KR20210081742A - Photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

A photosensitive resin composition of the present invention introduces a repeating unit represented by a chemical formula 1 and a repeating unit represented by chemical formulas 2 and/or 3 into a binder, and thus, it is possible to manufacture a cured film having excellent resolution by controlling developability while being sufficiently cured even at a low temperature by improving the degree of curing. Furthermore, the composition has chemical resistance, adhesion to a substrate, and stability over time, and thus, it is possible to form the cured film having better physical properties especially at side surfaces.

Description

Photosensitive resin composition and cured film prepared therefrom

The present invention relates to a photosensitive resin composition capable of forming a cured film excellent in developability, resolution and chemical resistance even at low temperature curing, and a cured film prepared therefrom.

A photosensitive resin composition is widely used in LCD, OLED, and quantum dot (QD)-based display devices.

The LCD is composed of upper and lower substrates and liquid crystal between both substrates, and a touch screen panel (TSP) may be connected to the upper substrate as necessary. In general, the TSP is manufactured after the assembly process of bonding the color filter and the thin film transistor (TFT). Accordingly, the cured film should be cured at a low temperature in order to minimize the effect on the color filter that has already been manufactured. However, there is a problem that a cured film is not formed because the composition is not sufficiently crosslinked during low temperature curing, or the strength is not sufficient, so a composition capable of low temperature curing is required. In addition, since the OLED and quantum dot (QD)-based display devices are manufactured at a low temperature, a composition suitable for low-temperature curing is required.

On the other hand, a technique for producing a cured film by curing a composition containing an acrylate-based resin as a binder at a low temperature is known in the field (Korean Patent Application Laid-Open No. 2010-0029479), but it was not sufficient to satisfy chemical resistance. In addition, there was a limit in terms of stability over time because the acid value of the binder practically implemented in the above patent was high,

Korean Patent Publication No. 2010-0029479

Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent developability, resolution, chemical resistance and stability over time, and a cured film prepared therefrom, while being sufficiently cured even at low temperatures.

In order to achieve the above object, the present invention provides (A) (a1) a repeating unit represented by the following formula (1) and (a2) a repeating unit represented by the following formula (2) and (a3) a repeating unit represented by the following formula (3) A copolymer comprising at least one selected from the group; (B) a photopolymerizable compound; And (C) a photopolymerization initiator; provides a photosensitive resin composition comprising:

[Formula 1] [Formula 2] [Formula 3]

In the above formula, R ₁ is hydrogen or substituted or unsubstituted C _1-20 alkyl, L ₁ and L ₂ are each independently substituted or unsubstituted C _1-10 alkylene, or substituted or unsubstituted C _6-20 arylene, R ₂ and R ₄ is each independently hydrogen or C _1-4 alkyl, R ₃ and R ₅ are each independently C _1-4 alkylene, and a, b and c are each independently an integer from 1 to 100.

In order to achieve the other object, the present invention provides a cured film formed from the photosensitive resin composition.

The photosensitive resin composition of the present invention is excellent by introducing the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 2 and/or 3 into the binder, thereby improving the degree of curing and thereby sufficiently curing even at low temperatures and controlling developability. A cured film having a resolution can be manufactured. Furthermore, the composition can form a cured film having better physical properties in terms of chemical resistance, adhesion to the substrate, and stability over time.

1 is a graph showing the results of evaluating the chemical resistance of cured films prepared from the compositions of Examples and Comparative Examples.

The present invention is not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the present invention is not changed.

In the present specification, "comprising" means that other components may be further included unless otherwise specified. In addition, it should be understood that all numbers and expressions indicating amounts of components, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.

The present invention relates to (A) a copolymer, (B) a photopolymerizable compound; And (C) a photoinitiator; provides a photosensitive resin composition comprising. The copolymer (A) includes a repeating unit represented by a specific chemical formula, and the related description will be described in detail in the corresponding section. The photosensitive resin composition may optionally further include (D) an adhesion aid, (E) a surfactant and/or (F) a solvent.

As used herein, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate"

The weight average molecular weight for each of the following components refers to the weight average molecular weight (g/mol or Da) in terms of polystyrene measured by gel permeation chromatography (GPC, using tetrahydrofuran as the elution solvent).

(A) copolymer

The copolymer (A) used in the present invention is a group consisting of (a1) a repeating unit represented by the following formula (1), (a2) a repeating unit represented by the following formula (2), and (a3) a repeating unit represented by the following formula (3) It contains one or more selected from.

[Formula 1] [Formula 2] [Formula 3]

In the above formula, R ₁ is hydrogen or substituted or unsubstituted C _1-20 alkyl, L ₁ and L ₂ are each independently substituted or unsubstituted C _1-10 alkylene, or substituted or unsubstituted C _6-20 arylene, R ₂ and R ₄ is each independently hydrogen or C _1-4 alkyl, R ₃ and R ₅ are each independently C _1-4 alkylene, and a, b and c are each independently an integer from 1 to 100.

( a1) a repeating unit represented by the formula (1)

The copolymer (A) may include (a1) a repeating unit represented by Formula 1 below. The repeating unit (a1) serves to improve resolution by controlling developability in the composition.

[Formula 1]

The _{definitions of R 1} , L ₁ , L ₂ and a are the same as described above.

Specifically, R ₁ is hydrogen or unsubstituted C _1-10 alkyl, L ₁ and L ₂ are each independently substituted or unsubstituted C _1-10 alkylene, and a is 1 to 80 is the integer of

More specifically, R ₁ is hydrogen or unsubstituted C _1-8 alkyl, L ₁ and L ₂ are each independently unsubstituted C _1-6 alkylene, and a is 1 to 50 is an integer

In the present invention, the repeating unit (a1) may be derived from an ethylenically unsaturated compound containing an acid group, and specifically may be derived from a long-chain compound containing a carboxy group. More specifically, it may be derived from a succinate-based acrylate-based compound.

For example, the succinate-based acrylate compound may be 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloylethyl succinate, or a mixture thereof.

The content of the repeating unit (a1) is more than 5 to 20 mol% or less, more than 5 to 18 mol% or less, 6 to 20 mol%, 6 to 18 mol% based on 100 mol% of the repeating unit constituting the copolymer (A). , 7 to 20 mol%, 7 to 18 mol%, or 7 to 15 mol%. When within the above range, the solubility of the composition is improved, the pattern is not peeled off, and excellent developability and chemical resistance can be obtained. If the amount is less than the above range, developability is deteriorated, and if the amount is excessive than the above range, copolymer polymerization is difficult.

(a2) a repeating unit represented by Formula 2

The copolymer (A) may include (a2) a repeating unit represented by Formula 2 below. The repeating units (a2) and (a3) can control the pattern flowability of the composition during low-temperature curing, and provide sufficient film strength and chemical resistance to the resulting cured film.

[Formula 2]

The _{definitions of R 2} , R ₃ and b are the same as described above.

Specifically, R ₂ is hydrogen or unsubstituted C _1-8 alkyl, R ₃ is C _1-3 alkylene, and b is an integer from 1 to 80.

More specifically, R ₂ is hydrogen or unsubstituted C _1-5 alkyl, R ₃ is C _1-3 alkylene, and b is an integer of 1 to 50.

The repeating unit (a2) represented by Formula 2 may be derived from an ethylenically unsaturated compound including an alicyclic epoxy group.

The ethylenically unsaturated compound containing the alicyclic epoxy group may be 2,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate.

The content of the repeating unit (a2) may be 10 to 30 mol%, 10 to 28 mol%, 15 to 30 mol%, or 15 to 28 mol% based on 100 mol% of the repeating unit constituting the copolymer (A). . When within the above range, the storage stability of the composition is maintained and the film remaining rate is improved.

(a3) the repeating unit represented by the above formula (3)

The copolymer (A) may include (a3) a repeating unit represented by Formula 3 below.

[Formula 3]

The _{definitions of R 4} , R ₅ and c are the same as described above.

Specifically, R ₄ is hydrogen or unsubstituted C _1-8 alkyl, R ₅ is C _1-3 alkylene, and c is an integer of 1 to 80.

More specifically, more specifically, R ₄ is hydrogen or unsubstituted C _1-5 alkyl, R ₅ is C _1-3 alkylene, and c is an integer of 1 to 50.

The repeating unit (a3) represented by Formula 3 may be derived from an ethylenically unsaturated monomer containing a non-alicyclic epoxy group.

The ethylenically unsaturated monomer containing the non-alicyclic epoxy group may be glycidyl (meth) acrylate or 4-hydroxybutyl acrylate glycidyl ether.

The content of the repeating unit (a3) may be 10 to 30 mol%, 10 to 28 mol%, 15 to 30 mol%, or 15 to 28 mol% based on 100 mol% of the repeating unit constituting the copolymer (A). have. When within the above range, the storage stability of the composition is maintained and the film remaining rate is improved.

According to one embodiment, the copolymer (A) may include the repeating units (a1) and (a2). According to one embodiment, the copolymer (A) may include the repeating units (a1) and (a3). According to one embodiment, the copolymer (A) may include the repeating units (a1) to (a3).

When the copolymer (A) contains the repeating units (a2) and (a3) simultaneously, the repeating units (a2) and (a3) are 50 to 99: 50 to 1, 50 to 90: 50 to 10, It may have a molar ratio of 50 to 85: 50 to 15, 50 to 80: 50 to 20, or 50 to 75: 50 to 25. In the above range, excellent stability over room temperature, heat resistance and chemical resistance can be obtained, and pattern implementation is improved.

(a4) a repeating unit different from the repeating units (a1) to (a3)

The copolymer (A) of the present invention may further include a repeating unit (a4) different from the repeating units (a1) to (a3). The repeating unit (a4) may include one or more, two or more, or three or more.

The repeating unit (a4) may be derived from ethylenically unsaturated compounds different from those presented above, but is not limited thereto.

For example, the ethylenically unsaturated compound is an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, an aromatic ring-containing unsaturated compound, an unsaturated carboxylic acid ester compound, an N-vinyl tertiary amine compound including N-vinyl, an unsaturated ether compound, an unsaturated compound It may be derived from de-based compounds or mixtures thereof.

Examples of the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acids and anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; and trivalent or higher unsaturated polycarboxylic acids and anhydrides thereof.

Examples of the aromatic ring-containing unsaturated compound include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, p-nonylphenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene , triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, fluoro styrene, chloro styrene, bromo styrene, iodine styrene, methoxy styrene, ethoxy styrene, propoxy styrene, p-hydroxy -?-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, etc. are mentioned.

Examples of the unsaturated carboxylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydro puffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxy Oxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol ( Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (meth) acrylic a rate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. are mentioned.

Examples of the N-vinyl tertiary amine compound containing N-vinyl include N-vinylpyrrolidone, N-vinylcarbazole, N-vinylmorpholine, and the like.

As an example of the said unsaturated ether type compound, vinyl methyl ether, vinyl ethyl ether, etc. are mentioned.

Examples of the unsaturated imide compound include N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. .

Specifically, the repeating unit (a4) may be derived from at least one unsaturated compound selected from the group consisting of an aromatic ring-containing unsaturated compound, an unsaturated carboxylic acid ester-based compound, and an unsaturated carboxylic acid.

According to one embodiment, the repeating unit (a4) may include a repeating unit derived from an aromatic ring-containing unsaturated compound and an unsaturated carboxylic acid ester-based compound.

According to one embodiment, the repeating unit (a4) may include a repeating unit derived from an aromatic ring-containing unsaturated compound and an unsaturated carboxylic acid.

According to one embodiment, the repeating unit (a4) may include a repeating unit derived from an aromatic ring-containing unsaturated compound, an unsaturated carboxylic acid ester-based compound, and an unsaturated carboxylic acid.

The content of the repeating unit derived from the aromatic ring-containing unsaturated compound is 10 to 50 mol%, 10 to 45 mol%, 10 to 40 mol%, 20 to 50 mol% based on 100 mol% of the repeating unit constituting the copolymer (A). 40 mol % or 20 to 35 mol %.

The content of the repeating unit derived from the unsaturated carboxylic acid ester compound is 10 to 30 mol%, 10 to 25 mol%, 15 to 30 mol%, or 15 to 30 mol% based on 100 mol% of the repeating unit constituting the copolymer (A). 25 mole %.

The content of the repeating unit derived from the unsaturated carboxylic acid is 1 to 15 mol%, 1 to 10 mol%, 1 to 8 mol%, 5 to 10 mol%, based on 100 mol% of the repeating unit constituting the copolymer (A). or 5 to 8 mol%.

The copolymer (A) used in the present invention may be synthesized by copolymerization by a known method. Specifically, the copolymer (A) may be prepared by adding a radical polymerization initiator, a solvent, and a monomer compound capable of inducing the repeating units, adding nitrogen, and then polymerizing while slowly stirring.

The radical polymerization initiator is not particularly limited, but 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, etc. have. These radical polymerization initiators can be used individually or in mixture of 2 or more types.

Any solvent may be used as long as the solvent is used for preparing the copolymer, and for example, propylene glycol monomethyl ether acetate (PGMEA) may be used.

The weight average molecular weight (Mw) of the copolymer (A) may be 5,000 to 20,000 Da, 5,000 to 15,000 Da, or 5,000 to 13,000 Da. When within the above range, excellent adhesion to the substrate, good physical and chemical properties, it is possible to maintain an appropriate viscosity.

In addition, the acid value of the copolymer (A) is 10-75 KOHmg/g, 30-75 KOHmg/g, 55-75 KOHmg/g, 55-70 KOHmg/g, 60-70 KOHmg/g or 65-75 KOHmg It can be /g. When within the above range, the stability over time (shelf-life) of the photosensitive resin composition can be further improved.

The content of the copolymer (A) is 30 to 80% by weight, 30 to 70% by weight, 30 to 65% by weight, 35 to 70% by weight, 35 to 65% by weight based on the total weight of the photosensitive resin composition on a solid basis, 35 to 60% by weight or 40 to 60% by weight. The solid content means the content of the entire composition excluding the remaining amount of the solvent. When it is in the said range, the pattern development after development is favorable, and characteristics, such as a residual film rate and chemical resistance, improve.

(B) photopolymerizable compound

The photopolymerizable compound used in the present invention is a compound capable of polymerization by the action of a photoinitiator.

Specifically, the photopolymerizable compound may include a monofunctional or polyfunctional ester compound having at least one ethylenically unsaturated group, and may preferably be a bifunctional or more polyfunctional compound in terms of chemical resistance.

Examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol Di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) ) acrylate, monoester product of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acryl rate, monoester product of dipentaerythritol penta(meth)acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (pentaerythritol triacrylate) and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol A epoxy acrylate and ethylene glycol monomethyl ether acrylate. One or more types may be used, but the present invention is not limited thereto.

In addition, a compound having a straight chain alkylene group and an aromatic ring structure and having two or more isocyanate groups, and three, four or five acryloyloxy groups and/or methacryloyloxy groups having one or more hydroxyl groups in the molecule and/or methacryloyloxy groups A polyfunctional urethane acrylate compound obtained by reacting a compound having the compound may be mentioned, but the present invention is not limited thereto.

Commercially available photopolymerizable compounds include monofunctional (meth)acrylates, Aronix M-101, Copper M-111, Copper M-114 (manufactured by Toagosei Co., Ltd.), AKAYARAD TC-110S , copper TC-120S (manufactured by Nippon Chemical Co., Ltd.), V-158, V-2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), etc., as a commercial product of bifunctional (meth)acrylate, Aronix M-210, Dong M-240, Dong M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, Dong HX-220, Dong R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335 HP (Osaka Yuki Chemical Co., Ltd. product), etc., and commercially available products of trifunctional or higher (meth)acrylates include Aronix M-309, Copper M-400, Copper M-403, Copper M-405, Copper M- 450, Dong M-7100, Dong M-8030, Dong M-8060, TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, Dong DPHA, Dong DPHA-40H, Dong DPC1-20, Dong-30, Bronze -60, Dong-120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, Dong-300, Dong-360, Dong-GPT, Dong-3PA, Dong-400 (manufactured by Osaka Yuki Chemical High School) and the like. The said photopolymerizable compound can be used individually or in combination of 2 or more types.

The content of the photopolymerizable compound is 10 to 99 parts by weight, 10 to 80 parts by weight, 20 to 80 parts by weight, 30 to 80 parts by weight, 40 to 80 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content. , 50 to 90 parts by weight, 50 to 80 parts by weight, or 50 to 70 parts by weight. When within the above range, it is possible to obtain excellent pattern developability and coating film characteristics while maintaining a constant residual film rate.

(C) photoinitiator

As the photopolymerization initiator used in the present invention, any known photopolymerization initiator may be used.

The photopolymerization initiator may serve to initiate a polymerization reaction of monomers that can be cured by visible light, ultraviolet light, deep-ultraviolet radiation, or the like.

The type of the photopolymerization initiator is not particularly limited, but one selected from the group consisting of acetophenone-based, benzophenone-based, benzoin-based and benzoyl-based, xanthone-based, triazine-based, halomethyloxadiazole-based and ropindimer-based photopolymerization initiators More than one can be used.

Specific examples of the photopolymerization initiator include p-dimethylaminoacetophenone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-hydroxy- 2-Methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, benzoinpropyl ether, diethylthioxanthone, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl -s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazine-2 -yl)amino)-3-phenylcoumarin, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2-(o-ethoxy) Carbonyl) oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(o-benzoyloxime), o-benzoyl-4'-(benzmercapto)benzoyl-hexyl- Ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphoro-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyldisulfide or mixtures thereof, but are not limited thereto.

As another example, the photopolymerization initiator may include at least one oxime-based compound.

The oxime-based compound is not particularly limited as long as it is a radical initiator including an oxime structure, and for example, may be an oxime ester-based compound, preferably an oxime ester-based fluorene-based compound.

The oxime-based compound is disclosed in Korean Patent Publication Nos. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753 , 2009-0009991, 2009-0093933, 2010-0097658, 2011-0059525, 2011-0091742, 2011-0026467, 2011-0015683, 2013-0124215, Republic of Korea It is preferable in terms of high sensitivity to use at least one of the oxime-based compounds described in Korean Patent Publication No. 10-1435652, International Patent Publication No. WO 2010/102502, and WO 2010/133077.

These trade names include OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA), NCI-831 (ADEKA), SPI-02 (Samyang EMS), SPI-03 (Samyang EMS) and the like.

The content of the photoinitiator is 0.1 to 20 parts by weight, 0.1 to 15 parts by weight, 1 to 20 parts by weight, 1 to 10 parts by weight, 1 to 8 parts by weight, or It may be 2 to 8 parts by weight. When it is within the above range, it is possible to obtain high sensitivity and excellent developability and coating film properties.

(D) Adhesive Aids

The photosensitive resin composition of the present invention may include an adhesion aid to improve adhesion to the substrate.

The adhesion aid may have at least one reactive group selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, and an epoxy group.

The type of the adhesion aid is not particularly limited, but for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanato Propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-isocyanatepropyltriethoxysilane, or mixtures thereof.

Preferably, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane or N-phenylaminopropyltrimethoxysilane is used to reduce the remaining film rate and Adhesiveness with a board|substrate can be improved more.

The content of the adhesive aid is 0.001 to 5 parts by weight, 0.01 to 5 parts by weight, 0.01 to 4 parts by weight, 0.1 to 4 parts by weight, 1 to 4 parts by weight, or It may be 1 to 3 parts by weight. When it is in the said range, adhesiveness with a board|substrate can be improved more.

(E) surfactant

The photosensitive resin composition of the present invention may contain a surfactant, if necessary, to improve coatability and prevent defect formation.

The type of the surfactant is not particularly limited, but preferably a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and other surfactants are mentioned.

Examples of the surfactant include BYK 307, BYK 333 (by BYK), BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F-482, F-489 (manufactured by Dainippon Ink Chemical Co., Ltd.), Florad FC-135, Florad FC-170C, Florad FC-430, Florad FC -431 (manufactured by Sumitomo 3M Co., Ltd.), Sufflon S-112, Sufflon S-113, Sufflon S-131, Suplon S-141, Sufflon S-145, Sufflon S-382, Sufflon S-382 Pron SC-101, Suflon SC-102, Suflon SC-103, Suflon SC-104, Suflon SC-105, Suflon SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, F-Top EF303, EFTOP EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Co., Ltd.) Manufactured), DC3PA, DC7PA, SH11PA, SH21PA, SH8400, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF-4440, TSF- Fluorine-based and silicone-based surfactants such as 4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (manufactured by GE Toshiba Silicone Co., Ltd.) and BYK-333 (manufactured by BYK Corporation); Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether and nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based copolymer polyflow No. 57 and 95 (manufactured by Kyoeisha Yuji Chemical Co., Ltd.) and the like. These can be used individually or in combination of 2 or more types. Among them, BYK 307 or BYK 333 manufactured by BYK may be preferably used in terms of dispersibility.

The content of the surfactant may be 0.001 to 5 parts by weight, 0.01 to 5 parts by weight, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.1 to 2 parts by weight based on 100 parts by weight of the copolymer (A) based on the solid content. have. When it is within the above range, the coating of the composition becomes smooth.

(F) solvent

The photosensitive resin composition of the present invention may preferably be prepared as a liquid composition in which the above components are mixed with a solvent.

As the solvent, any known solvent used in the photosensitive resin composition may be used as long as it has compatibility with but does not react with the above-described components of the photosensitive resin composition.

Examples of such a solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; lactic acid esters such as methyl lactic acid, ethyl lactic acid, n-propyl lactic acid and isopropyl lactic acid; aliphatic carboxylic acid esters such as ethyl acetic acid, n-propyl acetic acid, isopropyl acetic acid, n-butyl acetic acid, isobutyl acetic acid, n-amyl acetic acid, isoamyl acetic acid, isopropyl propionic acid, n-butyl propionic acid, and isobutyl propionic acid; esters such as methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid, methyl pyruvic acid, and ethyl pyruvic acid; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-butyrolactone; and mixtures thereof. The solvent may be used alone or in combination of two or more.

In the photosensitive resin composition according to the present invention, the content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the photosensitive resin composition, the solid content is 5 to 70% by weight based on the total weight of the photosensitive composition, 10 to 70% by weight, 10 to 60% by weight, or 10 to 55% by weight of the organic solvent may be included.

In addition, the photosensitive resin composition of the present invention may include other additives such as antioxidants and stabilizers within a range that does not reduce physical properties.

The present invention provides a cured film formed from the photosensitive resin composition.

Specifically, a cured film may be prepared by applying the photosensitive resin composition according to the present invention on a substrate and then curing it. In this case, the cured film may be obtained by thermosetting the photosensitive resin composition at a temperature of 150° C. or less, 50 to 150° C., 50 to 130° C., 70 to 150° C., or 70 to 130° C.

Specifically, the cured film may be prepared by a method known in the art. For example, the photosensitive resin composition is applied on a silicon substrate or a glass substrate by a spin coating method, and the solvent is removed by pre-bake at 50 to 150° C. for 30 to 130 seconds, and then a photomask having a desired pattern is used. A pattern can be formed on the coating layer by exposure to light and developing with a developer (eg, tetramethylammonium hydroxide solution (TMAH)). Thereafter, the patterned coating layer is thermally cured (post-bake) at 150° C. or less, 50 to 150° C., 50 to 130° C., 70 to 150° C. or 70 to 130° C. for 10 minutes to 5 hours to obtain the desired A cured film can be obtained.

The exposure may be performed by irradiating with an exposure dose of ^{10 to 100 mJ/cm 2} in a wavelength range of 200 to 450 nm.

As described above, in the photosensitive resin composition of the present invention, the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 and/or 3 are introduced into the binder, thereby improving the degree of curing and sufficiently curing even at low temperatures. By controlling the properties, a cured film having excellent resolution can be manufactured. Furthermore, since the composition can form a cured film having better physical properties in terms of chemical resistance, adhesion to a substrate, and stability over time, it can be usefully applied to a device apparatus including a touch panel.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

The weight average molecular weight described in Preparation Examples below is a polystyrene conversion value measured by gel permeation chromatography (GPC).

[Example]

Preparation Example 1. Preparation of copolymer (A-1)

In a 250 ml round bottom flask equipped with a reflux condenser and stirrer under nitrogen atmosphere, 14.24 g (32 mol%) of styrene, 10.68 g (25 mol%) of methyl methacrylate, 13.90 g of 2-acryloyloxyethyl succinate ( 15 mol%), a monomer mixture consisting of 15.10 g (18 mol%) of 2,4-epoxycyclohexylmethyl methacrylate and 6.07 g (10 mol%) of glycidyl methacrylate, V-65 3.0 as a radical polymerization initiator 5 mol% of dodecanethiol as mol% and molecular weight regulator was dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA). Then, the liquid mixture was added dropwise to a flask containing 40 g of PGMEA at 65° C. for 3 hours, followed by polymerization for 18 hours to obtain a copolymer A-1 having a solid content of 30 wt%. The resulting copolymer A-1 had a weight average molecular weight of 8.7 kDa, a polydispersity (Mw/Mn) of 2.9, and an acid value of 62 mgKOH/g.

Preparation Examples 2 to 6. Preparation of copolymers (A-2 to A-6)

As shown in Table 1, copolymers A-2 to A-6 were prepared in the same manner as in Preparation Example 1, except that the type and/or content was changed.

Examples and Comparative Examples: Preparation of photosensitive resin composition

Information on the components used in the following Examples and Comparative Examples is as follows.

Example 1.

60 parts by weight of Copolymer A-1 of Preparation Example 1, 40 parts by weight of DPHA as the photopolymerizable compound (B), 2.85 parts by weight of OXE-02 as the photopolymerization initiator (C), 2.85 parts by weight of KBE- as the adhesion aid (D) 1.45 parts by weight of 9007N and 0.95 parts by weight of BYK-307 as surfactant (E) were uniformly mixed. In this case, each of the above contents is the contents of the solid content except for the solvent. The mixture was dissolved in PGMEA so that the solids content was 25% by weight. This was stirred for 3 hours to obtain a liquid photosensitive resin composition.

Examples 2 and 3, and Comparative Examples 1 to 3.

A composition solution was obtained in the same manner as in Example 1, except that the type and/or content of each component was changed as shown in Table 3 below.

[Evaluation example]

Preparation of cured film from photosensitive resin composition

The photosensitive resin compositions prepared in Examples and Comparative Examples were respectively coated on a glass substrate using a spin coater, and then pre-cured at 100° C. for 60 seconds to form a coating film. A mask prepared so that 100% exposure was possible on the 5 cm wide and 5 cm vertical portions of the obtained coating film was applied so that the distance from the substrate was 25 μm. Thereafter, using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm, exposure was carried out for a certain period of time so as to be 30 mJ/cm 2 based on 365 nm, and 23° C. with an aqueous solution diluted with TMAH 2.38 wt% was developed until the unexposed part was completely washed out. After curing the formed pattern in an oven at 130° C. for 1 hour, a cured film having a final thickness of 2.5 (±0.5) μm was obtained.

Evaluation Example 1. Chemical resistance

According to the manufacturing method of the cured film, each composition obtained in Examples and Comparative Examples was coated on a glass substrate, and pre-cured, exposed and developed. The developed film was heated in a convection oven at 130° C. for 60 minutes to obtain a cured film. The cured film was immersed in an organic solvent (organic stripper (TOK-106); MEA 70% + DMSO 30%) at 50° C. for 1 minute and then taken out. In this case, the organic solvent was used by mixing 70% of monoethylamine (MEA) and 30% of dimethyl sulfoxide (DMSO) by weight. Then, the thickness of the film was measured with a non-contact thickness meter (SIS-2000, SNU), and chemical resistance (%) was calculated according to the following equation. The smaller the numerical value according to the following formula, the better the chemical resistance was evaluated. The results are shown in Table 4 and FIG. 1 below.

[Equation]

Chemical resistance (%) = (thickness after organic stripper treatment / thickness before organic stripper treatment) x 100.

◎ (very good): chemical resistance (%) less than 103%

○ (Excellent): Chemical resistance (%) greater than 103% and less than or equal to 104%

X (Poor): Chemical resistance (%) exceeds 104%

Evaluation Example 2. Adhesion

A cured film was formed on the substrate in the same manner as in Evaluation Example 1, a cross-cut test was performed according to ASTM D3359, and then the substrate was treated according to the chemical resistance evaluation method. At this time, the adhesive force was evaluated according to the following criteria. The results are shown in Table 4 below.

0B: Breaks into flakes and falls off more than 65%

1B: The edge of the cut part and the grid come off, and the area is 35% ~ 65%

2B: The edge of the cut part and the grid come off, and the area is 15% ~ 35%

3B: A small area falls off at the intersection of the cut area, and the area is 5% to 15%

4B: It falls off from the intersection of the cut part and the area is 5% or less

5B: The end of the cut part is smooth and there is no lattice falling off

Evaluation Example 3. Remaining film rate

The initial thickness after pre-curing was measured according to the above-mentioned cured film manufacturing method. After the cured film manufacturing process, the thickness of the cured film was measured after developing at 23 ° C with an aqueous solution diluted with 2.38 wt% of TMAH and curing at 130 ° C for 1 hour, and calculating the percentage of the thickness of the final cured film to the film thickness after pre-curing The remaining film rate was calculated.

Looking at the results of Table 4 and FIG. 1 , it was found that the cured films prepared from the compositions of Examples 1 to 3 did not have a large change in film thickness even before and after the organic solvent treatment, and thus had excellent chemical resistance. In addition, the adhesion evaluation result was good, and the residual film rate was also excellent.

On the other hand, the cured film prepared from the composition of Comparative Example 1 showed similar aspects to those of Examples in adhesion and residual film rate, but was significantly poor in chemical resistance, and the cured film prepared from the composition of Comparative Examples 2 and 3 had a pattern. It was not possible to proceed with the evaluation itself, including chemical resistance, because it did not form itself.

Claims (12)

(A) (a1) a repeating unit represented by the following formula (1),
(a2) a copolymer comprising at least one selected from the group consisting of a repeating unit represented by the following formula (2) and (a3) a repeating unit represented by the following formula (3);
(B) a photopolymerizable compound; and
(C) a photopolymerization initiator; containing, the photosensitive resin composition:
[Formula 1] [Formula 2] [Formula 3]

In the above formula,
R ₁ is hydrogen or a substituted or unsubstituted C _1-20 alkyl,
L ₁ and L ₂ are each independently a substituted or unsubstituted C _1-10 alkylene, or a substituted or unsubstituted C _6-20 arylene,
R ₂ and R ₄ is each independently hydrogen or C _1-4 alkyl;
R ₃ and R ₅ are each independently C _1-4 alkylene,
a, b and c are each independently an integer from 1 to 100; According to claim 1,
The copolymer (A) has a weight average molecular weight of 5,000 to 15,000 Da, and an acid value of 10 to 75 KOHmg/g, the photosensitive resin composition. According to claim 1,
The content of the repeating unit (a1) is more than 5 to 20 mol% or less based on 100 mol% of the repeating unit constituting the copolymer (A), the photosensitive resin composition. According to claim 1,
The content of the repeating unit (a2) and the repeating unit (a3) is 10 to 30 mol%, respectively, based on 100 mol% of the repeating unit constituting the copolymer (A), the photosensitive resin composition. According to claim 1,
The copolymer (A) further comprises a repeating unit (a4) different from the repeating units (a1) to (a3), the photosensitive resin composition. 6. The method of claim 5,
The repeating unit (a4) is derived from an ethylenically unsaturated compound,
The ethylenically unsaturated compound is at least one selected from the group consisting of an aromatic ring-containing unsaturated compound, an unsaturated carboxylic acid ester-based compound, and an unsaturated carboxylic acid, the photosensitive resin composition. 7. The method of claim 6,
The photosensitive resin composition, wherein the amount of the repeating unit (a4) derived from the aromatic ring-containing unsaturated compound is 10 to 50 mol% or less based on 100 mol% of the repeating unit constituting the copolymer (A). 7. The method of claim 6,
The photosensitive resin composition, wherein the amount of the repeating unit (a4) derived from the unsaturated carboxylic acid ester-based compound is 10 to 30 mol% or less based on 100 mol% of the repeating unit constituting the copolymer (A). 7. The method of claim 6,
The photosensitive resin composition, wherein the repeating unit (a4) derived from the unsaturated carboxylic acid is 1 to 15 mol% or less based on 100 mol% of the repeating unit constituting the copolymer (A). According to claim 1,
The photosensitive resin composition comprising the copolymer (A) in an amount of 30 to 80 wt% based on the total weight of the photosensitive resin composition based on the solid content, the photosensitive resin composition. The cured film formed from the photosensitive resin composition of Claim 1. 12. The method of claim 11,
The cured film obtained by thermosetting the said cured film at the temperature of 70-150 degreeC of the said photosensitive resin composition.

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