KR20010009058A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: Provided is a photosensitive resin composition, which has membrane property and photosensitivity by adding a linker component that can do chemical bond between a binder resin and a linking compound at the same time chemical bond of chain-to-chain of the binder resin. CONSTITUTION: The composition capable of developing in the alkaline aqueous solution contains i) 0.1-90wt%(based on the total photosensitive resin composition) of a binder resin containing carbonic acid being copolymer obtained from compound of one more selected from the formula:(CH2=C(R1)COOH), the formula :(CH2=C(R1)COOR2) and the formula:(CH2=C(R1)-R3 and an average molecular is 1,000-30,000; ii) 1-100mole%(based on carbonic acid group of the binder resin) of formula 1 selected from N,N-dimethylaminoethyl(metha)acylate, N,N-diethylaminoethyl(metha)acylate, N,N-dimethylaminopropyl(metha)acylate, N,N-diphenylaminoethyl(metha)acylate, and N,N-diaminoethyl(metha)acylate; and iii) a photopolymerization initiator containing carbonic acid and a photopolymerization initiator. In the formula 1, R1 and R2 are each other same or different H, methyl, ethyl, propyl or phenyl group, R3 is H or methyl group and n is integer 1-6. In the binder resin, R1 is H or methyl group; R2 is C1-C8 alkyl, alkyl group substituted hydroxyl group or compound selected from substituted or non-substituted C4-C12 aryl group or arylalkyl group; and R3 is benzene, C1-C8 alkyl, C1-C8 alkoxyl, benzene having C1-C6 alkylated substance, benzene having C1-C8 alkoxylated substance or benzene substituted hydroxyl group or halogen atom.

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition that can be developed under an aqueous alkali solution, and more particularly, to a film in a photosensitive resin composition useful as a color filter and thin film transistor (TFT) circuit passivation in a liquid crystal display (LCD) manufacturing process. The present invention relates to a photosensitive resin composition having improved characteristics and photosensitive characteristics.

Recently, due to the development of so-called photolithography, which forms images using active light such as ultraviolet (UV) light, there is an increasing demand for photosensitive resins that can be developed in aqueous alkali solution in many fields requiring the formation of microscopic images. .

Alkali-developable photosensitive resins have been used in dry film resists used in the manufacture of printed circuit boards, photoresists for the manufacture of semiconductor circuits, and in recent years, in the field of flat panel displays including semiconductors and LCDs, color filters and various Applications are also expanding as circuit protective films.

The photosensitive resin composition which can be developed in an aqueous alkali solution is generally a) a binder resin dissolved or swelled by an aqueous alkali solution; B) crosslinkable compounds having at least two ethylenically unsaturated bonds; C) Photopolymerization Initiator D) Consists of a solvent that can dissolve each of the components mentioned above, and may contain other additives that, if necessary, improve the dye, pigment, or film forming performance or adhesion to the substrate.

The a) is a binder resin dissolved or swelled by an aqueous alkali solution, and generally has a structure containing carboxylic acid or carboxylic anhydride or a hydroxyl group, an amino group, and an amide group in a polymer chain, and a noblel phenolic resin or an acrylic resin homopolymer or air. Coalescing is widely used.

As the acrylic binder resin soluble in an alkaline solution, a copolymer using acrylic acid or methacrylic acid and one or more compounds selected from the group consisting of alkyl esters thereof and substituted or unsubstituted aryl esters is mainly used.

U.S. Patent No. 4629680 and U.S. Patent No. 4139391 used a copolymer of benzyl acrylate / methacrylic acid, and Japanese Patent Application Publication No. 54-34327 discloses a ternary of methyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid. Copolymers are disclosed, and Japanese Patent Application Laid-open No. 55-6210 refers to a terpolymer consisting of methyl methacrylate / ethyl acrylate / acrylic acid. In addition, Japanese Patent Laid-Open No. 9-23059 describes a copolymer using allyl acrylate, hydroxyalkyl acrylate, methacrylic acid, and the like.

The compound of b) is a crosslinkable compound having at least two ethylenically unsaturated bonds, and specific examples thereof include polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,3-butanediol di (meth) acryl. Latene, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, pentaerythritol hexa (meth) acrylate, etc. are mentioned.

In the photosensitive resin composition of the prior art, such a crosslinkable compound is distributed in a binder resin in the composition, and when exposed by actinic light such as UV, a crosslinkable reaction is caused. The alkali-soluble resin is formed during the development process by forming a net structure. By preventing the solution from being dissolved by the developer, it serves to leave an image on the substrate as a result.

However, in the conventional photosensitive resin composition, the solubility difference between the exposed portion and the unexposed portion is not large enough, and in some cases, the binder resin, which should remain in the developing process, is partially melted by the developing solution, resulting in the desired fine pattern. In most cases, it was difficult to obtain a shape.

On the other hand, when the crosslinking compound is excessively used in order to prevent such a phenomenon, the surface hardness after exposure is lowered, thereby lowering the processability and increasing the exposure amount for causing a sufficient crosslinking reaction, thereby lowering the process yield.

In addition, in this case, the solubility of the unexposed portion is also lowered, resulting in a decrease in resolution as a resist.

In order to solve the problems as described above, the present invention, by adding a linker component that can cause chemical bonding between the binder resin and the crosslinkable compound in the exposed portion during the exposure process and at the same time the chemical bond between the binder resin chains, It is to provide a photosensitive resin having excellent resolution and maximizing solubility difference with an exposed site and reducing overall exposure by reducing the amount of crosslinkable compound, which is not only advantageous in process but also excellent in film properties.

The present invention provides a photosensitive resin composition containing a compound represented by the following formula (1) in the photosensitive resin composition comprising a carboxylic acid-containing binder resin and a photopolymerization initiator and developable in an aqueous alkali solution, in order to achieve the above object to provide.

Formula (1)

(Herein, R1 and R2 are each selected from the group consisting of hydrogen, methyl group, ethyl group, propyl group and phenyl group which are the same or different, and R3 is hydrogen or methyl group. N is an integer of 1 to 6.)

Compounds having an amino group and at least one ethylenically unsaturated group in one molecule of the formula (1) are N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate. Preference is given to compounds selected from the group consisting of N, N-dimethylaminopropyl (meth) acrylate, N, N-diphenylaminoethyl (meth) acrylate, and N, N-diaminoethyl (meth) acrylate.

The carboxylic acid-containing binder resin has a number average molecular weight of 1,000 to 30,000 and is a copolymer obtained from at least one compound among the compounds of the formula (2) and the compounds of the formulas (3) and (4), wherein the formula (1) Is a compound having an amino group and one or more ethylenically unsaturated groups in one molecule at the same time, the photopolymerization initiator is capable of generating radicals by actinic light.

Formula (2)

CH2 = C (R1) COOH

Formula (3)

CH2 = C (R1) COOR2

Formula (4)

CH2 = C (R1) -R3

Wherein R1 is hydrogen or methyl, R2 is an alkyl group having 1-8 carbon atoms, an alkyl group substituted by a hydroxy group, an aryl group having 4-12 carbon atoms substituted or unsubstituted, or an arylalkyl group R3 is benzene or an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, a benzene having an alkyl substituent having 1-6 carbon atoms, or 1 carbon atom. Is a compound selected from the group consisting of benzene, hydroxyl group or halogen substituted benzene having an alkoxy substituent of -8.)

As the compound of Formula (2), acrylic acid or methacrylic acid may be used.

The compound of formula (3) is benzyl (meth) acrylate, phenyl (meth) acrylate, hexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate or 2-ethylhexyl (meth) Compounds selected from the group consisting of acrylates are preferred, and more preferably benzyl (meth) acrylate or phenyl (meth) acrylate.

The compound of formula (4) is preferably a compound selected from the group consisting of styrene, 4-hydroxystyrene, 4-methylstyrene or vinyl acetate.

The content of the carboxylic acid-containing binder resin and the compound of formula (1) in the photosensitive resin composition is 0.1 to 90% by weight and preferably 1 to 50% by weight based on the total components.

The compound of the formula (1) is used in an amount of about 1 to 100 mol% based on the carboxylic acid-containing monomer (compounds of the formulas 2, 3 and 4) used in the preparation of the binder resin.

As the crosslinkable compound used in the present invention, a compound having at least two or more ethylenically unsaturated groups which are generally used may be used.

Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triacrylate can be used alone or in combination, preferably It is preferable to use dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The content of the crosslinkable compound in the photosensitive resin composition of the present invention is 0 to 90% by weight based on the total components, preferably 0 to 50% by weight.

Examples of the photopolymerization initiator include benzophenones such as benzophenone and acetophenone, substituted benzophenones such as bis-4,4`-dimethylaminobenzophenone, and bis-4,4`-diethylaminobenzophenone, 2,4 Triazines such as 6-tris (trichloromethyl) -triazine, ketones such as N-methyl-2-benzoylmethylene-β-naphthoazole, 2,2-dimethoxy-1,2-diphenylethanone and the like Compounds selected from the group consisting of photopolymerization initiators can be used alone or in combination.

The photopolymerization initiator is used in an amount of 0.01 to 20% by weight based on the total components, preferably 0.1 to 10% by weight.

As a solvent, it is a general thing mainly used for superposition | polymerization of an acryl polymer, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, a methyl cellosol part, a methyl cellosolve acetate, dimethylformamide, a propylene glycol methyl ether acetate, 2-methoxy It is used individually or in mixture as a compound chosen from the group which consists of ethyl ether.

In the photosensitive resin composition of this invention, in addition to the basic component mentioned above, a small amount of antifoaming agent, surfactant, a thermal polymerization inhibitor, an adhesion promoter, etc. for improving pigment, dye, or film forming performance can be used as needed.

The photosensitive resin composition solution of this invention finally obtained is filtered using the membrane filter of 0.1-5 micrometers.

Film formation can use the method of well-known spin coating, roll coating, spray coating, etc. It is preferable to use a spin coating method.

As the substrate for film formation, a glass plate or a silicon wafer can be used. At this time, the thickness of the film surface is determined by the film forming conditions such as the viscosity of the composition, the concentration of the solid content, the film forming speed and the like, it is possible to obtain a thin film of 0.1 to 500 ㎛ thickness with the composition of the present invention.

The obtained thin film is pretreated by maintaining for 10 seconds to 500 seconds in a heating plate or oven at a temperature of 50 to 150 ℃.

The thin film dried to some extent is irradiated with ultraviolet rays through a positive test photomask (manufactured by TOPPAN). At this time, the ultraviolet light source was irradiated with an illuminance of about 30 to 500 mJ / cm 2 using a 1 kW high-pressure mercury lamp containing g, h, and i rays, and no special optical filter was used.

The UV-irradiated portion shows a difference in solubility compared to the unirradiated portion as described above.

The thin film irradiated with ultraviolet rays was developed at a temperature of 20 to 30 ° C. by a spray method or a dip method. At this time, as the developer, an aqueous KOH solution having a pH of 9 to 12 or an aqueous solution of tetramethylammonium hydride of 0.1 to 5% by weight can be used.

The following presents preferred embodiments to aid the understanding of the present invention. However, the following examples are only for the understanding of the present invention and the present invention is not limited to the following examples.

Example 1

The photosensitive resin composition was manufactured with the following composition.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(Molar ratio = 70/30, number average molecular weight = 10,000)

(2) 1.58 g of N.N-dimethylaminoethyl methacrylate

(3) 2 g of pentaerythritol tetramethacrylate

(4) 2 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

The prepared composition solution was filtered using a 0.2 μm Teflon membrane filter. The photosensitive resin composition was applied on a glass plate by using a spin coating method, and then placed on a heating plate and maintained at a temperature of 80 ° C. for 3 minutes. Subsequently, a positive test photomask (manufactured by TOPPAN) was placed on the thin film by a contact method and irradiated with ultraviolet rays. In this case, a 1 kW high-pressure mercury lamp containing g, h, and i rays was used as the ultraviolet light source, and irradiated with an illuminance of 100 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried with blowing nitrogen gas, and heated in a heating oven at 250 ° C. for 1 hour. The thickness of the obtained film was 4 micrometers, and the clear pattern of line width and line spacing of 7 micrometers was obtained.

Example 2

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(2) 1.26 g of N, N-dimethylaminoethyl methacrylate

(3) 3 g of pentaerythritol tetramethacrylate

(4) 2 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

The film was formed and obtained by the method similar to Example 1.

The film thus obtained had an exposure dose of 100 mJ / cm 2, film thickness of 3.5 μm, and resolution of 7 μm.

Example 3

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(2) 0.787 g of N, N-dimethylaminoethyl methacrylate

(3) 4 g of pentaerythritol tetramethacrylate

(4) 2 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

The film was formed and obtained by the method similar to Example 1.

The film thus obtained had an exposure dose of 150 mJ / cm 2, a film thickness of 3.7 μm, and a resolution of 8 μm.

Example 4

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(2) 0.157 g of N, N-dimethylaminoethyl methacrylate

(3) 5 g of pentaerythritol tetramethacrylate

(4) 2 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

The film was formed and obtained by the method similar to Example 1.

The film thus obtained had an exposure dose of 150 mJ / cm 2, a film thickness of 3.8 μm, and a resolution of 9 μm.

Example 5

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(Molar ratio = 50/50, number average molecular weight = 15,000)

(2) 5 g of N, N-dimethylaminoethyl acrylate

(3) 3 g of bis-4,4`-diethylaminobenzophenone

(4) 40 g of propylene glycol methyl ether acetate

After the film was formed in the same manner as in Example 1, the film was exposed to light at an intensity of 100 mJ / cm 2 and then developed. The thickness of the obtained film was 2.8 micrometers, and the pattern of the line width and the line spacing of 7 micrometers was obtained clearly.

Example 6

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) ethyl methacrylate / methyl methacrylate / acrylic acid copolymer (molar ratio = 40/30/30, number average molecular weight = 12,500) 5 g

(2) 2.85 g of N, N-dimethylaminoethyl acrylate

(3) 2 g of pentaerythritol tetramethacrylate

(4) 3 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

After the film was formed in the same manner as in Example 1, the film was exposed to light at an intensity of 100 mJ / cm 2 and then developed. The thickness of the obtained film was 3.1 micrometers, and the pattern of the line width and the line spacing of 6 micrometers was clearly obtained.

Example 7

In the same manner as in Example 1, a photosensitive resin composition having the following composition was prepared.

(1) ethyl methacrylate / methyl methacrylate / acrylic acid copolymer

(Molar ratio = 40/30/30, number average molecular weight = 12,500) 5 g

(2) 2.70 g of N, N-dimethylaminoethyl acrylate

(3) 2 g of pentaerythritol tetramethacrylate

(4) 3 g of bis-4,4`-diethylaminobenzophenone

(5) 40 g of propylene glycol methyl ether acetate

After the film was formed in the same manner as in Example 1, the film was exposed to light at an intensity of 100 mJ / cm 2 and then developed. The thickness of the obtained film was 3.1 micrometers, and the pattern of the line width and the line spacing of 7 micrometers was clearly obtained.

Comparative Example 1

The photosensitive resin composition which has the following composition was manufactured.

(1) benzyl methacrylate / methacrylic acid copolymer 5 g

(Molar ratio = 70/30, number average molecular weight = 10,000)

(2) 5 g of pentaerythritol tetra (meth) acrylate

(3) 2 g of bis-4,4`-diethylaminobenzophenone

(4) 40 g of propylene glycol methyl ether acetate

After the film was formed in the same manner as in Example 1, the film was exposed to light at an intensity of 100 mJ / cm 2 and then developed. The pattern thus produced was lost.

Comparative Example 2

After preparing the photosensitive resin composition which has a composition similar to the comparative example 1, after forming a film by the method similar to Example 1, it developed after exposing to the roughness of 150 mJ / cm <2>. The thickness of the obtained film was 3.0 micrometers, and the pattern of 20 micrometers of line widths and line spaces was obtained.

Comparative Example 3

After preparing the photosensitive resin composition which has a composition similar to the comparative example 1, after forming a film by the method similar to Example 1, it developed after exposing to the roughness of 200 mJ / cm <2>. The thickness of the obtained film was 3.8 micrometers, and the pattern of the line width and the line spacing 10 micrometers was obtained.

In Examples 1 to 7 prepared according to the present invention, a photosensitive resin composition was prepared using N, N-diethylaminoethyl methacrylate, which is a compound having an amino group and at least one ethylenically unsaturated group simultaneously in one molecule. In this case, the fine resolution was obtained with the line width and the line spacing being 6 to 9 mu m. However, in Comparative Examples 1 to 3, in which N, N-diethylaminoethyl methacrylate was not used, the pattern was lost or had a resolution of 10 μm or more depending on the exposure amount, so that the resolution was higher than that of the photosensitive resin manufacturing method according to the embodiment. Not only was it remarkably dropped, but also a uniform and thin film thickness of 2.8 to 4 µm was obtained in the film thickness. However, in the case of the comparative example, a thick film having a thickness of 3.0 µm or more was produced.

Claims (10)

In the photosensitive resin composition containing a carboxylic acid containing binder resin and a photoinitiator, and developable in aqueous alkali solution, Photosensitive resin composition containing the compound represented by following General formula (1): Formula (1) Here, R1 and R2 are the same or different from each other selected from the group consisting of hydrogen, methyl group, ethyl group, propyl group, phenyl group, R3 is hydrogen or methyl group, n is an integer of 1 to 6. The method of claim 1, The photosensitive resin composition containing the compound of the said General formula (1) 1-100 mol% with respect to the carboxylic acid group of binder resin. The method of claim 1, The compound of formula (1) is N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate. N, N-dimethylaminopropyl (meth) acrylate, N, N-diphenylaminoethyl (meth) acrylate, N, N-diaminoethyl (meth) acrylate Photosensitive resin composition which is a compound chosen from the group which consists of . The method of claim 1, The binder resin is a photosensitive resin composition which is a copolymer obtained from at least one compound among the compounds selected from the group consisting of compounds represented by the following general formula (2) and general formula (3) and (4): Formula (2) CH2 = C (R1) COOH Formula (3) CH2 = C (R1) COOR2 Formula (4) CH2 = C (R1) -R3 Here, R1 is hydrogen or methyl group, R2 is an alkyl group having 1-8 carbon atoms, an alkyl group substituted with a hydroxy group, an aryl group or an arylalkyl having 4-12 carbon atoms substituted or unsubstituted. R3 is benzene or an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, a benzene having an alkyl substituent having 1-6 carbon atoms, or 1 carbon atom. It is a compound selected from the group consisting of benzene, hydroxyl group or halogen substituted benzene having an alkoxy substituent which is -8. The method of claim 4, wherein Formula (2) is acrylic acid or methacrylic acid, and Formula (3) is benzyl (meth) acrylate, phenyl (meth) acrylate, hexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) Acrylate, a compound selected from the group consisting of 2-ethylhexyl (meth) acrylate, the formula (4) is a compound selected from the group consisting of styrene, 4-hydroxy styrene, 4-methyl styrene, vinyl acetate Photosensitive resin composition. The method of claim 1, The content of the binder resin is 0.1 to 90% by weight of the total photosensitive resin composition components of the photosensitive resin composition. The method of claim 4, wherein The photosensitive resin composition which is a binder resin whose content of the compound of the said General formula (2) is 1-99 mol% with respect to the combined amount of the said General formula (3) or the said General formula (4). The method of claim 4, wherein The photosensitive resin composition whose number average molecular weights of the said binder resin are 1,000-30,000. The film obtained using the photosensitive resin composition of Claim 1. The method of claim 9, The film has a thickness of 3 to 4 µm and a resolution of 6 to 9 µm.