WO2004107053A1

WO2004107053A1 - Positive photoresist composition for spinless (slit) coating

Info

Publication number: WO2004107053A1
Application number: PCT/KR2004/001301
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: TWI266952B; TWI274962B; KR20040104053A; WO2004107052A1; KR100579832B1; TW200428152A; TW200428140A

Abstract

A positive photoresist composition for spinless (slit) coating is disclosed. The positive photoresist composition includes 5 ~ 50 parts by weight of an acrylic or novolac binder resin, 0.1 ~ 50 parts by weight of a photoactive compound, 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. A solvent is added to the composition so that viscosity becomes 2~20 cps. The positive 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

POSITIVE 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 positive 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 positive 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 positive

photoresist composition comprising: 5 ~ 50 parts by weight of an acrylic or novolac binder resin; 0.1 ~ 50 parts by weight of a photoactive compound, 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 more detail.

The positive photoresist composition for spinless (slit) coating of the present invention comprises 5 ~ 50 parts by weight of an acrylic or novolac binder resin. As for the acrylic binder resin, any conventional acrylic binder resin for a positive 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--RR2₂--^s^ \ (K)

T*

CH₂=C-CO -N-Rj X- X. (X)

^C-CO-N-rV ^^-QH (ffl)

_(χvm)

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, 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

In the general formula 2, 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, dicyclopentenylethyloxy methacrylate, and so on, B is selected from the group consisting of glycidyl methacrylate, hydroxyethyl, dimethylaminomethacrylate, 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 positive 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 copolymer, 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.

As for a novolac resin, any well-known novolac resin may be used, which can be synthesized by the means described in "Chemistry and Application of Phenolic Resins, Knop A and Scheib, W.; Springer Verlag, New York, 1979 Chapter 4".

Moreover, the photoresist composition of the present invention comprises 0.1 ~ 50 parts by weight of a photoactive compound. As for the photoactive compound, any conventional photoactive compound may be used, such as l,2-diazonaphthoquinone-4- or 5-sulfonates of 2,2',3,4,4'-pentahydroxybenzophenone,

2,2',3,4,4',5-hexahydroxybenzophenone, 2,2',3,4,4'-pentahydroxydiphenylpropane,

2,2',3,4,4',5-hexahydroxydiphenylpropane, 2,3,4-trihydroxybenzophenone,

2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenyl hexyl ketone,

2,4,4 '-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,2',4,4'-tetrahdroxybenzophenone,

2,3,4,4'-tetrahydroxybenzophenone, and so on.

A silicon compound containing epoxy or amine group in the positive 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 positive 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 positive photoresist composition

if necessary.

Preferably, a solvent is added so that the positive 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 ~ 20

A positive photoresist composition was prepared according to the components

and contents of table 1 as below.

Cresol-formaldehyde novolac resin : 10wt% l,2-Diazonaphthoquinone-5-sulfonate of 2,2,5,5 '-tetrahydroxybenzophenone : 2wt% (3-glycidoxypropyl)trimethoxysilane : 0.05wt% Fluorine-based surfactant : 0.03wt%

Solvent : residual quantity

Megaface F142D (manufactured by Dainippon Ink & Chemicals co.) was used as the fluorine-based surfactant.

The viscosity of the formed photoresist composition was about 4 cps.

Embodiments 21 ~ 39

A positive photoresist composition was prepared according to the components

and contents of table 2 as below.

Acrylic binder resin : 10wt%

l,2-Diazonaphthoquinone-5-sulfonate of 2,2,5,5 '-tetrahydroxybenzophenone :

2wt%

(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 ( LT ) having R_\ of methyl), was used.

Megaface F142D (manufactured by Dainippon Ink & Chemicals co.) was used

as the fluorine-based surfactant.

The viscosity of the formed photoresist composition was about 4 cps.

Embodiments 40 - 71 The positive photoresist composition was prepared in the same manner as in the embodiment 21, except that DMC was used as a solvent, and the kind and content of the surfactant were changed according to the table 3. The viscosity of the formed photoresist composition was about 4 cps.

The evaluations of the positive 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 to 3.

(1) Coating property

The positive 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 positive 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 positive 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

Table 3

INDUSTRIAL APPLICABILITY

As described above, the positive 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

become apparent to those skilled in the art from this detailed description.

Claims

WHAT IS CLAIMED;

1. A positive photoresist composition for spinless (slit) coating, comprising: 5 ~ 50 parts by weight of an acrylic or novolac binder resin; 0.1 ~ 50 parts by weight of a photoactive compound, 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 positive 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 Y is selected from the group consisting of compounds having the

structure of the following chemical formulas (I) to (XX);

R, OH ^ /

CHa==C-CO-0-Ra-CH— ^

OH (XVΠD

where Ri is hydrogen atom or methyl, R₂ is alkylene having 1 to 10 carbon atoms,

R₃ is hydrocarbon having 1 to 10 carbon atoms, Rt 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> ^ _^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 positive 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.

4. The positive 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), -butyrolactone, diethyl ether, ethylene glycol

heptane, and octane.

5. The positive 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.