KR20020048674A - Photosensitive resin composition for overcoating CCD color filter and the CCD color filter - Google Patents

Abstract

PURPOSE: Provided are a photosensitive resin composition having improved chemical resistance and developing property without adding a separate epoxy resin, and a CCD color filter. CONSTITUTION: The composition comprises (1) 1-40 wt% of binder resin obtained by copolymerizing 9,9'-bis-(4-hydroxyphenyl)fluorene of formula 1, a compound of formula 2, and a compound of formula 3: CH2=CRCOOH with a molecular ratio of 1:2-4:2-8, which has a molecular weight of 3000-9000; (2) 1-20 wt% of photopolymerizable acrylated monomer; (3) 0.05-5 wt% of photopolymerization initiator; and (4) 40-80 wt% of solvent. The binder resin and photopolymerizable acrylated monomer are treated with an acid anhydride of formula 4. In the formulae, each of R, R1 and R2 represents hydrogen atom, an alkyl group, aryl group, phenyl group, benzyl group having C1-C10, or an ethoxy group having C1-C8, and X represents a halogen atom.

Description

Photosensitive resin composition for CCD color filter overcoat and its CCD color filter {Photosensitive resin composition for overcoating CCD color filter and the CCD color filter}

The present invention relates to a photosensitive resin composition for CCD color filter overcoat, and a CCD color filter thereof, and more particularly, to a photosensitive resin composition for CCD color filter overcoat comprising a cardo binder resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, and a solvent; And a protective film layer made of the composition.

A color liquid crystal display (CCD) is composed of tens or millions of photoelectric conversion elements and converts light into an electrical signal according to the amount of light received. These CCDs are used in digital input devices to enable recording of pre-digitized images as digital images, and the demand is exponentially used for various security devices and digital porters in line with the rapid development of the times. The situation is increasing.

In response to this, researches to improve conventional interless CCDs into progressive CCDs have been actively conducted, and in particular, the role of the photosensitive resin composition for color filter overcoat has emerged. The reason for this is that in the case of an interless CCD, the screen recognition system is a mixture of two types of A and B fields, whereas the recent progressive CCD is one recognition, so the resolution and transmittance of color are important factors. Because it works.

To date, research and development has been actively conducted on overcoat photosensitive resin compositions for liquid crystal display (LCD), plasma display (PDP) or fluorescent display tubes (VFD) used in office automation equipment, portable small televisions, and viewfinders of video cameras. Although various resin compositions have been put to practical use, little has been studied about the photosensitive resin composition for overcoat used for the production of CCD on G-line.

In order to show high transmittance and developability when the photosensitive resin composition is applied to the G-line, (1) the wavelength of the G-line must be well absorbed (436 nm), and (2) the proper flatness is maintained for constant transmission of light. (3) have sufficient hardness to prevent physical penetration into other materials, (4) have sufficient chemical resistance to acidic stripper, alkaline developer, solvent of alignment film coating composition, etc., and (5) visible light region. It should have a high transmittance at and (6) have good adhesion to the glass as a substrate as well as the pattern of the coloring composition.

In order to satisfy such conditions, Japanese Patent Application Laid-Open No. 60-216307 proposes a thermosetting resin composition composed of an epoxy resin and a polycarboxylic acid or anhydride thereof, and Japanese Patent Publication No. 63-131103 discloses a melamine compound and an epoxy. The thermosetting resin composition which consists of resin is proposed. However, the resin composition containing the epoxy resin as described above has a disadvantage in that it is difficult to obtain a uniform and precise film thickness because the viscosity increases over time, so that time can be properly processed.

In order to solve this problem, Japanese Patent Publication No. 57-42009, Japanese Patent Publication No. 60-244932, Japanese Patent Publication No. 59-7317, and Japanese Patent Publication No. 60-216307 have UV light which causes a curing reaction upon exposure. Cured photosensitive resin composition was proposed. However, there is a need for selective protective film coating in the process of manufacturing a variety of substrates using such a UV-curable photosensitive resin composition, and thus, a photosensitive resin composition that can be developed with an aqueous alkali solution is disclosed in Japanese Patent Application Laid-Open No. 3-126950, Japanese Patent. Proposed in publication 52-132091. However, due to insufficient chemical resistance, these resin compositions may have low flatness of the protective film or corrosion or peeling of the protective film due to a release agent other than a developer, an acid etching solution, a solvent of the alignment film coating composition, or the like.

As an alternative to this, Japanese Patent Laid-Open No. 7-3122 discloses a method for producing a photosensitive resin composition for overcoat using a cardo-based binder resin. In general, the cardo-based binder resin is highly sensitive and is not affected by oxygen, and is excellent in heat resistance, shrinkage resistance, transparency, and the like. However, since such photosensitive resin composition does not have a place to react with alkali developing aqueous solution in itself, developability is low and it is not developed well in many cases. In this regard, Japanese Patent Laid-Open No. 4-363311 seeks to improve developability by treating cardo-based binder resins with acid anhydrides to make alkali-soluble resins. However, even after treatment with acid anhydride, a considerable amount of undeveloped parts remain after development, which is due to components that are not easily dissolved in an aqueous alkali solution, and a representative one of such components is added to satisfy the chemical resistance of the photosensitive resin composition. Epoxy resin. Therefore, the development of a photosensitive resin composition with improved developability while maintaining chemical resistance is urgently required.

An object of the present invention is to solve such a problem of the prior art, by using a cardo-based binder resin of the appropriate molecular weight treated with an acid anhydride to meet the excellent chemical resistance and addition developability without adding an additional epoxy resin It is to provide this significantly improved photosensitive resin composition.

That is, one aspect of the present invention is (1) 1,9'-bis- (4-hydroxyphenyl) fluorene of the following formula (1), a compound of the formula (2) and a compound of the formula (3) is 1 mol: 2-4 Mole: 1.00-40.00% by weight of cardo-based binder resin having a molecular weight of 3000-9000, (2) 1.00-20.00% by weight of acrylic photopolymerizable monomer, (3) 0.05-5.00 weight of copolymerization copolymer In the photosensitive resin composition for CCD color filter overcoat containing 4% to 8% by weight (4) and (4) solvent, the cardo-based binder resin and the acrylic photopolymerizable monomer is a CCD characterized in that the acid anhydride of the following formula (4) Provided is a photosensitive resin composition for color filter overcoat.

(Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom)

CH ₂ = CRCOOH

(Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group, or an ethoxy group having 1 to 8 carbon atoms)

(Wherein R ₁ and R ₂ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, allyl groups, phenyl groups, benzyl groups or ethoxy groups having 1 to 8 carbon atoms)

According to another aspect of the present invention, the photosensitive resin composition is coated on a glass substrate for color filters so as to have a thickness of 0.5 to 10 μm by spin coating, roller coating, or spray coating method, and UV rays, electron beams or the like in a 190 to 450 nm region. The present invention provides a color filter for CCD comprising a protective film layer prepared by irradiating X-rays to form a pattern and treating the coating film on which the pattern is formed with an alkali developer to dissolve the unilluminated portion.

Hereinafter, the present invention will be described in more detail.

The photosensitive resin composition for CCD color filter overcoat of the present invention includes a cardo-based binder resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, and a solvent, which will be described in more detail below.

The cardo-based binder resin (hereinafter referred to as component (1)) used in the present invention is 9,9'-bis (4-hydroxyphenyl) fluorene of the formula (1), a compound of the formula (2) and a compound of the formula (3) It is a copolymer superposed | polymerized in the ratio of 1 mol: 2-4 mol: 2-8 mol, and molecular weight is 3000-9000.

[Formula 1]

[Formula 2]

(Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom)

[Formula 3]

CH ₂ = CRCOOH

(Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group, or an ethoxy group having 1 to 8 carbon atoms)

The content of the component (1) is preferably 1.00 ~ 40.00% by weight based on the total composition, it can not achieve the object of the present invention outside the above range.

In preparing the composition of the present invention, the component (1) is added after being made easy to dissolve in an alkaline developer by treating with an acid anhydride of the following formula (4).

[Formula 4]

(Wherein R ₁ and R ₂ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, allyl groups, phenyl groups, benzyl groups or ethoxy groups having 1 to 8 carbon atoms)

The acrylic photopolymerizable monomer (hereinafter referred to as component (2)) used in the present invention is a conventional acrylic photopolymerizable monomer, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate. , 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate Latex, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimetha Acrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate Sites, and the like 1,6-hexanediol dimethacrylate monomer.

The content of the component (2) is preferably 1.00 ~ 20.00% by weight based on the total composition, it can not achieve the object of the present invention outside the above range.

In the preparation of the composition of the present invention, the component (2) may be added after being made easy to be dissolved in an alkaline developer by treating with an acid anhydride of the formula (4) as in the component (1).

As the photopolymerization initiator (hereinafter referred to as component (3)) used in the present invention, it is preferable to use 3,3'-carbonylbis (7-diethylaminocoumarin) which exhibits strong absorbance at 449 nm, and activates photopolymerization more. If necessary, a triazine-based compound, trimethylolpropane triethacrylate, or the like can be used in combination.

The content of the component (3) is preferably 0.05 to 5.00% by weight based on the total composition, it can not achieve the object of the present invention outside the above range.

As the solvent (hereinafter referred to as component (4)) used in the present invention, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or mixtures thereof It is preferable to use.

The content of the component (4) is preferably 40.00 ~ 80.00% by weight based on the total composition.

In addition to the above components, various additives for ordinary photosensitive resin compositions such as surfactants, coupling agents, and the like can be added to the resin composition of the present invention as necessary without departing from the characteristics of the present invention.

Hereinafter, a color filter for CCD including a protective film layer made of the photosensitive resin composition of the present invention will be described in detail.

The photosensitive resin composition of this invention is apply | coated so that the thickness of a coating film may be set to 0.5-10 micrometers on the glass substrate for color filters by methods, such as spin coating, roller coating, or spray coating. After application, UV-rays, electron beams or X-rays in the region of 190 to 450 nm, preferably 200 to 450 nm are irradiated to form a pattern required for the color filter. After irradiation, the coating film is treated with a normal alkaline developer to dissolve the unilluminated portion, thereby completing the protective film layer required for the color filter.

The color filter of the present invention manufactured as described above can further improve crack resistance, solvent resistance, and the like through a post-process of reheating the image pattern or curing by active ray irradiation, as necessary.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example 1

After dissolving 0.1 g of photopolymerization initiator BC (Midori-Kagakusa) and 2.0 g of TAZ-110 (Midori-Kagakusa) in a mixed solvent of 50.0 g of propylene glycol monomethyl ether and 10.0 g of cyclohexanone, at room temperature for 2 hours. Stirred at. Then, the molar ratio of 10.0 g of the photopolymerizable monomer pentaerythritoltriacrylate and 9,9'-bis (4-hydroxyphenyl) fluorene: epichlorohydrin: acrylic acid is 1: 2: 2 and the molecular weight is 4000 Phosphorus cardo-based binder resin was added to the reaction mixture and stirred at room temperature for 2 hours, followed by adding 0.2 g of a rosin salt as a surfactant and further stirring at room temperature for 1 hour. After stirring was complete, impurities were removed by repeating filtration three times to obtain a photosensitive resin composition. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1 except for using a cardo-based binder resin having a molecular weight of 8000 and increasing BC from 0.1 g to 0.15 g. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Comparative Example 1

A photosensitive resin composition was manufactured in the same manner as in Example 1, except that a cardo-based binder resin having a molecular weight of 2000 was used. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the cardo-based binder resin of 12000 was used. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Comparative Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that a phenol novolac epoxy resin (EPPN-201; Nippon Kayaku) was used. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Comparative Example 4

A photosensitive resin composition was prepared in the same manner as in Example 1, except that an acrylate binder resin having a molar ratio of methyl methacrylate: methacrylic acid of 1: 1 and a molecular weight of 50000 was used. The physical properties of the resin composition thus obtained were evaluated, and the evaluation results are shown in Table 1 below.

Transmittance Flatness Developability Chemical resistance Example 1 ○ ○ ○ ○ Example 2 △ ○ ○ ○ Comparative Example 1 × △ ○ × Comparative Example 2 × ○ × ○ Comparative Example 3 × △ × × Comparative Example 4 × × ○ ×

[Property evaluation method]

* Transmittance

: A photosensitive resin composition was applied to a glass substrate having a thickness of 1 mm at a thickness of 0.8 μm, and dried at 80 ° C. for 1 minute in a hot air circulation drying furnace to form a coating film. After drying, the mixture was cooled to room temperature and further dried at 230 ° C. for 30 minutes in a hot air circulation drying furnace, and then the average transmittance in the visible light region (400-450 nm) was measured with a color analyzer (MCPD COLOR ANALYZER, Otsukasa). Measured.

○: 85% or more transmittance

△: transmittance of 80 to 85%

X: transmittance 80% or less

* Flatness

: A photosensitive resin composition was applied on a glass substrate having a chromium coated thickness of 1 mm to a thickness of 1 to 2 μm, and dried at 80 ° C. for 1 minute in a hot air circulation drying furnace to form a coating film. The photomask was placed on the coating film and exposed to light using a high pressure mercury lamp having a wavelength of 436 nm, followed by development for 80 seconds at 30 ° C. and 1 atmosphere using a 1% aqueous KOH solution. After development, the film was dried at 230 ° C. for 30 minutes in a hot air circulation drying furnace to form a protective film, and the surface roughness of the protective film was measured by a P-10 analyzer (TENCO).

○: excellent flatness (surface roughness less than 60 Hz)

(Triangle | delta): Good flatness (surface roughness 60 GPa-80 GPa)

X: poor flatness (surface roughness of 80 kPa or more)

* Developability

: A protective film made of a photosensitive resin composition was formed on a glass substrate coated with chromium in the same manner as in the evaluation of the flatness, and an unexposed part of the protective film was observed by an optical microscope.

○: Excellent developability (no undeveloped portion remains on non-exposed part)

X: Poor developability (the undeveloped part remains on a non-exposed part)

* Chemical resistance

: A protective film made of a photosensitive resin composition was formed on a glass substrate coated with chromium in the same manner as in the evaluation of the flatness, and immersed in 5% aqueous HCl solution, 5% aqueous NaOH solution, xylene, NMP, IPA and acetone for 30 minutes. After that, the peeling and infiltration of the protective film were observed by visual observation and optical microscope.

○: Excellent chemical resistance (no invasion or peeling phenomenon)

X: poor chemical resistance (invasion and peeling phenomenon)

As described in detail above, the use of the photosensitive resin composition of the present invention can easily provide a color filter for CCD excellent in physical properties of all aspects such as transmittance, flatness, developability and chemical resistance.

Claims (4)

(1) The ratio of 9,9'-bis- (4-hydroxyphenyl) fluorene of the following formula (1), the compound of the following formula (2) and the compound of the following formula (3) is 1 mol: 2-4 mol: 2-8 mol 1.00-40.00 wt% of cardo-based binder resin having a molecular weight of 3000-9000, (2) 1.00-20.00 wt% of acrylic photopolymerizable monomer, (3) 0.05-5.00 wt% of photopolymerization initiator, and (4) solvent 40.00- A photosensitive resin composition for a CCD color filter overcoat comprising 80.00% by weight, wherein the cardo-based binder resin and the acrylic photopolymerizable monomer are treated with an acid anhydride of the following formula (4). [Formula 1] [Formula 2] (Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom) [Formula 3] CH ₂ = CRCOOH (Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group, a benzyl group, or an ethoxy group having 1 to 8 carbon atoms) [Formula 4] (Wherein R ₁ and R ₂ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, allyl groups, phenyl groups, benzyl groups or ethoxy groups having 1 to 8 carbon atoms) The method of claim 1, The acrylic photopolymerizable monomer is ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol di Acrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate Rate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol At least one member selected from the group consisting of dimethacrylate and 1,6-hexanediol dimethacrylate The photosensitive resin composition for CCD color filter overcoats characterized by the above-mentioned. The method of claim 1, The photoinitiator is 3,3'-carbonylbis (7-diethylaminocoumarin), and the solvent is ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone And propylene glycol methyl ether or a mixture thereof. The photosensitive resin composition for CCD color filter overcoat. The photosensitive resin composition of claim 1 is coated on the glass substrate for color filter by spin coating, roller coating or spray coating to have a thickness of 0.5 to 10 μm, and irradiates UV rays, electron beams, or X rays in the 190 to 450 nm region. And a protective film layer prepared by forming a pattern, treating the coating film on which the pattern is formed with an alkali developer, and dissolving the unilluminated portion.