WO2004107052A1

WO2004107052A1 - Negative photoresist composition for spinless (slit) coating

Info

Publication number: WO2004107052A1
Application number: PCT/KR2004/001300
Authority: WO
Inventors: You-Lee Pae; Young-Keun Kim; Suk-Young Choi; Hyuk-Jin Cha; Jae-Hwan Lee; Keun-Joo Lee; Mi-Sun Ryu; Hyun-Jin Seo; Seung-Woo Woo; Je-Sun Woo; Kwon-Yil Yoo; Su-Hyun Lee; Yong-Man Jeong; Bum-Young Choi; Cheol Han; Woong Kim; Nak-Chil Jung; Seong-Jae Hong; Min-Ji Kim; Young-Soo Choi
Original assignee: Adms Technology Co., Ltd.
Priority date: 2003-06-02
Filing date: 2004-06-01
Publication date: 2004-12-09
Also published as: WO2004107053A1; KR20040104053A; TWI274962B; TW200428140A; TW200428152A; TWI266952B; KR100579832B1

Abstract

A negative photoresist composition for spinless (slit) coating is disclosed. The negative photoresist composition includes 5~50 parts by weight of acrylic binder resin, 2~200 parts by weight of multifunctional monomer containing unsaturated aliphatic groups, 0.005~100 parts by weight of an photoinitiator, 0.001~5 parts by weight of silicon compound containing epoxy or amine group, and 0.001~5 parts by weight of fluorine-based or silicon-based surfactant. A solvent is added to the composition so that viscosity becomes 2~20 cps. The negative photoresist composition may form a uniform coating layer without any coating defects when a layer such as an organic insulating layer is formed on a substrate with a spinless coater, and is easy to control edge profile of the coating layer.

Description

NEGATIVE PHOTORESIST COMPOSITION FOR SPINLESS (SLIT)

COATING

TECHNICAL FIELD The present invention relates to a phororesist composition for spinless (slit) coating, and more particularly, to a negative photoresist composition for spinless (slit) coating, which may form a uniform coating layer without coating defects when a layer is formed on a substrate with a spinless coater, and is easy to control the edge profile of the coating layer.

BACKGROUND ART

Flat panel displays such as liquid crystal displays (LCDs) are currently being large-sized, and substrates used in the LCDs are also being large-sized accordingly. At present, production lines for the 5th-generation substrate have been installed, and larger substrates like the 6th- or 7th generation are under development. With the trend of enlargement of the substrate, the coating method of photoresist is changed accordingly. In other words, for the 4th-generation glass substrate, the slit and spin coating method was used, in which a photoresist composition was applied through a slit on the substrate and then spin-coated. However, for the 5th- or later generation substrate having a size

of more than lOOOmmx 1000mm, spinless (slit) coating method has been used due to its

inability of spinning, in which photoresist composition was applied through a slit on a substrate and then the coating process is completed without spinning. As mentioned above, since the coating method has been changed, the photoresist composition currently being used should be changed. Particularly, in case the spinless (slit) coating method is applied to large-sized substrates, the coating layer formed by photoresist composition should be uniformed and coated without any defects. Moreover, the edge profile of the coating layer should be easily controlled during the spinless (slit) coating process.

DISCLOSURE OF INVENTION

The present invention is designed to solve the problems of the prior art, and therefore it is an object of the present invention to provide a negative photoresist composition, which may form a uniform and defect-free coating layer when a layer such as an organic insulating layer is formed on a substrate, and is easy to control the edge profile of the coating layer.

To achieve the above mentioned object, the present invention provides a negative photoresist composition comprising: 5 ~ 50 parts by weight of an acrylic binder resin; 2 ~ 200 parts by weight of a multifunctional monomer containing unsaturated aliphatic groups; 0.005 ~ 100 parts by weight of a photoinitiator, 0.001 ~ 5 parts by weight of a silicon compound containing epoxy or amine group; and 0.001 ~ 5 parts by weight of a fluorine-based or silicon-based surfactant, wherein a solvent is added thereto so that viscosity is 2 ~ 20 cps.

BEST MODES FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The negative photoresist composition for spinless (slit) coating of the present invention comprises 5 ~ 50 parts by weight of an acrylic binder resin. As for the acrylic binder resin, any conventional acrylic binder resin for a negative photoresist composition may be used. Preferably, a resin having the structure of the following general formula 1 or 2 is used alone or by their mixture.

General formula 1

In the general formula 1, X is hydrogen atom or methyl, Y¹ is alkyl or hydroxyalkyl, which has 1 to 16 carbon atoms, and Y² is selected from the group consisting of compounds having the structure of the following chemical formulas (I) to (XX).

CH₂= CC--CCOO--NN--RRaa--^ ^ \ (K)

=C-CO-N-R₂ XX (HI)

C^^C-CO-O-Ra-GH-^^Λ.^ (XViπ)

In the chemical formulas (I) to (XX), Ri is hydrogen atom or methyl, R₂ is alkylene having 1 to 10 carbon atoms, R₃ is hydrocarbon having 1 to 10 carbon atoms, R_Λ is hydrogen atom or methyl, R₅ is hydrocarbon having 1 to 10 carbon atoms, and k is an integer from 0 to 10.

General formula 2

In the general formula 2, the repeating unit A is selected from the group

consisting of benzyl methacrylate, styrene, α -methyl styrene, isobonyl acrylate and

isobonyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanylethyloxy acrylate, dicyclopentanylethyloxy methacrylate, dicyclopentenylethyloxy acrylate, dicyclopentenylethyloxy methacrylate, and so on, B is selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate, acryl amide, and so on, and C is acrylic acid or methacrylic acid, wherein the binder resin having the structure of the general formula 2 contains random copolymer regardless of the order of A, B, and C.

The binder resin having the structure of the general formula 1 is a copolymer composed of a monomer containing carboxylic acid and a monomer containing double bonds. In case the negative photoresist composition of the present invention comprising the copolymer is applied on a substrate and then formed patterns, the uniformity is excellent without any defects such as residue after developing. In other words, Y¹ in the general formula 1 is alkyl or hydroxyalkyl having 1 to 16 carbon atoms, thereby improving adhesion. Moreover, Y² contains bulky cyclic aliphatic structures unlike conventional binder resins of acrylic copόlymer, which contain aromatic groups, thereby improving film retention, and heat resistance according to high glass transition temperature.

Moreover, the binder resin having the structure of the general formula 2 shows almost the same effect as the binder resin of the general formula 1. As for the binder resin of the general formula 2, another kind of repeating unit, for example, alkylacrylate or alkylmethacrylate having 2 to 16 alkyl groups as shown in general formula 3 (D), may be introduced within the scope of the present invention. More specifically, the repeating unit may be methyl methacrylate, butyl methacrylate, lauryl methacrylate, methyl acrylate, butyl acrylate, lauryl acrylate, styrene, and so on.

General formula 3

In particular, when the mixture of the binder resin of the general formula 1 and the binder resin of the general formula 2 is used, the hardness of pattern can be improved, and whitening phenomena can be disappeared, since the compatibility between the binder resin and other photoresist components in the composition is increased.

A multifunctional monomer containing unsaturated aliphatic groups comprises at least one selected from the group consisting of: a compound obtained by esterification

of polyhydric alcohol with α , β -unsaturated carboxylic acid, which is selected from the

group consisting of ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 14 ethyleneoxide groups, trimethylolpropane

di(meth)acrylate, trimemethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propylene glycol di(meth)acrylate having 2 to 14 propyleneoxide groups, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol tri(meth)acrylate; a compound obtained by adding (meth)acrylic acid to a compound having glycydyl group, which is selected from the group consisting of trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; an ester compound of polycarboxylic acid or an adduct of polyisocyanate with a compound having hydroxyl group and unsaturated aliphatic groups, which is selected from the

group consisting of phthalic acid diester of β -hydroxyethyl (meth)acrylate and toluene

diisocyanate adduct of β -hydroxyethyl (meth)acrylate,; and a (meth)acrylic acid alkyl

ester selected from the group consisting of methyl(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and so on. The content is 2 to 200 parts by weight, and preferably 5 to 50 parts by weights.

By regulating the ratio between the multifunctional monomer containing above unsaturated aliphatic groups and the binder resin, a negative photoresist having high heat resistance, high transparency, good uniformity, and pattern stability can be formed.

Moreover, a photoinitiator of acetophenone or benzophenone type is generally used. Since a colored photoinitiator lowers transparency, high transparency may be achieved by using of a photoinitiator having suitable sensitivity at the wavelength of exposure and having no color in itself. Generally, a photoinitiator used in a crosslinking reaction of an acrylic multifunctional monomer is chosen considering UV wavelength used. Since mercury lamp, which is most commonly used, has the wavelength of 310 ~ 420 nm, a photoinitiator that generates radicals within this wavelength range is most preferably used.

For such a photoinitiator, it is preferred to use an acetophenone, benzophenone, or triazine type photoinitiator such as Irgacure 369, Irgacure 651, Irgacure 907, TPO, CGI124, and EPD BMS mixture. For example, benzophenone, phenyl biphenyl ketone,

1-hydroxy-l-benzoylcyclohexane, benzyldimethylketal, 1-benzyl-l-dimethylamino-l- (4-morpholino-benzoyl)propane, 2-morpholyl-2-(4-methylmercapto)benzoylpropane, thioxanthone, l-chloro-4-propoxythioxanthone, 2-chloro or 4-chlorothioxanthone, 2,4-dimethyl thioxanthone, isopropylthioxanthone, diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoinbutylether,

2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, l,7-bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis

(2-morpholino-isobutyroyl)carbazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazine,

2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s- triazine, and so on. In order to improve transparency and minimize exposure doses, the content of the photoinitiator is 0.005 to 100 parts by weight, and preferably 0.5 to 10 parts by weight.

A silicon compound containing epoxy or amine group in the negative photoresist composition of the present invention, improves adhesion between ITO electrode and the composition, and heat resistance after hardening. The silicon compound comprises at least one selected from the group consisting of (3-glycidoxypropyl)trimethoxysilane, (3- glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane,

(3 -glycidoxypropyl)methyldiethoxysilane, (3 -glycidoxypropyl)dimethylmethoxysilane, (3 -glycidoxypropyl)dimethylethoxysilane, 3 ,4-epoxybutyltrimethoxysilane,

3 ,4-epoxybutyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, and so on. The content of the silicon compound is 0.001 to 5 parts by weight, and preferably 0.05 to 0.1 parts by weight.

Moreover, the negative photoresist composition of the present invention comprises 0.001 to 5 parts by weight of a fluorine-based or silicon-based surfactant. The fluorine-based or silicon-based surfactant is sold in the commercial names of Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471, F-475 (manufactured by Dainippon Ink & Chemicals), FC-170C, FC-430, FC-431 (manufactured by Sumotomo 3M co., Ltd.), BYK 306, 307, 310, 331,333 (manufactured by BYK-Chemie), and so on.

Additionally, additives such as photosensitizer, thermal polymerization inhibitor, defoaming agent, and leveling agent, can be used in the negative photoresist composition if necessary.

Preferably, a solvent is added so that the negative photoresist composition of the present invention has 2 ~ 20 cps of viscosity. More preferably, the viscosity is regulated to be 3 ~ 10 cps, which is more advantageous to controlling the thickness of a thin layer without a pinhole. The solvent comprises at least one selected from the group consisting of ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethylethyl ether, methylmethoxy propionate, ethylethoxy propionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methylcellosolvacetate, ethylcellosolvacetate, diethylene glycol methylacetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc),

N-methyl-2-pyrrolidone (NMP), Y -butyrolactone, diethyl ether, ethylene glycol

dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methylcellosolve, ethylcellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, and so on. Hereinafter, the present invention will be described in detail. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Embodiments 1 ~ 19

A negative photoresist composition was prepared according to the components and contents of table 1 as below. Acrylic binder resin : 10wt%

Multifunctional monomer containing unsaturated aliphatic groups : 10wt% Irgacure 907 : 5wt%

(3-glycidoxypropyl)trimethoxysilane : 0.05wt% Fluorine-based surfactant : 0.03wt%

Solvent : residual quantity

The acrylic binder resin of the general formula 1 (where X is methyl, Y¹ is

methyl, and Y² is the chemical formula (LI) having Ri of methyl), was used.

Moreover, dipentaerythritol penta/hexa acrylate (DPHA) was used as the multifunctional monomer containing unsaturated aliphatic groups, and R08 (manufactured by Dainippon Ink & Chemicals) was used as the fluorine-based surfactant. The viscosity of the formed photoresist composition was about 4 cps.

Embodiments 20 ~ 51 The negative photoresist composition was prepared in the same manner as in the embodiment 1, except that DMC was used as a solvent, and the kind and content of the surfactant were changed according to the table 2. The viscosity of the formed photoresist composition was about 4 cps.

The evaluations of the negative photoresist composition according to the embodiments, was performed on Cr glass. Coating property, uniformity, and edge profile of the coating layer was tested as below. The results are shown in the tables 1 and 2. (1) Coating property

The negative photoresist composition was applied on Cr glass with a spinless

coater, and then prebaked at 90 °C for 2min. Then, the coating layer was observed

under sodium lamp in naked eye. In case of no coating defect, we denoted 'good', otherwise 'bad'.

(2) Uniformity

The negative photoresist composition was applied on Cr glass with a spinless

coater, and then prebaked at 90 ^°C for 2min . Then, the thickness of the coating layer

was measured with nanospec at 10 points. In case the difference between maximum

and minimum values of the thickness is less than 500 A, we denoted 'good', otherwise

'bad'.

(3) Edge Profile

The negative photoresist composition was applied on Cr glass with a spinless

coater, and then prebaked at 90 ^°C for 2min. Then, the edge area was scanned with a profiler. In case of more than 55° of the angle between pattern sidewall and the substrate, we denoted 'good', otherwise 'bad'.

Table 1

Table 2

INDUSTRIAL APPLICABILITY

As described above, the negative phtoresist composition of the present invention may form a uniform coating layer without any coating defects when a layer such as an organic insulating layer is formed on a substrate with a spinless coater, and is easy to control edge profile of the coating layer.

The present invention has been described in detail. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Claims

WHAT IS CLAIMED:

1. A negative photoresist composition for spinless (slit) coating, comprising:

5 ~ 50 parts by weight of an acrylic binder resin; 2 ~ 200 parts by weight of a multifunctional monomer containing unsaturated aliphatic groups; 0.005 ~ 100 parts by weight of a photoinitiator; 0.001 ~ 5 parts by weight of a silicon compound containing epoxy or amine group; and 0.001 ~ 5 parts by weight of a fluorine-based or silicon-based surfactant, wherein a solvent is added thereto so that viscosity is 2 ~ 20 cps.

2. The negative photoresist composition for spinless (slit) coating according to claim 1, wherein the acrylic binder resin is selected from the group consisting of a resin having the structure of the following general formula 1, a resin having the structure of the following general formula 2, and their mixture:

where X is hydrogen atom or methyl, Y¹ is alkyl or hydroxyalkyl, which has 1 to 16 carbon atoms, and Y² is selected from the group consisting of compounds having the structure of the following chemical formulas (I) to (XX);

CH₂==C-CO-0— (0-R₃-CO)k-0— R nέT^^^-^^^nOH 01)

where Ri is hydrogen atom or methyl, R₂is alkylene having 1 to 10 carbon atoms,

R₃ is hydrocarbon having 1 to 10 carbon atoms, R₄ is hydrogen atom or methyl, R₅ is

hydrocarbon having 1 to 10 carbon atoms, and k is an integer from 0 to 10;

<General Formula 2> ^K^M^ ^

where the repeating unit A is selected from the group consisting of benzyl methacrylate, styrene, α -methylstyrene, isobonyl acrylate and isobonyl methacrylate,

dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanylethyloxy acrylate, dicyclopentanylethyloxy methacrylate, dicyclopentenylethyloxy acrylate, and dicyclopentenylethyloxy methacrylate, B is selected from the group consisting of glycidyl methacrylate, hydroxyethyl methacrylate, dimethylamino methacrylate, and acryl amide, and C is acrylic acid or methacrylic acid, wherein the binder resin having the structure of the general formula 2 contains random copolymer regardless of the order of A, B, and C.

3. The negative photoresist composition for spinless (slit) coating according to claim 1, wherein the multifunctional monomer containing unsaturated aliphatic groups comprises at least one selected from the group consisting of: a compound obtained by esterification of polyhydric alcohol

with α , β -unsaturated carboxylic acid, which is selected from the group consisting of

ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate having 2 to 14 ethyleneoxide groups, trimethylolpropane di(meth)acrylate, trimemethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propylene glycol di(meth)acrylate having 2 to 14 propyleneoxide groups, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol tri(meth)acrylate; a compound obtained by adding (meth)acrylic acid to a compound having glycydyl group, which is selected from the group consisting of trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; an ester compound of polycarboxylic acid or an adduct of polyisocyanate with a compound containing hydroxyl group and unsaturated aliphatic groups, which is

selected from the group consisting of phthalic acid diester of β -hydroxyethyl

(meth)acrylate and toluene diisocyanate adduct of β -hydroxyethyl (meth)acrylate; and

a (meth)acrylic acid alkyl ester selected from the group consisting of methyl(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

4. The negative photoresist composition for spinless (slit) coating according to claim 1, wherein the silicon compound containing epoxy or amine group comprises at least one selected from the group consisting of (3-glycidoxypropyl)trimethoxysilane, (3- glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane,

(3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,

2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and aminopropyltrimethoxysilane.

5. The negative photoresist composition for spinless (slit) coating according to claim 1, wherein the solvent comprises at least one selected from the group consisting of ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethylethyl ether, methylmethoxy propionate, ethylethoxy propionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methylcellosolvacetate, ethylcellosolvacetate, diethylene glycol methylacetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N,N-dimethylacetamide (DMAc),

N-methyl-2-pyrrolidone (NMP), y -butyrolactone, diethyl ether, ethylene glycol

dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, isopropanol, methylcellosolve, ethylcellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, and octane.

6. The negative photoresist composition for spinless (slit) coating according to claim 1, wherein the fluorine-based or silicon-based surfactant resin is selected from the group consisting of Megaface F142D, F172, F-172D, F177P, R-08, F-470, F-471,

F-475(manufactured by Dainippon Ink & Chemicals), FC-170C, FC-430, FC-431(manufactured by Sumotomo 3M co., Ltd.), BYK 306, 307, 310, 331,333

(manufactured by BYK-Chemie), and their mixture.