WO2007051403A1

WO2007051403A1 - An edge bead remover composition

Info

Publication number: WO2007051403A1
Application number: PCT/CN2006/002900
Authority: WO
Inventors: Qiming Jin; Xuegang Chen; Junqing Dong; Qing Gong; Zhiqi He
Original assignee: Byd Company Limited
Priority date: 2005-11-03
Filing date: 2006-10-30
Publication date: 2007-05-10
Also published as: CN1958763A; CN100526448C

Abstract

An edge bead remover composition comprising a basic compound, a surfactant, and a solvent, wherein said surfactant is a Gemini type surfactant represented by formula (I): in the formula (I), R1, R2, R3, R4, R5, R1’, R2’, R3’, R4’ and R5’ being independently selected from hydrogen, alkyl, aryl, aralkyl, and halogen, R6 being an alkylene having 2 to 6 carbon atoms, and n is an integer of 6 to 23. The edge bead remover composition of the present invention has excellent removing performance, defoaming performance, dispersion stability, and has no residue left on the substrate.

Description

AN EDGE BEAD REMOVER COMPOSITION

FIELD OF THE INVENTION

The present invention relates to an edge bead remover composition, and in particular relates to an edge bead remover composition for removing the edge bead after photoresist being coated.

BACKGROUND

Photoresist is widely used in the formation of the wiring pattern of the integrated circuit, printed circuit board, colored liquid crystal display devices or color filter. The formation of the wiring pattern typically includes: a pigment dispersion, a solvent, an actinic ray- sensitive resin, and suitable additives are firstly mixed to prepare a photoresist; the photoresist is coated on a base plate by a coating method such as dye method, printing method, electro-deposition method, and pigment dispersing method, then the base plate coated with the photoresist is preroasted; after having been exposed to the light using a photomask, the photoresist on the unexposed region is washed away with the edge bead remover composition.

After the photoresist was coated on the base plate, the edge and the back of the base plate will stuck to some photoresist, which will easily be broken during the preroasted and peel off from the base plate during portage and produce some debris, which will affect the subsequent process. For example, the photoresist will stuck to the photo-mask and result in the frequency of removing the photoresist increase and decrease the productivity of the final products. Therefore, it is necessary to remove the edge bead of the base plate before the process of the developing. According to the edge bead removing techniques of the prior art, after the potoresist is coated, preroasted, although the undesired edge bead can be removed by the conventional edge bead remover composition, particles or undissolved substance residues would be generated while removing, and the organic solvent including glycol and the derivatives thereof, ketones such as acetone, methyl ethyl ketone, and esters such as methyl acrylate comprised in the composition will pollute the enviroment (Japanese Unexamined Patent Publication No. Hei 63-69563, 01-188361, and 01-188358). US Patent No. 6503694 discloses a method of using KOH aqueous solution comprising surfactants as an edge bead remover to remove the photoresist materials stuck to the edge of the base plate. The surfactant mainly used is poly glycols derivatives and this basic aqueous composition possesses the effect of being friendly to environment. However, this edge bead composition is poor in the cleaning performance, defoaming performance and the dispersion stability of the photoresist and has residue, hence it is not ideal for use. When air enters the edge bead remover composition during removing edge bead, the edge bead remover composition would foam and the foam would accumulate in the edge bead remover composition if it is not fully removed. The foam generated in the edge bead remover composition is hard to remove, along with the increase of the photoresist dissolved or dispersed in the edge bead remover composition. The foam hinders the edge bead remover composition from contacting with the photoresist, and thereby it is difficult to fully remove the edge bead. Besides, the spraying method which is now commonly used would cause foaming in the edge bead remover composition more easily, because the edge bead remover composition is fully sprayed onto the base plate. In order to suppress the foaming of the edge bead remover composition, a defoaming agent is generally added to the edge bead remover composition. For example, acetylene alcohol based surfactants (Japanese Unexamined Patent Publication No. Hei 04-51020), polyalkylene glycols and derivatives thereof(Japanese Unexamined Patent Publication No. Hei 07-128865, 08-10600, 08-87382, 09-172256, 10-319606, and 2001-222115), and higher fatty acid monoglycerides (Japanese Unexamined Patent Publication No. Hei 09-293964) are used as the defoaming agent of the edge bead remover composition. However, the prior defoaming agents in the edge bead remover composition would aggregate and form oily scum, which would stuck on the surface of the photoresist or the substrate, leading to the pollution of the substrate. Besides, although these defoaming agents possess some defoaming effect in the early stage of the use, the defoaming effect would rapidly drop along with the increase of the slushing agent dissolved or dispersed in the edge bead remover composition.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an edge bead remover composition which simultaneously possesses improved removing performance, defoaming performance and dispersion stability without adding the defoaming agents, to overcome the disadvantages of the prior edge bead remover composition that it is impossible to simultaneously improve the removing performance, defoaming performance, dispersion stability, and it is necessary to add defoaming agents to enhance the defoaming performance of the edge bead remover composition.

The inventor of the present invention has unexpectedly discovered that through the combination of a Gemini type surfactant represented by formula (III) with a basic substance, the removing performance could be greatly improved and the residues present in the edge bead remover composition during the removing could be greatly decreased or even completely eliminated, the defoaming performance and dispersion stability of the edge bead remover composition could be greatly improved simultaneously, and thus the comprehensive performance of the edge bead remover composition could be significantly improved.

The edge bead remover composition provided by the present invention comprises a basic substance, a surfactant, and a solvent, wherein said surfactant is a Gemini type surfactant represented by formula (I),

in the formula (I), Ri , R₂, R₃, R₄, R₅, Ri ^', R₂ ^', R₃ ^', R₄ ^' and R₅ ^' being independently selected from hydrogen, alkyl, aryl, aralkyl, and halogen, R₆ being an alkylene having 2 to 6 carbon atoms, and n is an integer of 6 to 23.

The edge bead remover composition provided by the present invention can attain greatly improved removing performance, greatly decrease or even completely eliminate the residues during the removing of the edge bead and attain excellent comprehensive performance (i.e. strong defoaming performance, no residue, and good dispersion stability) without additional defoaming agents due to the surprising and suitable combination of Gemini type surfactant with basic substances. No residue can be observed in the edge bead remover composition provided by the present invention even under a microscope with a magnification of 1000. When it is shaken, the height of the foam of the present edge bead remover composition is lowered from 1.5 cm of the prior edge bead remover composition to less than 0.5 cm, so the height of the foam is lowered by 67% or more. The dispersion stability is also greatly enhanced

DETAILED DESCRIPTION OFTHE PREFERRED EMBODIMENTS

The edge bead remover composition provided by the present invention comprises a basic substance, a surfactant, and a solvent, wherein said surfactant is a Gemini type surfactant represented by formula (I)₅

in the formula (I), Rj, R₂, R₃, R₄, R₅, Rj , R₂ , R₃ , R₄ and R₅ being independently selected from hydrogen, alkyl, aryl, aralkyl, and halogen, R₆ being an alkylene having 2 to 6 carbon atoms, and n is an integer of 6 to 23.

Referring to the surfactant, although the object of the present invention can be realized by any Gemini type surfactant, it is still preferred that in formula (I), at least two of R₁, R₂, R₃, R₄, Rs, R₁ ^', R₂ ^', R₃ , R₄ and R₅ are aryl or aralkyl,

namely, at least two Of R₁, R₂, R₃, R₄, R₅, Rj , R₂ , R₃ , R₄ and R₅ are aryl, at least two are aralkyl, or at least one is aryl and at least one is aralkyl. And the alkyl is preferably an alkyl having carbon atoms of 6 to 20 and more preferably an alkyl having carbon atoms of 8 to 14, the aryl is preferably an aryl having carbon atoms of 6 to 18 and more preferably an aryl having carbon atoms of 6 to 12, and the aralkyl is preferably an aralkyl having carbon atoms of 6 to 20 and more preferably an aralkyl having carbon atoms of 8 to 14. According to the edge bead remover composition provided by the present invention, the amount of said surfactant comprised in the edge bead remover composition is not specially limited. For example, based on the total amount of the edge bead remover composition, the amount of the Gemini type surfactant is generally 0.01-10.00% by weight, preferably 0.05-2.00% by weight, and more preferably 0.10-1.0% by weight.

The Gemini type surfactant represented by formula (I) according to the present invention includes but is not limited to the following compounds:

1) bis-(polyoxyethylene-3,5-diphenylethyl ethyl ether)-ethane with the following particular structure formula, denoted as Pj:

2) bis-(polyoxyethylene-3,5-diphenylethyl ethyl ether)-ethane with the following particular structure formula, denoted as P₂:

3) bis-(polyoxyethylene-3,5-diphenylethyl ethyl ether)-butane with the following particular structure formula, denoted as P₃:

4) bis-(polyoxyethylene-3,5-diphenylethyl ethyl ether)-butane with the following particular structure formula, denoted as P₄:

5) bis-(polyoxyethylene-3,5-diphenylethyl ethyl ether)-butane with the following particular structure formula, denoted as P₅:

The above Gemini type surfactants can be synthesized by the conventional processes, or purchased from, e.g., Xeogia Fluorine-silicon Chemical Co., Ltd.

The present invention has no special restriction on the kind or the amount of both said basic substance and solvent because the present invention only relates to the improvement of the surfactant in the edge bead remover composition. Said basic substance may be various known basic substances used in the edge bead remover composition of the prior art, and the content thereof in the composition may be conventional. For example, said basic substance may be organic basic compound selected from the group consisting of tetramethyl-ammonium hydroxide, 2-hydroxyl-trimethyl-ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoisopropylamine, diisopropylamine, and aminoethanol and/or inorganic compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium phosphate, sodium hydrophosphate, monosodium phosphate, potassium phosphate, potassium hydrophosphate, monopotassium phosphate, lithium phosphate, lithium silicate, potassium silicate, sodium silicate, lithium carbonate, potassium carbonate, sodium carbonate, lithium borate, and sodium borate. Based on the total amount of the edge bead remover composition, the amount of the above basic substance is generally 0.01-10.00% by weight, preferably 0.06-2.00% by weight, and more preferably 0.10-0.20% by weight.

The remaining of the edge bead remover composition is the solvent used as a dispersion medium, and the solvent may be an organic solvent or water. Trichloroethane and trichloromethane are typically used as the organic solvent. Because the organic solvent may do harm to the environment, hygiene, and safety, it is gradually replaced by water having low toxicity, incombustibility, easiness in management, convenience in the liquid waste treatment, and low cost. Therefore, said solvent in the present edge bead remover composition is preferably water.

The edge bead remover composition provided by the present invention is suitable for removing edge bead of various photoresists such as the positive and negative photoresist. The structure and composition of said photoresist have been known to the skilled in the art, e.g., the photoresist generally comprises an organic or inorganic pigment, an alkali-soluble base resin, a photosensitive monomer, a photoinitiator, and a solvent. Said alkali-soluble base resin may be selected from the thermoplastic phenol formaldehyde resin, the acrylate based resins, polymers of maleic anhydride or the semiester thereof, and polyhydroxybenzene, and is preferably the acrylate based resins containing (methyl) acrylate and/or (methyl) acrylic acid as maj or components .

The following examples will further describe the present invention. The concentrations in the examples of the present invention are expressed by weight percent except where otherwise noted.

Examples

Example 1

The surfactant consisting of 0.5 part by weight of P₁ and 1.0 part by weight of NaOH were added to 98.5 parts by weight of deioned water, and the resulting mixture were uniformly stirred at the ambient temperature to yield the edge bead remover composition Sl .

Examples 2-16

The procedure in Example 1 was repeated to respectively prepare edge bead remover compositions S2-16, except that the compositions of the edge bead remover compositions are as shown in Table 1. Comparative Examples 1-4

The procedure in Example 1 was repeated to respectively prepare edge bead remover compositions C 1-4, except that the surfactant in the edge bead remover compositions are polyoxy ethylene-3, 5 -bis(l -phenyl ethyl) phenyl ether, wherein the poly oxyethylene-3, 5 -bis(l -phenyl ethyl) phenyl ether with 9 oxy ethylene units is called as Bi for short, with the polyoxyethylene-3,5-bis(l-phenyl ethyl) phenyl ether with 12, 18 and 21 oxyethylene units are respectively called as B₂ ,B₃ and B₄ for short. The particular compositions of the edge bead remover compositions C 1-4 are shown in Table 1.

Table 1

Note: Ex. represents example and CE. represents comparative example. Removing edge bead with the edge bead remover compositions

Photoresist Fijifilm CB-B252 was coated on a glass base plate, and preroasted at 110 "C for 21 seconds to form the substrate coated with photoresist film thereon to be removed. The substrates thus prepared were respectively impregnated in the edge bead remover compositions S 1-16 and C 1-4 prepared in the above Examples 1-16 and Comparative Examples 1-4 for about 20 seconds, and then washed with deionized water. After being washed, the physical properties, namely the comprehensive performances of the edge bead remover compositions were evaluated by the following methods and the results are shown in Table 2.

The performances of the edge bead remover compositions were evaluated by the following methods:

1.Removing performance: the planeness of the photoresist layer edges on the glass base plates were observed using a length measuring machine, and evaluated as follows:

O: Good Δ: General x: Bad 2.Residues: the glass base plate was observed under a scanning electro microscope with a magnification of 1000 to determine whether there was residue or not, and evaluated as follows: O: No residue Δ: Small amount of residue x: Large amount of residue

3.Defoaming performance: 20 ml edge bead remover composition was placed in a 100 ml measuring cylinder, shaken by a vertical shaker with a frequency of 150 time/min for 30 min, and then standed for 1 hr. Then the height of the foam was measured and evaluated as follows: O: below 0.5 cm

Δ: 0.5-1.0 cm x: above 1.0 cm

4.Dispersion stability: 1 g photoresist was added to 200 ml edge bead remover composition and the mixture was filtered with a filter paper having a pore diameter of 5 μm after stirring. The filter paper was roasted at 100^°C until its weight did not change. The filter paper was weighed, and the variation in the weight of the filter paper before and after the filtering was calculated and evaluated as follows:

O: The variation in the weight is below 0.02 g

Δ: The variation in the weight is 0.02-0.04 g x: The variation in the weight is above 0.04 g

The particular operation of the above evaluation is known to the skilled in the art, so the unnecessary details were omitted.

Table 2

It can be seen from Table 2 that the edge bead remover composition of the present invention can possess excellent removing performance and good deforming performance, dispersion stability without additional defoaming agents. Furthermore, there are no residues left on the substrate. Compared with the edge bead remover composition of the prior solution, the comprehensive performance of the compositions provided by the above examples are all superior to the corresponding performances of the comparative examples.

Claims

1. An edge bead remover composition comprising a basic substance, a surfactant, and a solvent, wherein said surfactant is a Gemini type surfactant represented by formula (I),

(I) in the formula (I), Ri, R₂, R₃, R₄, R₅, Ri , R₂ , R₃ , R₄ and R₅ being independently selected from hydrogen, alkyl, aryl, aralkyl, and halogen, R₆ being an alkylene having 2 to 6 carbon atoms, and n being an integer of 6 to 23.

2. The edge bead remover composition according to claim 1, wherein at least two of Ri, R₂, R₃, R₄, R₅, R₁ , R₂ , R₃ , R₄ and R₅ are aryl and/or aralkyl.

3. The edge bead remover composition according to claim 1, wherein the amount of the Gemini type surfactant is 0.01-10.0% by weight based on the total amount of the edge bead remover composition.

4. The edge bead remover composition according to claim 3, wherein the amount of the Gemini type surfactant is 0.05-2.0% by weight based on the total amount of the edge bead remover composition.

5. The edge bead remover composition according to claim 4, wherein the amount of the Gemini type surfactant is 0.1-1.0% by weight based on the total amount of the edge bead remover composition.

6. The edge bead remover composition according to claim 1, wherein the amount of the basic substance is 0.01-10.0% by weight based on the total amount of the edge bead remover composition.

7. The edge bead remover composition according to claim 1, wherein the basic substance is an organic basic compound selected from the group consisting of tetramethyl ammonium hydroxide, 2-hydroxyl-trimethyl-ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoisopropylamine, diisopropylamine, and aminoethanol; and/or an inorganic basic compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium phosphate, sodium hydrophosphate, monosodium phosphate, potassium phosphate, potassium hydrophosphate, monopotassium phosphate, lithium phosphate, lithium silicate, potassium silicate, sodium silicate, lithium carbonate, potassium carbonate, sodium carbonate, lithium borate, and sodium borate; said solvent is water.