified dipenta The acrylate of erythritol, caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, etc. are mentioned.

The photo-curable polyfunctional acrylic compound may be included in an amount of 1 to 50 parts by weight, or 5 to 40 parts by weight, or 10 to 30 parts by weight, based on 100 parts by weight of the polyamide-imide resin.

That is, in order to achieve a sufficient crosslinking effect, the light-curable polyfunctional acrylic compound is included in an amount of 1 part by weight or more based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin. desirable. However, when an excessive amount of the photocurable polyfunctional acrylic compound is applied to the photosensitive resin composition, low-temperature curability by the polyamide-imide resin may be reduced. Therefore, the light-curable polyfunctional acrylic compound is preferably included in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin.

Optionally, the photosensitive resin composition may include an epoxy resin.

The epoxy resin may serve to help exhibit high adhesion and adhesion to a substrate used in a semiconductor device or a display device.

Examples of the epoxy resin include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolak epoxy resin, phenol furnace Volak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy Resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin and epsilon- It may include at least one selected from the group consisting of caprolactone-modified epoxy resins, and preferably may include a liquid N-glycidyl epoxy resin.

The epoxy resin may be included in an amount of 5 to 100 parts by weight, or 10 to 100 parts by weight, or 10 to 75 parts by weight, based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin. have.

When the above epoxy resin is used, a thermal acid generator may be used. Examples of the thermal acid generator are not particularly limited, and compounds commonly known to be used as the thermal acid generator may be used.

Meanwhile, the photosensitive resin composition may further include one or more curing accelerators selected from the group consisting of an imidazole-based compound, a phosphine-based compound, and a tertiary amine compound.

The imidazole-based compound may be, for example, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 2-phenyl-4-methyl-5-hydroxymethylimidazole, and a phosphine-based compound. may be, for example, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, and the tertiary amine compound is, for example, dicyandiamide, benzyldimethylamine, 4 -(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine.

The curing accelerator may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin.

The photosensitive resin composition may contain a solvent.

As the solvent, a compound known to enable the formation of the photosensitive resin composition layer in the art to which the present invention pertains may be applied without particular limitation.

As a non-limiting example, the solvent may be at least one compound selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

The ester solvent is 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, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, 3-methoxypropionic acid) methyl, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate ethyl, etc.), 2-oxypropionate alkyl esters (eg, 2-oxypropionate methyl, 2-oxypropionate ethyl, 2- Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-oxy- 2-methylpropionate and 2-oxy-2-methylpropionate ethyl (eg, 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

The ether solvent is diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, di 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, and the like.

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

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

The sulfoxide solvent may be dimethyl sulfoxide or the like.

The solvent is used in an amount of 50 to 500 parts by weight, or 100 to 500 parts by weight, based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin from the viewpoint of the applicability of the photosensitive resin composition. , or 100 to 300 parts by weight, or 100 to 250 parts by weight, or 100 to 150 parts by weight.

In addition, the photosensitive resin composition, in the range that does not impair the above-described effects, as needed, additives such as surfactants, coupling agents, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, corrosion inhibitors, defoamers, and anti-gelling agents. may include

For example, as the adhesion promoter, a silane coupling agent having a functional group such as epoxy, carboxyl group, or isocyanate may be used, and specific examples thereof include trimethoxysilyl benzoic acid, triethoxysilyl benzoic acid, and the like. acid), gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane glycidoxypropyltrimethoxysilane), gamma-glycidoxypropyltriethoxysilane, or a mixture thereof. The adhesion promoter may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyamide-imide resin.

In addition, the surfactant can be used without any particular limitation as long as it is known to be usable in the photosensitive resin composition, but it is preferable to use a fluorine-based surfactant or a silicone-based surfactant. The surfactant may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyamide-imide resin.

According to another embodiment of the present invention, there is provided a cured film including a cured product of the photosensitive resin composition.

As the photosensitive resin composition includes the above-described first polyamide-imide resin and the second polyamide-imide resin, it can be cured with high efficiency even at a temperature of 250° C. or less, 200° C. or less, or 150° C. to 250° C. And it is possible to provide a cured film having excellent mechanical properties even under such curing conditions.

In particular, the cured film can have excellent adhesion and chemical resistance while being cured with high efficiency at a low temperature, and can also secure a high elongation with a high level of tensile strength and modulus.

In addition, the cured film may be applied to a photoresist, an etching resist, a solder top resist, or the like.

In addition, according to another embodiment of the present invention, there may be provided a method for producing a cured film comprising the step of curing the photosensitive resin composition at a temperature of 250 ℃ or less.

As described above, the photosensitive resin composition can be cured with high efficiency even at a temperature of 250 °C or less, 200 °C or less, or 150 °C to 250 °C.

The cured film is a step of applying the photosensitive resin composition to a substrate, a step of exposing the photosensitive resin composition applied to the substrate by irradiating actinic light or radiation, a step of developing the exposed photosensitive resin composition, and the development It may be formed through a process of heating the treated photosensitive resin composition or the like.

The process of applying the photosensitive resin composition to the substrate may be performed by spinning, dipping, doctor blade application, suspension casting, application, spraying, electrostatic spraying, reverse roll application, and the like. In this case, the amount of the photosensitive resin composition applied and the type of substrate depend on the use and application field of the cured film. After applying the photosensitive resin composition to the substrate, it is preferable to dry it under suitable conditions.

In the exposure process, a predetermined pattern of actinic light or radiation is irradiated to the photosensitive resin composition applied to the substrate. In the exposure process, actinic light or radiation having a wavelength of 200 to 600 nm may be applied. As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a scanner, a stepper, proximity, contact, micro lens array, laser exposure, and lens scanner may be used.

In the said developing process, the unexposed part of the photosensitive resin composition is developed using a developing solution. In this case, an aqueous alkaline developer, an organic solvent, or the like may be used as the developer.

According to another embodiment of the invention, forming a resist film on a substrate using the above-described photosensitive resin composition; irradiating a pattern on the resist film using a high energy ray; and developing the resist film using an alkali developer.

In the resist pattern forming method of the above embodiment, a conventionally known cured film manufacturing method and resist pattern forming method and apparatus may be used without particular limitation.

According to the present invention, a photosensitive resin composition that can have excellent adhesion and chemical resistance while being cured with high efficiency at a low temperature, and can also secure a high elongation while maintaining the tensile strength and modulus of the finally obtained cured film at a high level; , a cured film formed from the photosensitive resin composition, and a cured material that can have excellent adhesion and chemical resistance while being cured with high efficiency at a low temperature and that can also secure a high elongation with a high level of tensile strength and modulus. It is intended to provide a method for manufacturing a cured film that can be

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

[Production Example]

Preparation Example 1: Synthesis of polyamide-imide resin (A1)

5 g (0.0156 mol) of 2,2'-bis(trifluoromethyl)benzidine) in a 250 mL round flask equipped with a dean-stark apparatus and condenser ); 1.904 g (0.0052 mol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane); 3.226 g (0.0104 mol) of 4,4'-oxydiphthalic anhydride; 2.111 g (0.0104 mol) of isophthaloyl dichloride; And 30 g of N,N-dimethylacetamide (N,N-dimethylacetamide) was added, and the polymerization reaction was carried out by stirring in a nitrogen atmosphere for 3 hours.

2.34 g of acetic anhydride and 0.32 g of pyridine were added to the polyamic acid solution obtained by the polymerization reaction, and stirred for 18 hours in an oil bath at a temperature of 60 ° C. The imidization reaction was carried out.

After completion of the reaction, the solid content was precipitated using water and ethanol, the precipitated solid content was filtered, and then dried at 40° C. under vacuum for 24 hours or more to obtain a polyamideimide block copolymer having the following repeating units (weight average molecular weight 120,000). g/mol).

Preparation Example 2: Synthesis of polyamide-imide resin (A2)

5 g (0.0156 mol) of 2,2'-bis(trifluoromethyl)benzidine) in a 250 mL round flask equipped with a dean-stark apparatus and condenser ); 1.124 g (0.0052 mol) of 3,3'-dihydroxy-4,4'-diaminobiphenyl (3,3'-dihydroxy-4,4'-diaminobiphenyl); 3.226 g (0.0104 mol) of 4,4'-oxydiphthalic anhydride; 2.111 g (0.0104 mol) of isophthaloyl dichloride; And 30 g of N,N-dimethylacetamide (N,N-dimethylacetamide) was added, and the polymerization reaction was performed by stirring in a nitrogen atmosphere for 3 hours.

2.34 g of acetic anhydride and 0.32 g of pyridine were added to the polyamic acid solution obtained by the polymerization reaction, and stirred for 18 hours in an oil bath at a temperature of 60 ° C. The imidization reaction was carried out.

After completion of the reaction, the solid content was precipitated using water and ethanol, and the precipitated solid content was filtered and dried under vacuum at 40° C. for at least 24 hours to obtain a polyamideimide block copolymer having the following repeating units (weight average molecular weight 93,000) g/mol)

Preparation Examples 3 to 5: Synthesis of polyamide-imide resin (B1 to B3)

An epoxy group was introduced into the resin obtained in Production Example 1 to prepare a resin applicable to a negative photosensitive resin composition. In a 250 ml round flask, add 4 g of Resin A1 to 16 g of N,N-dimethylacetamide and stir to dissolve it completely. To this, 2-isocyanatomethyl oxirane (2-isocyanatomethyl oxirane) was added in the amount shown in Table 1 and stirred at 50° C. for 4 hours to obtain a negative photosensitive resin solution B1 to a resin solution B4.

Preparation Example 6: Synthesis of polyamide-imide resin (C1)

A photocuring group was introduced into the resin obtained in Production Example 4 to prepare a resin applicable to a negative photosensitive resin composition. In a 250ml round flask, put 4 g of Resin A1 to Resin A4 into 16 g of N,N-dimethylacetamide and stir to dissolve it completely. To this, add 1.29 g (0.0083 mol) of 2-isocyanatoethyl methacrylate, add , and stir at 50° C. for 4 hours to obtain negative photosensitive resin solution B1 to resin solution B4. .

Comparative Preparation Example 1: Synthesis of polyimide resin (D1)

2,2'-bis(3-amino-4-hydroxylphenyl)hexafluoropropane (2,2'-bis(3- amino-4-hydroxyphenyl)hexafluoropropane) 7.618 g (0.0208 mol); 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(hexafluoropropylidene)diphthalic anhydride) 9.24 g (0.0208 mol); 0.13 g (0.0008 mol) of Nadic anhydride; And 40 g of N,N-dimethylacetamide (N,N-dimethylacetamide) was added, and the polymerization reaction was carried out by stirring in a nitrogen atmosphere for 4 hours.

2.34 g of acetic anhydride and 0.32 g of pyridine were added to the polyamic acid solution obtained by the polymerization reaction, and stirred for 18 hours in an oil bath at a temperature of 60 ° C. The imidization reaction was carried out.

After completion of the reaction, the solid content was precipitated using water and ethanol, and the precipitated solid content was filtered and dried under vacuum at 40° C. for at least 24 hours to obtain a polyamideimide block copolymer having the following repeating units (weight average molecular weight 55,000). g/mol)

Comparative Preparation Example 2: Synthesis of polyimide resin (D2)

Except for the types and usage ratios of monomers shown in Table 1, the method of Preparation Example 1 was followed to obtain a polyamide-imide resin, and then a polyimide resin having a photocuring group was introduced according to the method of Preparation Example 5.

Production Example Resin Amine component ① Amine component ② Acid dianhydride component ① Acid dianhydride component ② end sealant epoxy group
substitute Acrylic Substituent A1 TFMB
(0.0156 moles) BisAPAF
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - - A1 TFMB (0.0156 moles) HAB
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - - B1 TFMB
(0.0156 moles) BisAPAF
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - Isocyanato methyl oxirane (0.0083 moles) B2 TFMB (0.0156 moles) BisAPAF
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - Isocyanato methyl oxirane (0.0104 moles) B3 TFMB (0.0156 moles) BisAPAF
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - Isocyanato methyl oxirane (0.0125 mol) C1 TFMB
(0.0156 moles) HAB
(0.0052 moles) ODPA
(0.0104 moles) IPDC
(0.0104 moles) - MOI (0.0083 moles) D1 - BisAPAF
(0.0208 moles) 6FDA
(0.0208 moles) - NDA
(0.0008 mole) - D2 - BisAPAF (0.0208 moles) 6FDA
(0.0208 moles) - NDA
(0.0008 mole) MOI (0.0021 moles)

TFMB: 2,2'-bis(trifluoromethyl)benzidineBisAPAF: 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

ODPA: 4,4'-oxydiphthalic anhydride

IPDC: isophthaloyl dichloride

MOI: Karenz MOI??

NDA: Nadic anhydride

[Examples and Comparative Examples: Preparation of photosensitive resin composition]

By mixing the components shown in Table 2 below, the photosensitive resin compositions of Examples and Comparative Examples were prepared, respectively. In Table 2 below, the content of each component is a value based on 100 parts by weight of the polymer resin according to Preparation Example.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Polymer resin of production example B1 50 B2 - 50 25 B3 50 C1 50 50 75 50 D2 100 Light-curable polyfunctional acrylic compound TEGDM 50 50 50 50 50 initiator OXE-01 2 2 2 2 2 additive KBM-503 One One One One One

Light-curable polyfunctional acrylic compound: Tetraethyleneglycol Dimethacrylate / Sigma-Aldrich/ Initiator compound: OXE-01 (product of Basf)

Additive: KBM-503 (from Shin-Etsu)

[Experimental Example: Preparation of cured film and measurement result of physical properties]

Test Example 1: Adhesion of cured film

Each of the photosensitive resin compositions according to the Examples and Comparative Examples was coated on a 4-inch silicon wafer and a silicon wafer substrate coated with Cu to a thickness of 300 nm by spin coating, dried at a temperature of 120 ° C. for 2 minutes, and broadband Exposure was carried out with an energy of 200 mJ/cm 2 in an aligner exposure apparatus. Then, the substrate was cured at a temperature of 200° C. for 2 hours to obtain a substrate on which a cured film having a thickness of about 10 to 11 μm was formed.

In addition, the substrate on which the cured film was formed was evaluated for adhesion (adhesion to the substrate) of the cured film through a taping test according to the TPC-TM-650 method. Specifically, using a dedicated taping test knife (Cross Hatch Cutter, YCC-230/1), make 10 X 10 grid-shaped cuts only on the upper cured film without damaging the lower wafer (the size of each grid) is 100 μm, the number of grids is 100 in total), and Nichibang tape was firmly adhered to the surface of the cured film. After 60 seconds of adhesion, the end face of the tape was bent 180 degrees and peeled off with the same force. At this time, adhesion to the substrate was evaluated by counting the number of grids of the cured film peeled off together with the tape, and the results are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 peeled off
grid number 0/100 0/100 0/100 0/100 10/100

test example 2: of cured film chemical resistance

Each of the photosensitive resin compositions according to the above Preparation Examples was coated on a 4-inch silicon wafer using a spin coating method at 800 to 1200 rpm, dried at 120° C. for 2 minutes, and a broadband aligner exposure apparatus was exposed with an energy of 200 mJ/cm 2 to obtain a substrate on which a photosensitive resin film having a thickness of 10.0 μm was formed. And it hardened again at 200 degreeC temperature for 2 hours, and obtained the board|substrate with a cured film.

The obtained substrate was immersed in acetone (AC), dimethylformamide (DMF) or gamma-butyrolactone (GBL) for 30 minutes, washed with isopropyl alcohol, dried under nitrogen, and then the state of the surface was observed through a microscope. As a result of observation, it was evaluated as ○ or X depending on the presence or absence of damage such as melt marks or cracks on the cured film, and the results are shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 AC O O O O O DMF O O O O X GBL O O O O x

test example 3: Low temperature curing properties

In order to evaluate the low-temperature curing possibility of each photosensitive resin composition according to the preparation examples, proceed in the same manner as in Test Example 2, but the curing temperature was increased to 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃ In another way, a substrate on which a cured film was formed was obtained.

The obtained substrate was immersed in gamma-butyrolactone (GBL) for 30 minutes, washed with isopropyl alcohol, dried under nitrogen, and then the state of the surface was observed through a microscope. As a result of observation, it was evaluated as ○ or X depending on the presence or absence of damage such as melt marks or cracks on the cured film, and the results are shown in Table 5 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 160 ℃ X O X O X 180 ℃ X O O O X 200 ℃ O O O O X 220 ℃ O O O O X 300 ℃ O O O O O

test example 4: film strength

Each of the photosensitive resin compositions according to the above Preparation Examples was coated on a 4-inch silicon wafer using a spin coating method at 800 to 1200 rpm, dried at 120° C. for 2 minutes, and a broadband aligner exposure apparatus was exposed with an energy of 200 mJ/cm 2 to obtain a substrate on which a photosensitive resin film having a thickness of 10.0 μm was formed. And it hardened at 200 degreeC temperature for 2 hours, and obtained the board|substrate with a cured film.

The obtained substrate is immersed in 4.8 wt% HF aqueous solution for 10 minutes, and then the film is peeled off. The peeled film is washed with distilled water and dried at room temperature for 30 minutes. The dried film is cut into 10m*40mm size and evaluated by UTM (Zwich/Roell Z0.5). Specifically, it is measured under the conditions of load cell 0.5kN, pre-load 0.01kgh, 1mm/min, and strain rate 12.5mm/min.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Tensile strength (MPa) 120 130 126 143 120 Elongation (%) 10 9 12 9 6 Modulus (GPa) 3.6 4.0 3.9 4.5 3.1

As shown in Tables 3 to 6, the compositions of Examples can have excellent adhesion and chemical resistance while being cured with high efficiency at a relatively low temperature, and while maintaining the tensile strength and modulus of the finally obtained cured film at a high level It was confirmed that a high elongation rate could also be secured.

Claims (12)

a first polyamide-imide resin including an imide repeating unit substituted with an epoxy group; and (meth) a second polyamide-imide resin comprising 5 to 50 wt% of an imide repeating unit substituted with an acrylate group; including,
The weight ratio of the first polyamide-imide resin to the second polyamide-imide resin is 0.5 to 5, the photosensitive resin composition.
According to claim 1,
The first polyamide-imide resin comprises 30 to 80 mol% of an imide repeating unit substituted with an epoxy group, the photosensitive resin composition.
delete According to claim 1,
The first polyamide-imide resin and the second polyamide-imide resin each have a weight average molecular weight of 5,000 to 200,000 g/mol, the photosensitive resin composition.
According to claim 1,
The photosensitive resin composition, wherein the first polyamide-imide resin and the second polyamide-imide resin each include an imide group, a carboxyl group, or a derivative thereof at a terminal thereof.
delete According to claim 1,
The photosensitive resin composition is a negative photosensitive resin composition,
further comprising a photoinitiator,
photosensitive resin composition
8. The method of claim 7,
The photosensitive resin composition further comprising the photosensitive compound containing the photocurable polyfunctional acrylic compound.
9. The method of claim 8,
A photosensitive resin composition comprising 1 to 50 parts by weight of the photosensitive compound and 0.5 to 50 parts by weight of the photoinitiator based on 100 parts by weight of the total of the first polyamide-imide resin and the second polyamide-imide resin.
The cured film containing the hardened|cured material of the photosensitive resin composition of Claim 1.
A method for producing a cured film, comprising the step of curing the photosensitive resin composition of claim 1 at a temperature of 250° C. or less.
forming a resist film on a substrate using the photosensitive resin composition of claim 1;
irradiating a pattern on the resist film using a high energy ray; and
A resist pattern forming method comprising a; developing the resist film using an alkali developer.