KR101949589B1 - Chemically-amplified Binder Resin and Positive type Photosensitive Organic Insulation layer Composition including the same - Google Patents

Abstract

The present invention relates to a chemically amplified type binder resin capable of forming a resist pattern having high resolution and high transparency as well as high sensitivity in the formation of an organic insulating film of a display material such as a liquid crystal display device or an organic light emitting device (OLED) And a positive photosensitive organic insulating film composition containing the same, wherein the specific structure having a high refractive index includes a resin whose solubility in alkali is increased by an acid.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified binder resin and a positive photosensitive high-

The present invention relates to a chemically amplified binder resin and a positive photosensitive high-refractive-index organic insulating film composition containing the same, and more particularly to a positive photosensitive organic insulating film composition used for forming an organic insulating film included in an electronic device, To a chemical amplification type binder composition constituting the composition.

In a display device such as a thin film transistor (TFT) type liquid crystal display device, a protective film for protecting and insulating a thin film transistor (TFT) circuit is formed.

Conventionally, an inorganic material such as silicon nitride (SiOx or SiNx) has been used as the protective film. However, when a protective layer is formed using an inorganic material, the dielectric constant of the protective layer is relatively high, which makes it difficult to increase the open area ratio. Furthermore, when the vacuum evaporation process for forming the protective film is performed, the process cost and the process time are excessively high.

In order to overcome the above-mentioned problem, studies have been made on a protective film using a liquid organic insulating material having a relatively low dielectric constant and capable of a coating process. Hereinafter, a protective film using an organic insulating material is referred to as an organic insulating film.

The organic insulating layer may be provided with a photosensitive function on the insulating layer itself, so that a separate additional process for forming a fine pattern for providing interconnecting paths between circuits may be omitted. That is, after forming a photoresist film on a protective film made of a conventional inorganic material, an exposure process is required for the photoresist film, but it is not necessary to form a separate photoresist film for the organic insulating film. Therefore, there is an effect of higher productivity and cost reduction.

As the organic insulating material constituting such an organic insulating film, a photosensitive resin which is a macromolecule compound which is chemically reacted by light or electron beam to change its solubility to a specific solvent is generally used.

In addition, for micro-processing for forming a circuit pattern, a polarity change or cross-linking reaction of the polymer may occur due to a photoreaction with respect to a substance constituting the organic insulating film. Particularly, the organic insulating material constituting the organic insulating film utilizes the property of change in solubility in a developer such as an aqueous alkali solution after exposure.

The organic insulating material constituting the organic insulating film is classified into a positive type and a negative type depending on the solubility of the photosensitive portion in development. In the positive type photoresist, the exposed portion is dissolved by the developing solution due to the change in polarity, and the exposed portion is dissolved in the developing solution through the crosslinking reaction and the unexposed portion is dissolved to form the pattern.

The negative type organic insulating film is disadvantageous in that foreign matters are generated when mixed with an alkali developing solution which is widely used in existing mass production processes.

On the other hand, the positive type organic insulating film is not only advantageous from the viewpoint of work environment because there is no problem in the compatibility of the developer, but also has the advantage that the resolution is improved as the swelling phenomenon of the portion not exposed to ultraviolet rays is theoretically suppressed. Further, since the organic insulating film can be easily removed by using the removing liquid after forming the organic insulating film on the substrate, the substrate recovery and reusability can be significantly improved by removing the organic insulating film in the event of a defect.

In recent years, as a representative binder resin contained in the composition of the positive-type organic insulating film, a composition obtained by mixing an acrylic polymer resin with a quinonediazide photoactive compound (PAC) (photoactive compound) is used. Particularly, since a high aperture ratio can be realized, various high-brightness devices having an organic insulating film widely applied are being developed.

However, the conventional positive type organic insulating film can not sufficiently satisfy the sensitivity problem, and has a limitation in resolution to cope with miniaturization for higher integration.

Recently, in order to solve the sensitivity problem of a positive organic insulating film including a PAC (Photo Active Compound), a protective agent of a polymer binder is removed through an acid catalysis reaction using an acid generated through exposed light, A chemically amplified positive organic insulating film for solubilizing a developing solution has been introduced (Korean Patent Registration No. 0964773).

However, since the conventional organic insulating film has a relatively low refractive index, refractive index matching between the organic insulating film and its upper and lower layers is not performed, resulting in a decrease in visibility (brightness). In order to solve this problem, there is a problem that the power consumption of the display device must be increased. Accordingly, there is a demand for a high-refractive-index organic insulating film that minimizes refraction and diffuse reflection of light adjacent to the display device by matching the refractive index between the constituent elements of the display device for improving the visibility (brightness) of the display device and reducing power consumption .

An object of the present invention is to provide a chemical amplification type binder resin capable of implementing chemical amplification using a photoacid generator.

Another object of the present invention is to provide a positive photosensitive high refractive index organic insulating film composition which can realize improved sensitivity and miniaturization by using the chemically amplified binder resin, and has a relatively high refractive index.

The present invention provides a chemically amplified binder resin comprising a repeating unit represented by the following general formula (1).

Formula 1

또는

이며, R₂ 및 R₃은 탄소수 1 내지 20의 알킬기, 아릴기, 아랄킬기 및 사이클로알킬기 중 하나이다.상기 식1에서 R₄ 및 R₄'는 각각 탄소수 1내지 20인 헤테로 원소를 포함하거나 포함하지 않는 알킬기, 탄소수 6내지 20인 헤테로 원소를 포함하거나 포함하지 않는 아릴기, 또는 -RC(=O)R' 치환기이며, R₅는 탄소수 1 내지 20인 헤테로 원소를 포함하거나 포함하지 않는 4가의 방향족 또는 지환족(cycloaliphatic) 이고, A는 하기 화학식 1-1 내지 1-4로 표시되는 치환기이며, n은 1내지 6인 정수이고, p는 1내지 30의 정수이다.Wherein R < ₁ >

or

And R ₂ and R ₃ are each an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 20 carbon atoms. In the formula 1, R ₄ and R ₄ 'each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Or an -OR (= O) R 'substituent, and R < ₅ > is a tetravalent aromatic group containing or not containing a heteroatom of 1 to 20 carbon atoms A is a substituent represented by the following general formula (1-1) to (1-4), n is an integer of 1 to 6, and p is an integer of 1 to 30.

(1-1)

1-2

1-3

Formula 1-4

In the general formulas 1-1 to 1-4, R ₆ and R ₆ 'each represent a hydrogen atom, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) Halogen group, and X represents O, S or Se.

The chemical amplification type binder resin according to the embodiments of the present invention can realize chemical amplification using a photoacid generator.

The positive photosensitive organic insulating film composition according to embodiments of the present invention can realize improved sensitivity and miniaturization using the binder resin, and can have a relatively high refractive index.

FIG. 1 is a photograph of a hole pattern formed in an organic insulating film using the positive photosensitive organic insulating film composition according to Example 1. FIG.
2 is a photograph of a hole pattern formed by the resin composition according to the comparative example.

Embodiments of the present invention will now be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing. In the accompanying drawings, the dimensions of the structures are enlarged to illustrate the present invention, and are actually shown in a smaller scale than the actual dimensions in order to understand the schematic structure.

Also, the terms first and second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Chemically amplified binder resin

The chemical amplification type binder resin comprises a repeating unit represented by the following formula (1).

Formula 1

또는

이며, R₂ 및 R₃은 탄소수 1 내지 20의 알킬기, 아릴기, 아랄킬기 및 사이클로알킬기 중 하나이다.Wherein R < ₁ >

or

And R ₂ and R ₃ are any of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms.

In the formula 1, R ₄ and R ₄ 'each represent an alkyl group with or without a heteroatom of 1 to 20 carbon atoms, an aryl group with or without a heteroatom of 6 to 20 carbon atoms, or -RC (═O) R 'substituent, R ₅ is a tetravalent aromatic or aliphatic cycloaliphatic with or without a heteroatom of 1 to 20 carbon atoms, A is a substituent represented by the following formulas 1-1 to 1-4, n Is an integer of 1 to 6, and p is an integer of 1 to 30.

(1-1)

1-2

1-3

Formula 1-4

In Formula 1-1 or 1-4, R ₆ and R ₆ 'each represent hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) Halogen group, and X represents O, S or Se.

The chemical amplification type binder resin according to an embodiment of the present invention may have an average molecular weight ranging from 500 to 50,000. Here, the average molecular weight can be adjusted according to the repetition number of repeating units.

The chemical amplification type binder resin according to one embodiment of the present invention may have a degree of dispersion ranging from 1.0 to 5.0.

또는

R₁이 결합함에 따라, 화학증폭형 바인더 수지에 광산발생제를 포함하는 유기 절연막이 형성될 경우, 화학 증폭 특성이 개선될 수 있다. The chemical amplification type binder resin according to one embodiment of the present invention includes

or

When R ₁ is bonded, the chemical amplification characteristics can be improved when an organic insulating film containing a photoacid generator is formed on the chemically amplified binder resin.

Therefore, when exposed to light such as ultraviolet light in the exposure process for the organic insulating film, the exposed region is deprotected at a very high rate in a chemical amplification manner due to the action of an acid generated by the photoacid generator to increase the solubility, The non-exposed region exhibits dissolution inhibiting ability, and the contrast and resolution of the organic insulating film composition can be increased to form a fine circuit pattern.

The chemical amplification type binder resin corresponds to a photosensitive polymer resin having a high refractive index. Therefore, the organic insulating film including the chemically amplified binder resin may have an increased refractive index.

Positive photosensitive high-refractive-index organic insulating film composition

The positive photosensitive organic insulating film composition according to embodiments of the present invention includes a chemical amplification type binder water support, a photo acid generator, and an organic solvent.

1. Chemically amplified binder resin

Since the chemical amplification type binder resin has been described above, a detailed description thereof will be omitted.

2. Photo acid generator

The photoacid generator is a compound which generates an acid by irradiation with an actinic ray or radiation. The photoacid generator may be at least one selected from the group consisting of a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, A sultonate-based compound and a triazine-based compound may be used singly or two or more of them may be used in combination. Any material other than the above-described photoacid generator may be used as long as the photoacid generator does not adversely affect the film formation. However, the photoacid generator may have appropriate light absorption at a wavelength of 250 nm to 400 nm and maintain transparency of the organic insulating material at a visible light range of 400 nm or more It is preferable to use a substance.

Preferably, photoacid generators represented by the following formula (3) or (4) can be used.

(3)

Formula 4

According to one embodiment of the present invention, it is preferable that the photoacid generator comprises 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the chemical amplification type binder resin. When the content of the photoacid generator is less than 0.1 part by weight, acid generation is difficult. When the amount is more than 10 parts by weight, there is a fear of precipitation due to a decrease in solubility in the composition.

3. Organic solvent

The organic solvent is not particularly limited as long as it can dissolve the polymer in an organic solvent such as acetate, ether, glycol, ketone, alcohol, or carbonate used in a general photopolymerizable composition. Examples of the solvent include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, N, N-dimethylacetamide , N-methylpyrrolidone, N-methylcaprolactam, and the like, or a mixture of two or more thereof.

The content of the organic solvent is 20 to 95 parts by weight, preferably 30 to 90 parts by weight based on 100 parts by weight of the total composition. When the content of the solvent is less than 20 parts by weight, it is difficult to form a thin film by the conventional coating method. When the amount of the solvent is more than 95 parts by weight, a thin film having a desired thickness can not be obtained after coating.

4. Additives

The positive photosensitive organic insulation film composition according to the present invention may further include additives. Examples of additives include heat stabilizers, heat crosslinking agents, photocuring accelerators, surfactants, and base quenchers. If necessary, the above-mentioned additives may be used alone or in combination.

Among the additives that are typically included among the above additives, the adhesion promoting agent acts to improve the adhesion with the substrate. The adhesive enhancer includes, for example, a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group. Specifically, the adhesive enhancer may be at least one member selected from the group consisting of trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The content of the adhesion promoting agent is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the chemically amplified binder resin.

The surfactant acts to improve coatability, coatability, uniformity and stain removal on the substrate. As the surfactant, one or more selected from the group consisting of a fluorine-based surfactant, a silicon-based surfactant and a nonionic surfactant may be used in combination. The content of the surfactant is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the binder resin.

Monomer Manufacturing example

Bis (methylene)) bis (oxirane) Synthesis of 2,2 '- (((9H-fluorene-9,9-diyl) bis (4,1-

Step A: After setting the reflux condenser and thermometer on the 3-neck flask, 42.5 g of 9,9-bisphenolfluorene was added and 220 mL of 2- (chloromethyl) oxirane was injected and injected. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90 캜 while stirring was started. After confirming that the unreacted content was less than 0.3%, it was distilled under reduced pressure.

Step B: After lowering the temperature to 30 ° C, dichloromethane was injected and NaOH was slowly added. The product was confirmed to be 96% or more by a high performance liquid chromatography (HPLC) method, and 5% HCl was added dropwise to terminate the reaction. The reaction product was extracted and layered, and the organic layer was washed with water and neutralized. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and methanol was added to the solution while the temperature was raised to 40 ° C. The solution temperature was lowered and stirred. The resulting solid was filtered and vacuum-dried at room temperature to obtain 52.7 g (yield 94%) of a white solid powder, which was confirmed by 1H NMR.

2H NMR (CDCl3): 7.75 (2H), 7.36-7.25 (6H), 7.09 (4H) ).

Step 2: 3,3 '- (((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis

Synthesis of bis (1- (phenylthio) propan-2-ol) (BTCP)

A reflux condenser and a thermometer were set in a 3-neck flask, and then a first-stage reaction product (1000 g), 524 g of thiophenol and 617 g of ethanol were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC) method, the reaction was terminated. After completion of the reaction, the ethanol was distilled off under reduced pressure. The organics were dissolved in dichloromethane, washed with water and then dichloromethane was removed by distillation under reduced pressure. The concentrated organic material was dissolved in ethyl acetate, ether solvent was added dropwise, and the mixture was stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield: 64%) of pale yellow oil. Its structure was confirmed by 1H NMR.

2H NMR (CDCl3): 7.82 (2H), 7.38-6.72 (2H), 6.51 (4H), 4.00 (2H), 3.97 ).

Monomer Synthesis 2  To 4

Synthesis was carried out in the same manner as in the above-mentioned monomer synthesis example 1, except that 9,9-bisphenolfluorene was replaced with a monomer having the structure shown in Table 1 below.

division Fluorene derivative monomer Weight (g) Monomer Production Example 2

54.6 Monomer Preparation Example 3

44.2 Monomer Production Example 4

44.4

Preparation of spare binder

Step 3: BTCP / BPDA prebinder manufacturing example 1

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 31.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise at 115 DEG C, and the mixture was stirred at 115 DEG C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, followed by further stirring for 2 hours, and the reaction was terminated. After cooling, a binder solution having a weight average molecular weight of 3,500 g / mol was obtained.

Preparation of spare binders 2 to 4

The preparation was carried out in the same manner as in Preparation of Preparative Binder 1, except that BTCP was replaced with a monomer having the structure shown in Table 2 below.

division The second stage fluorene derivative monomer Weight (g) Spare Binder Example 2

200 Spare Binder Example 3

200 Spare Binder Example 4

200

Chemically amplified binder resin synthesis

Step 4: Synthesis of chemically amplified binder resin

Synthesis Example 1

상기 3단계에서 제조된 예비바인더1의 Polymer 30g에 프로필렌글리콜모노메틸에테르아세테이트 25g을 가해 용해한 후, 인산0.013g, 3,4-Dihydro-2H-pyran 1.18g을 혼합하고 상온에서 24시간 반응시켜 수지를 얻었다.

25 g of propylene glycol monomethyl ether acetate was added to 30 g of the polymer of the preliminary binder 1 prepared in the above step 3, and then 0.013 g of phosphoric acid and 1.18 g of 3,4-Dihydro-2H-pyran were mixed and reacted at room temperature for 24 hours, .

The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 2

 25 g of propylene glycol monomethyl ether acetate was added to 30 g of the BTCP polymer of the preliminary binder 1 prepared in step 3, and 0.013 g of phosphoric acid and 1.00 g of ethyl vinyl ether were mixed and reacted at room temperature for 24 hours to obtain a resin. The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 3

delete

25 g of propylene glycol monomethyl ether acetate was added to 30 g of the BTCP polymer of the preliminary binder 1 prepared in the above step 3, and 0.013 g of phosphoric acid and 1.36 g of n-butyl vinyl ether were mixed and reacted at room temperature for 24 hours to obtain a resin. The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 4

25 g of propylene glycol monomethyl ether acetate was added to 30 g of the polymer of the preliminary binder 2 prepared in the above step 3 and 0.013 g of phosphoric acid and 1.13 g of 4-Dihydro-2H-pyran were mixed and reacted at room temperature for 24 hours to prepare a resin . The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 5

25 g of propylene glycol monomethyl ether acetate was added to 30 g of the polymer of the preliminary binder 3 prepared in the above step 3 and 0.013 g of phosphoric acid and 1.13 g of 4-Dihydro-2H-pyran were mixed and reacted at room temperature for 24 hours, . The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 6

상기 3단계에서 제조된 예비 바인더4의 Polymer 30g에 프로필렌글리콜모노메틸에테르아세테이트 25g을 가해 용해한 후, 인산0.013g, ,4-Dihydro-2H-pyran 1.19g 을 혼합하고 상온에서 24시간 반응시켜 수지를 얻었다. 상기 생성물은 IR에서 카르복실기 및 알릴기로부터 유래하는 흡수 피크의 변화를 통해 반응이 진행되었음을 확인하였다.

25 g of propylene glycol monomethyl ether acetate was added to 30 g of the polymer of the preliminary binder 4 prepared in the above step 3 and 0.013 g of phosphoric acid and 1.19 g of 4-Dihydro-2H-pyran were mixed and reacted at room temperature for 24 hours, . The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Positive Photosensitive Organic Insulating Film Composition (Examples 1 to 6 and Comparative Example)

Example 1

35 g of the chemically amplified binder resin prepared in Synthesis Example 1 and 0.08 g of 1,3-dioxo-1H-benzo [de] isoquinolin-2 (3H) -yl trifluoromethanesulfonate photoacid generator (Formula 2) were added to the organic solvent PGMEA And 0.03 g of a surfactant (BYK333) and 0.02 g of an adhesive preparation (KBM303) were added to the solution and mixed. Thus, a positive photosensitive organic insulating film composition was prepared.

Example 2

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 2 was used.

Example 3

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 3 was used.

Example 4

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 4 was used.

Example 5

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 5 was used.

Example 6

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 6 was used.

[Comparative Example]

35.5 g of a novolac resin and 10.5 g of a photoactive compound (PAC) compound containing a naphthoquinone diazide group were dissolved in an amount of 35 parts by weight based on the organic solvent PGMEA. To this solution, 0.03 g of a surfactant (BYK333) 0.02 g were added and mixed.

[Property evaluation]

Each of the above positive photosensitive organic insulating film compositions obtained in Examples 1 to 3 and Comparative Examples was applied to a spin coater at 800 to 900 rpm for 15 seconds and then dried on a hot plate at 90 캜 for 100 seconds. Using a predetermined mask, the resist film was exposed as a light source using an ultra-high pressure mercury lamp, and then spin-developed in a TMAH 2.38% developer at 25 DEG C for 60 seconds and then washed with water. After washing with water and drying, it was baked at 230 ° C for 40 minutes to obtain a pattern. The following evaluation was made on the obtained pattern.

(1) Sensitivity evaluation

Each of the thus formed positive photosensitive organic insulating film compositions was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Incorporated) with a spin coater and dried at 90 degrees for 1 minute with a hot plate. After drying, an organic insulating film was obtained by measuring with a contact-type film thickness meter (KLA-Tencor, α-step 500). Next, this sample was exposed through a mask with a high-pressure mercury lamp. Thereafter, the resist pattern was spray-developed with a concentration of TMAH 2.38% developer to obtain a resist pattern. (MJ / sqcm) capable of forming the same dimensions as the mask pattern of 20 microns. That is, a resist having a small exposure dose shows high sensitivity because an image can be formed even with a small light energy.

(2) Residual film ratio after development

In the sensitivity evaluation process, the evaluation of the residual film ratio can be performed by measuring the pattern thickness after development.

(3) Transmittance

The composition was spin-coated on a glass substrate to form the same thickness of 3 microns, and then subjected to front exposure at 100 mJ and post-baking at 240 degrees and 40 minutes. Using a UV-spectrometer at each step, The transmittance was measured.

(4) taper angle

In the above evaluation, the pattern substrate on which the sensitivity of the same dimension as that of the 20 micron mast pattern was formed was subjected to post-baking at 240 degrees for 40 minutes, and then the patter angle of the pattern was measured through an electron microscope.

(5) Adhesion

According to the test method of JIS D 0202, a crosscut was formed in a lattice shape on a coated film heated at 240 캜 for 40 minutes after exposure and then subjected to a peeling test by cellophane take, and the lattice peeling state was observed and evaluated. &Amp; cir & ≤ & cir &

(6) Refractive index

The composition was spin-coated on a glass substrate to form the same thickness of 3 microns, and post-baked at 240 degrees for 40 minutes. The refractive index was measured at a wavelength of 632 nm using a refractive index meter.

The results of the results of sensitivity, residual film ratio and adhesion are shown in Table 1 below.

Results of physical property evaluation Example Polymer compound Sensitivity (mJ) Remaining film ratio after development (%) Residual film ratio after post-curing (%) Adhesiveness One Synthesis Example 1 60 97 94 ○ 2 Synthesis Example 2 30 96 95 ○ 3 Synthesis Example 3 100 99 97 ○ 4 Synthesis Example 4 110 99 94 ○ 5 Synthesis Example 5 60 96 93 ○ 6 Synthesis Example 6 60 97 93 ○ Comparative Example Novolac resin 120 95 91 ×

In order to confirm the heat resistance, the results of the measurement of the toughness angle and the measurement results of the refractive index by the process steps are shown in Table 2 below.

Taeper angle, transmittance and refractive index Example Polymer compound TaePeugak After coating
Permeability (%) After development
Permeability (%) Post curing
Post-permeability (%) Refractive index
(@ 633 nm) One Synthesis Example 1 58 97.4 97.3 97.6 1.648 2 Synthesis Example 2 65 98.3 97.5 98.2 1.642 3 Synthesis Example 3 60 98.1 98.2 97.9 1.643 4 Synthesis Example 4 58 96.6 96.5 96.1 1.651 5 Synthesis Example 5 57 98.2 98.7 98.1 1.664 6 Synthesis Example 6 56 98.3 98.2 98.3 1.663 Comparative Example Novolac resin 42 92.8 91.2 88.7 1.544

From the results shown in Tables 1 and 2, it can be seen that according to the positive type high sensitive organic insulating film composition of the present invention, excellent sensitivity and excellent heat resistance can be achieved, thereby controlling the taper angle and gas emission, It is possible to provide a photoresist for an insulating film which is excellent and has a high transmittance and a high refractive index.

FIG. 1 is a photograph of a hole pattern formed in an organic insulating film using the positive photosensitive organic insulating film composition according to Example 1. FIG.

2 is a photograph of a hole pattern formed by the resin composition according to the comparative example.

Referring to FIGS. 1 and 2, it can be seen that the inclination angle of the hole pattern formed by the composition according to Example 1 is closer to vertical than the comparative example. Therefore, it can be confirmed that fine patterning can be performed on the organic insulating film using the composition according to the first embodiment.

Claims (11)

delete delete delete A chemical amplification type binder resin comprising a repeating unit represented by the following formula (2).
(2)

Wherein R < ₁ >

or

And R ₂ and R ₃ are any of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms. A chemical amplification type binder resin according to claim 4;
Photoacid generators; And
And the remaining organic solvent. The positive photosensitive organic insulating film composition according to claim 5, wherein the photoacid generator has a composition ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. The photoacid generator according to claim 5, wherein the photoacid generator is at least one selected from the group consisting of a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, A nitrobenzylsulfonate-based compound, and a triazine-based compound. The positive photosensitive organic insulating film composition according to claim 7, wherein the photoacid generator is represented by the following formula (3) or (4).
(3)

Formula 4

6. The positive photosensitive organic insulating film composition according to claim 5, wherein the organic solvent comprises at least one of acetate, ether, glycol, ketone, alcohol, and carbonate. delete The positive photosensitive organic insulating film composition according to claim 5, wherein the positive photosensitive organic insulating film composition has a light refractive index in the range of 1.64 to 1.66 for light having a wavelength of 633 nm.

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