KR100773281B1 - Resist composition and method of forming resist pattern - Google Patents

Abstract

(A) Alkali-soluble resin containing 30 to 95 weight% of polyvinyl phenol and 5 to 70 weight% of novolak resin, (B) Irradiation of actinic light, or irradiation of actinic light, and crosslinking alkali-soluble resin by heat processing following it The resist composition containing the component and (C) black pigment.

A resist pattern formation method which bakes this resist pattern after forming a resist pattern on a board | substrate using this composition.

Description

RESIST COMPOSITION AND METHOD OF FORMING RESIST PATTERN

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to resist compositions used in the field of photolithography, and more particularly, it is possible to form a resist pattern that is remarkably excellent in heat resistance and good adhesion to a substrate, and is suitable for use as a light shielding film such as a black matrix. It relates to a composition. Moreover, this invention relates to the method of forming resist patterns, such as a patterned light shielding film, using this resist composition. The resist composition of this invention is especially suitable for the use of the black matrix of a color filter in a liquid crystal display panel, the black matrix, an electrically insulating partition, an insulating layer, etc. in an organic electroluminescent display panel.

In recent years, in display devices, such as a liquid crystal display panel, in order to improve display quality, a light shielding film is essential. For example, in the color filter of the liquid crystal display panel, a pixel of a plurality of colors such as red (R), green (G), blue (B) is formed on a transparent substrate, and a black matrix is disposed between the pixels. This prevents a decrease in contrast and color purity due to light leaking from between the pixels. The black matrix is a patterned light shielding film formed on a substrate using a light shielding material.

In the photolithography technique, a photomask serving as an original plate when transferring an electronic circuit is composed of a light shielding film forming a pattern and a transparent substrate supporting the light shielding film. As the light shielding film, a chromium film having high light shielding property and easy microprocessing is generally used. However, since the chromium film has a high surface reflectance, when it is used as the light shielding film of the color filter, the display quality is degraded by the reflected light. Although the reflectance can be reduced by arranging the interference film of chromium oxide on the surface or both surfaces of the chromium film, the film forming process is complicated and the effect of reducing the reflectance is also insufficient.

Therefore, in the field of display devices, such as a liquid crystal display panel, the technique of forming a light shielding film using the resist composition containing a black pigment is proposed. For example, Japanese Unexamined Patent Application Publication No. 4-190362 discloses a light shielding film containing a black organic pigment and / or a pseudo blackened mixed color organic pigment and a light shielding material such as carbon black in a photosensitive resin. Forming resists have been proposed. As the photosensitive resin, an acrylic acid ultraviolet curable resist is used. Japanese Unexamined Patent Application Publication No. 6-230215 proposes a positive resist composition for black matrices containing an alkali-soluble resin, a quinonediazide compound, a black pigment, and a solvent.

Japanese Unexamined Patent Application Publication No. 11-24269 proposes a photosensitive coloring composition for color filters containing a hydroxystyrene copolymer, a crosslinking agent, a photoacid generator, and grafted carbon black. Japanese Patent Laid-Open No. 11-143056 contains an alkali-soluble resin obtained by condensing phenols and aldehydes containing cresol, an acid crosslinkable methirolylated melamine resin, a compound that absorbs light to generate an acid, and a black pigment. A black matrix forming material for a color liquid crystal display device is proposed.

On the other hand, in the field of display devices, such as a liquid crystal display panel and an organic electroluminescent display panel, the resist material used for forming a light shielding film is (1) excellent in resolution and capable of sufficient microprocessing, (2) A sufficient black density as the light shielding film, (3) good adhesion of the resist pattern to the substrate, and the like are required, in addition to (4) being able to form a resist pattern having high heat resistance, and (5) necessary. As a result, it is desired that the cross-sectional shape be able to form a forward taper shape, an inverse taper shape (including an overhang shape), or a rectangular resist pattern. In view of these required performances, conventional resist materials are in need of further improvement.

The heat resistance and the shape of the resist pattern will be described by taking an electrically insulating partition of the organic electroluminescent display panel as an example. In the photoresist for forming an electrically insulating partition wall in an organic electroluminescent display panel, it is required to be able to form a resist pattern profile having an inverse taper shape. The organic electro luminescence (hereinafter referred to as "organic EL" abbreviation) display is self-luminous and has no limitation of viewing angle, high brightness, thin panel, low voltage drive, fast response speed, It is possible to make full colors by the three primary colors of RGB (red and blue green). However, since the organic EL material is low in resistance to organic solvents and cannot be etched, there is a problem that a matrix structure as a display element cannot be formed by micromachining using photolithography technology. Therefore, the use of the organic EL display as a backlight for a liquid crystal display is mainly used.

Therefore, Japanese Patent Laid-Open No. 8-315981 proposes a new proposal regarding a technology for forming a display element using an organic EL material. Specifically, (1) a plurality of stripe-shaped patterns of indium tin oxide (ITO) are formed on the transparent substrate to form a first display electrode (anode), and (2) a negative resist on the entire surface of the substrate therefrom. The composition is applied to form a resist film, (3) exposed through a stripe-shaped photomask orthogonal to the stripe-shaped pattern of ITO, (4) post-exposure baking, and then developed to form a stripe negative resist pattern. And (5) depositing an organic EL material (hole transporting material and electron transporting material) on the substrate in this order, and (6) depositing a metal such as aluminum on it again to produce an organic EL display panel. It is becoming.

In this organic EL display panel, the negative resist pattern serves as an electrically insulating partition. That is, as shown in FIG. 1, on the transparent substrate 1, the ITO film | membrane (anode) 2 patterned by stripe shape is formed, and then the stripe negative resist pattern 3 orthogonal to this is formed. do. If the cross section of this negative resist pattern is an inverse taper shape or an overhang shape, when the organic electroluminescent material is vapor-deposited on it, the vapor-deposited film of the organic electroluminescent material of stripe shape orthogonal to the ITO film 2 on the board | substrate 1 ( 4) is formed independently. Even if an organic EL material is deposited on the negative resist pattern, the deposited film 4 'exists independently of the deposited film 4 on the substrate.                 

When the metal such as aluminum is further deposited from above, the independent metal deposition films 5 and 5 are respectively deposited on the deposited film 4 of the organic EL material on the substrate and on the deposited film 4 'of the organic EL material on the negative resist pattern. 5 ') is formed. The metal deposition film 5 formed on the vapor deposition film 4 of the organic EL material becomes a second display electrode (cathode). Adjacent second display electrodes (cathodes) are electrically isolated from each other by a negative resist pattern. The ITO film (anode) 2 and the metal deposition film (cathode) 5 are separated by the vapor deposition film 4 of the organic EL material and do not short.

In the organic EL display panel having such a structure, the first display electrode and the second display electrode cross each other, and the evaporation film portion of the organic EL material sandwiched between the positive electrodes becomes a light emitting portion. The negative resist pattern is not removed and is left as an electrically insulating partition. Therefore, the resist pattern is required to be excellent in adhesiveness with a board | substrate.

DESCRIPTION OF RELATED ART Conventionally, the method of forming an inverse taper resist pattern by the image reversal method using the positive photoresist which consists of a novolak resin and a quinonediazide compound is known. However, this image reversal method is not only complicated in operation, but also has a narrow tolerance of the heating temperature during the heat treatment (amine diffusion and heating), making it difficult to obtain a resist pattern having a good shape.

Japanese Unexamined Patent Publication (Kokai) No. 5-165218 includes at least a compound that absorbs (A) a component that crosslinks by exposure to light or heat treatment followed by exposure, (B) alkali-soluble resin, and (C) light to be exposed. A negative resist composition containing 1 type and using alkaline aqueous solution as a developing solution is proposed. This negative resist composition can form a resist pattern of an inverse taper shape or an overhang shape, and is suitable for formation of the conductor pattern by a lift-off method. However, this resist pattern did not have sufficient heat resistance.

The electrically insulating partition in the organic EL display panel must maintain its shape to withstand the respective processes of vapor deposition and metal deposition of the organic EL material under high temperature conditions. In particular, in the case of depositing an organic EL material, in order to widen the margin (acceptability) of the sublimation temperature, it is required to improve the heat resistance of the electrically insulating partition wall made of a resist pattern. In addition, since the organic EL display panel is used in a portable device, a vehicle-mounted device, or the like, it is required to have durability that can withstand high temperature conditions such as temperature rise in a vehicle. However, the resist pattern of the conventional reverse taper cross section had the problem that heat resistance was still not enough.

At the time of vapor deposition of an organic EL material, when organic EL material of each color of RGB is vapor-deposited using a vapor deposition mask, the organic electroluminescent display panel which has the pixel of each color and is capable of color display can be obtained. Since the electrically insulating partition is arrange | positioned between each pixel, when this is formed from the resist material containing a black pigment, it can have a function as a black matrix.

In addition, even if the entire electrically insulating partition wall is not black, a color display can be obtained if the portion in contact with the ITO film is black. For example, as shown in FIG. 2, when the resist pattern 24 of the reverse taper cross section is formed on the transparent substrate 21 in which the ITO film | membrane (anode) 22 was formed, through the insulating film 23, a transparent substrate The insulation between the 21 and the resist pattern 24 can be further improved. The vapor deposition films 25 and 25 'of organic EL material are formed on a board | substrate and a resist pattern. Even when the resist pattern 24 of the reverse tapered cross section is formed using a resist material containing no black pigment or low concentration of the black pigment, the insulating film 23 is formed of a resist material containing black pigment, The function as a black matrix can be provided to the insulating film 23. The insulating film 23 is also required to be heat resistant to withstand deposition of organic EL materials and metal materials and to withstand use in high temperature environments.

Considering the use conditions of the various display devices, the black matrix of the color filter is also required to have sufficient heat resistance to withstand use in a high temperature environment. In addition, in the manufacture of a color filter, a pixel of each color may be formed on a transparent substrate on which a black matrix is formed in advance using a resist material containing an organic pigment or the like, but various heat treatments are applied in the pixel formation process. Therefore, it is preferable that a black matrix is excellent in heat resistance. Further, the black matrix of the color filter preferably has a rectangular cross section or a forward taper shape, and therefore, a resist material capable of forming such a cross sectional shape is preferable.

Disclosure of the Invention

An object of the present invention is to provide a resist composition which is remarkably excellent in heat resistance and has good adhesion to a substrate, and is suitable for use as a light shielding film such as a black matrix. Moreover, the objective of this invention is providing the resist composition which cross-sectional shape can form a forward taper shape, an inverse taper shape (including the overhang shape), or a rectangular resist pattern as needed. Another object of the present invention is to provide a method of forming a resist pattern such as a light shielding film having a pattern shape using the resist composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that (A) alkali-soluble resin, (B) irradiation of actinic light (exposure), or a component which bridge | crosslinks alkali-soluble resin by irradiation with actinic light and subsequent heat processing (Crosslinked component) and (C) Resist composition containing black pigment WHEREIN: As a alkali-soluble resin of (A) component, heat resistance is used by using the resin composition containing polyvinyl phenol and a novolak resin in a specific ratio. It has been found that a significantly improved resist pattern can be formed and the adhesion of the resist pattern to the substrate is also good.

When a black pigment is used, the resist composition suitable for formation of light shielding films, such as a black matrix, can be obtained. When the resist pattern formed using the resist composition of the present invention is fired, the light shielding property can be further improved.

Moreover, in the resist composition of this invention, the compound (B1) which generate | occur | produces an acid by irradiation of actinic light as a crosslinking component (B), and the compound (B2) which bridge | crosslinks alkali-soluble resin using this acid as a catalyst are combined The weight ratio (B1: B2) of both is preferably 1: 1 to 1:30, more preferably 1: 2 to 1:25, still more preferably 1: 3 to 1:20, The heat resistance of a resist pattern can be improved further. In order to obtain high heat resistance, the weight ratio (B1: B2) of both is 1: 4 to 1:30, more preferably 1: 5 to 1:25, and particularly preferably 1: 6 to 1:20. It is desirable to adjust.

Alkali image development is possible for the resist composition of this invention, and the cross-sectional shape can form a forward taper shape, an inverse taper shape (including the overhang shape), or a rectangular resist pattern by adjusting an exposure amount. The present invention has been completed based on these findings.

According to the present invention, (A) alkali-soluble resin containing 30 to 95% by weight of polyvinylphenol and 5 to 70% by weight of novolak resin, (B) irradiation of actinic rays, or irradiation of actinic rays followed by heat treatment The resist composition containing the component which bridge | crosslinks alkali-soluble resin, and (C) black pigment is provided.

Moreover, according to this invention, (A) alkali-soluble resin containing 30 to 95 weight% of polyvinyl phenols and 5 to 70 weight% of novolak resin, (B) irradiation of actinic light, or irradiation of actinic light and subsequent heat processing The resist pattern formation method of baking a resist pattern after forming a resist pattern on a board | substrate by the photolithographic method using the component which crosslinks alkali-soluble resin by this, and (C) black pigment, Is provided.

1 is an explanatory diagram showing an example of microfabrication of an organic EL display panel.

2 is an explanatory diagram showing another example of microfabrication of an organic EL display panel.                 

The symbols in each drawing are as follows.

1: substrate

2: ITO membrane pattern

3: resist pattern of inverse tapered cross section

4: vapor deposition film of organic EL material

4 ': vapor deposition film of organic EL material

5: metal deposition film

5 ': metal film

21: substrate

22: ITO membrane pattern

23: electrically insulating bulkhead

24: resist pattern of inverse tapered cross section

25: vapor deposition film of organic EL material

25 ': vapor deposition film of organic EL material

Best Mode for Carrying Out the Invention

1. (A) Alkali-soluble resin

In this invention, the resin composition containing 30 to 95 weight% of polyvinylphenol and 5 to 70 weight% of novolak resin is used as alkali-soluble resin. Conventionally, as an alkali-soluble resin, the novolak resin which addition-condensed m-cresol / p-cresol (weight ratio 80: 20-20: 80) and formaldehyde is used (for example, Unexamined-Japanese-Patent No. 5-165218). Example 2 of the call. When novolak resin is used as alkali-soluble resin, the heat resistance of the obtained resist pattern is not enough, and there existed a problem that the cross-sectional shape of a resist pattern collapsed at the temperature of about 120-130 degreeC.

The present inventors found that even in the case of a resist composition using a novolak resin as the alkali-soluble resin, the heat resistance temperature can be improved to about 150 ° C by performing ultraviolet irradiation while heating the resist pattern formed on the substrate. However, for the deposition of the organic EL material, a heat resistance temperature exceeding that may be required. On the other hand, a resist composition using polyvinylphenol as the alkali-soluble resin has a problem that the resist pattern is easily peeled off from the substrate after forming the resist pattern, and in the technical field in which a metal or an organic EL material is deposited from the resist pattern. It was actually difficult to use.

The inventors of the present invention have surprisingly found that by using polyvinylphenol and a novolak resin together as an alkali-soluble resin, the heat resistance temperature can be remarkably improved while suppressing peeling of the resist pattern from the substrate.

As polyvinyl phenol, the homopolymer of vinyl phenol, the copolymer of vinyl phenol, and the monomer copolymerizable with this is mentioned. Examples of the monomer copolymerizable with vinylphenol include isopropenylphenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic acid imide, and vinyl acetate. Among these, the homopolymer of vinylphenol is preferable and the homopolymer of p-vinylphenol is especially preferable.

The average molecular weight of the polyvinylphenol is usually 3000 to 20,000, preferably 4000 to 15000, more preferably 5000 to 10000 in terms of the weight average molecular weight (Mw) of monodisperse polystyrene in terms of gel permeation chromatography (GPC). to be. If the weight average molecular weight of the polyvinyl phenol is too low, the molecular weight does not sufficiently increase even if the exposure region crosslinks, so that the polyvinylphenol is easily dissolved in the alkaline developer, and the effect of improving heat resistance is lowered. If the weight average molecular weight of the polyvinyl phenol is too large, the difference in solubility in the alkaline developer in the exposed region and the unexposed region becomes small, so that it is difficult to obtain a good resist pattern.

As a novolak resin, what is widely used in the technical field of a resist can be used. The novolak resin can be obtained by, for example, reacting phenols with aldehydes or ketones in the presence of an acidic catalyst (for example, oxalic acid).

Examples of the phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol and 2,4-dimethyl Phenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2- Methylresolecinol, 4-methylresolecinol, 5-methylresolecinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4 -Propyl phenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, isothymol and the like. These can be used individually or in combination of 2 types or more, respectively.

Examples of the aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenyl propylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m- Hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzene Terephthalic acid aldehyde etc. are mentioned. Acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, etc. are mentioned as ketones. These can be used individually or in combination of 2 types or more, respectively.

Among the above, novolak resins obtained by condensing metacresol and paracresol in combination with formaldehyde, formalin or paraformaldehyde are particularly preferable from the viewpoint of controllability of resist. The injection weight ratio of metacresol and paracresol is usually 80:20 to 20:80, preferably 70:30 to 50:50. It is also preferable to use 3,5-dimethylphenol (ie, 3,5-xylenol). In this case, the injection weight ratio of cresols (total amount of metacresol and paracresol) and 3,5-xylenol is usually 50:50 to 80:20, preferably 60:40 to 70:30.

The average molecular weight of the novolak resin is usually 1000 to 10,000, preferably 2000 to 7000, and more preferably 2500 to 6000 in terms of the weight average molecular weight in terms of monodisperse polystyrene measured by GPC. If the weight average molecular weight of the novolak resin is too low, even if crosslinking reaction of the exposed portion occurs, the effect of increasing the molecular weight is small and easily dissolved in the alkaline developer. If the weight average molecular weight of the novolak resin is too high, the difference in solubility in the alkaline developer of the exposed portion and the unexposed portion is small, and it is difficult to obtain a good resist pattern.                 

The weight average molecular weight of polyvinyl phenol and a novolak resin can be controlled to a desired range by adjusting synthetic | combination conditions. In addition, for example, (1) a method of pulverizing a resin obtained by synthesis and solid-liquid extraction with an organic solvent having a suitable solubility, (2) a resin obtained by synthesis is dissolved in a good solvent and added dropwise into a poor solvent, The weight average molecular weight can be controlled by dropping a poor solvent and extracting the solid-liquid or liquid-liquid.

Measurement of the weight average molecular weight by GPC is performed on condition of the following using SC8020 (made by TOSO Corporation) as a GPC measuring apparatus.

Column: TOSO manufactured TSKGEL G3000HXL and G200HXL1000 each one combination

Temperature: 38 ℃

Solvent: Tetrahydrofuran

Flow rate: 1.0ml / min

Sample: 0.1 ml of a sample with a concentration of 0.05-0.6 wt%

When the use ratio of polyvinyl phenol and a novolak resin is represented by weight ratio, it is 30: 70-95: 5 normally, Preferably it is 35: 65-95: 5, More preferably, it is the range of 40: 60-90: 10. As the proportion of the polyvinylphenol increases, the heat resistance of the resist pattern becomes better, but the peeling off of the substrate becomes easier. When the ratio of novolak resin increases, the problem of peeling of the resist pattern from a board | substrate is solved, but heat resistance falls. Therefore, the balance of heat resistance and peeling resistance becomes favorable by making ratio of both into the said range.

2. (B) crosslinking component

The crosslinking component used by this invention is a component which bridge | crosslinks alkali-soluble resin by irradiation of actinic light or a heat treatment following irradiation of actinic light. By the action of the crosslinking component, the molecular weight of the alkali-soluble resin in the exposure region is increased, and the dissolution rate in the alkaline developer is extremely reduced. Thereby, the resist composition of this invention functions as a negative resist which can be developed by alkaline developing solution.

As a crosslinking component (B), (1) Photoinitiator which generate | occur | produces a radical by irradiation of actinic light (for example, a benzophenone derivative, a benzoin derivative, a benzoin ether derivative etc.), and the unsaturated hydrocarbon superposed | polymerized by this radical A compound having a group (for example, pentaerythritol tetra (meth) acrylate, etc.) and a sensitizer for enhancing the efficiency of the photoreaction if necessary, and (2) a compound which generates an acid by irradiation with active light (Hereinafter, referred to as "photoacid generator") and a compound which crosslinks an alkali-soluble resin using an acid generated by light as a catalyst (substance-sensitive substance: hereinafter referred to as "crosslinking agent"). have. Among them, the photoacid generator (B1) and the crosslinking agent (B2) of (2) are excellent in terms of compatibility with alkali-soluble resins, and in combination with alkali-soluble resins, a crosslinking chemically amplified resist having good sensitivity can be provided. Preferred is a crosslinking component consisting of a combination of

<Mine generator>

The compound which generates an acid by actinic radiation is not particularly limited as long as it is a substance that generates bristed acid or Lewis acid when exposed by activating radiation, and there are no onium salts, halogenated organic compounds, quinonediazide compounds, α, Known ones such as α'-bis (sulfonyl) diazomethane compounds, α-carbonyl-α'-sulfonyldiazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds Can be. Among these, aromatic sulfonic acid esters, aromatic iodonium salts, aromatic sulfonium salts, aromatic compounds having a halogenated alkyl residue, and the like are preferable. It is preferable to select these photo-acid generators in terms of spectral sensitivity according to the wavelength of the light source which exposes a pattern.

Examples of the onium salts include iodonium salts such as diazonium salts, ammonium salts and diphenyl iodonium triplates, sulfonium salts such as triphenylsulfonium triplates, phosphonium salts, arsonium salts, and oxonium salts.

Halogenated organic compounds include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetphenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds Compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenyl halide compounds, and the like. .

Specific examples of the halogenated organic compound include tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl) phosphate, tetrabromochlorobutane, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloroγmethyl) -S-triazine, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromosi Clododecene, hexabromobiphenyl, allyl tribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (chloroethyl) ether of tetrachlorobisphenol A, bis (bromoethyl of tetrabromobisphenol A ) Ether, bis (2,3-dichloropropyl) ether of bisphenol A, bis (2,3-dibromopropyl) ether of bisphenol A, bis (2,3-dichloropropyl) ether of tetrachlorobisphenol A, tetra Bis (2,3-dibromopropyl) ether of bromobisphenol A, tetrachlorobis Nol S, tetrabromobisphenol S, bis (chloroethyl) ether of tetrachlorobisphenol S, bis (bromoethyl) ether of tetrabromobisphenol S, bis (2,3-dichloropropyl) ether of bisphenol S, bisphenol Bis (2,3-dibromopropyl) ether of S, tris (2,3-dibromopropyl) isocyanurate, 2,2, -bis (4-hydroxy-3,5-dibromo Halogen flame retardants such as phenyl) propane and 2,2-bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) propane; Dichlorodiphenyltrichloroethane, pentachlorophenol, 2,4,6-trichlorophenyl, 4-nitrophenylel, 2,4-dichlorophenyl, 3'-methoxy-4'-nitrophenylether, 2,4 -Dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2 Organic chloro pesticides such as -trichloroethanol, 2,4,4 ', 5-tetrachlorodiphenyl sulfide, 2,4,4', 5-tetrachlorodiphenyl sulfone, and the like.

Specific examples of the quinone diazide compound include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5 Sulfonic acid esters of quinonediazide derivatives such as sulfonic acid esters, 2,1-naphthoquinonediazide-4-sulfonic acid esters, and 2,1-benzoquinonediazide-5-sulfonic acid esters; 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5- Sulfonic acid chlorides of quinonediazide derivatives such as sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride and 1,2-benzoquinone-1-diazide-5-sulfonic acid chloride have.

Examples of the α, α'-bis (sulfonyl) diazomethane-based compound include an unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic, or heterocyclic group Bis (sulfonyl) diazomethane etc. are mentioned.

Specific examples of the α-carbonyl-α-sulfonyldiazomethane-based compound include α-carbons having unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups. Bonyl- (alpha)-sulfonyl diazomethane etc. are mentioned.

Specific examples of the sulfone compound include unsubstituted, symmetrically or asymmetrically substituted alkyl groups, alkenyl groups, aralkyl groups, aromatic groups, or sulfone compounds having a heterocyclic group, disulfone compounds and the like.

Examples of the organic acid esters include carboxylic acid esters, sulfonic acid esters, and phosphoric acid esters. Examples of the organic acid amides include carboxylic acid amides, sulfonic acid amides, and phosphoric acid amides. Acid imide, sulfonate imide, phosphide imide and the like.

In addition, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-oxocyclohexyl (2- Norbornyl) sulfonium trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate , Diphenyl iodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, phenyl paratoluenesulfonate, and the like.

The photoacid generator is usually used in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. If the ratio of the photoacid generator is too small or too large, the shape of the resist pattern may be deteriorated.

<Bridge school>

A crosslinking agent is a compound (subduction substance) which can crosslink alkali-soluble resin in presence of the acid generate | occur | produced by irradiation of actinic light (exposure). As such a crosslinking agent, well-known acid crosslinkable compounds, such as an alkoxy methylation amino resin, such as an alkoxy methylation urea resin, an alkoxy methylation melamine resin, the alkoxy methylation uron resin, and the alkoxy methylation glycoluril resin, are mentioned, for example. In addition, alkyl ether melamine resin, benzoguanamine resin, alkyl ether benzoguanamine resin, free ia resin, alkyl ether urea resin, urethane-formaldehyde resin, resol type phenol formaldehyde resin, alkyl ether resol type phenol form Aldehyde resin, an epoxy resin, etc. are mentioned.

Among these, an alkoxy methylated amino resin is preferable, and specific examples thereof include methoxymethylated amino resin, ethoxymethylated amino resin, n-propoxymethylated amino resin, n-butoxymethylated amino resin, and the like. Among these, methoxymethylated amino resins such as hexamethoxymethylmelamine are particularly preferable in view of good resolution. As a commercial item of the alkoxy methylated amino resin, PL-1170, PL-1174, UFR65, CYMEL300, CYMEL303 (above, Mitsui Cytech Co., Ltd.), BX-4000, Nikarak MW-30, MX290 (above, Sanwa Chemical Co., Ltd. make) ), And the like.

These crosslinking agents can be used individually or in combination of 2 types or more, respectively. The crosslinking agent is usually used in an amount of 0.5 to 60 parts by weight, preferably 1 to 50 parts by weight, and more preferably 2 to 40 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. If the amount of the crosslinking agent is too small, the crosslinking reaction is difficult to proceed sufficiently, and the residual film ratio of the resist pattern of the developer using the alkaline developer is lowered, or the deformation of the resist pattern, such as swelling or meandering, is likely to occur. When the usage-amount of a crosslinking agent is too much, there exists a possibility that a resolution may fall.

<Ratio of photoacid generator and crosslinking agent>

As a crosslinking component (B), the combination of a photo-acid generator (B1) and a crosslinking agent (B2) is preferable from a viewpoint of further improving the heat resistance of a resist pattern. The weight ratio (B1: B2) of the photoacid generator (B1) and the crosslinking agent (B2) is usually about 1: 1 to 1:30, but is preferably 1: 2 to 1:25, more preferably 1: 3 to 1 : 20. High heat resistance can be obtained by the weight ratio of both being in this range.

The inventors have further studied that the weight ratio (B1: B2) of both is preferably 1: 4 to 1:30, more preferably 1: 5 to 1:25, and particularly preferably 1: 6 to 1: 1. As a result of raising the lower limit of the ratio of the crosslinking agent to the photoacid generator at 20, it was found that the heat resistance of the resist pattern was remarkably improved. In this case, the use ratio of the photoacid generator (B1) to 100 parts by weight of the alkali-soluble resin is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, and the use ratio of the crosslinking agent (B2). Preferably it is 4-60 weight part, More preferably, it is 8-50 weight part, It is preferable to raise each minimum. In most cases, very high heat resistance can be achieved in the weight ratio (B1: B2) of both in the range of 1: 7 to 1:15.

3. (C) black pigment

Since black pigment acts as a compound which absorbs actinic light, and absorbs the exposure light which goes to the depth direction of a resist film at the time of exposure, a cross section is rectangular, pure taper shape, or inverted cross section by adjusting exposure amount. A resist pattern that is tapered or overhanged can be obtained. The shape of the resist pattern is also affected by the reflection of light exposed by a substrate or an ITO film formed on the substrate. Therefore, component (C) is needed also for the reflection prevention of exposure light. In particular, a resist using a combination of a photoacid generator and an acid crosslinkable component (crosslinking agent) as a crosslinking component (B) is a chemically amplified type, and crosslinks to an area where acid generated by irradiation of light diffuses in the resist film and is not exposed to light. Therefore, it is important to control the shape of the resist pattern by having a component (C) that absorbs actinic light.

In this invention, a black pigment is used as a component (C) which absorbs actinic light. As described above, the resist using a combination of a photoacid generator and an acid crosslinkable component as the crosslinking component (B) is a crosslinking chemically amplified resist, and crosslinks to an area where the acid generated by irradiation of light diffuses in the resist film and is not exposed to light. Causes a reaction. By using such a characteristic, a relatively large amount of black pigment can be contained and a resist composition for light shielding film formation, such as a black matrix, can be obtained.

As the black pigment, any of black inorganic pigments and organic pigments may be used, or a mixture thereof. In addition, the black pigment may be a mixed color organic pigment obtained by mixing two or more types of organic pigments other than black. Preferred black pigments include inorganic pigments such as titanium black (titanium oxide), carbon black, chromium oxide, iron oxide, and zinc oxide; Phthalocyanine pigments such as phthalocyanine blue, anthraquinone pigments such as chromophthal red, azo or azo lake pigments such as lake red, isoindolinone pigments such as monovalent yellow, dioxazine pigments such as dioxazine violet, naphthol Organic pigments such as nitroso pigments such as green B, lake pigments such as rhodamine lake, quinacridone pigments, and quinacridine pigments. The black pigment may be a mixed color organic pigment which is pseudo blackened by mixing at least two organic pigments selected from the group consisting of red, blue, green, purple, sulfur, cyanine, and magenta (Japanese Patent Laid-Open No. 4-190362). ).

Among these black pigments, inorganic pigments such as titanium black and carbon black are preferable from the viewpoint of heat resistance and light resistance. However, when applying to the use which requires high electrical insulation in a resist pattern, it is preferable to reduce the usage-amount of inorganic pigments, such as carbon black, and to increase the usage-amount of organic pigments (including a mixed organic pigment). The usage-amount of a black pigment is 0.1-200 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 0.5-150 weight part.

When applying the resist composition of this invention to the use of light shielding films, such as a black matrix, the black pigment which is a component (C) is 10-200 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 20-150 weight Part, and more preferably 30 to 100 parts by weight. When a high electrical insulation property is required for a resist pattern, it is preferable to make the usage-amount of inorganic black pigment which has electroconductivity, such as carbon black, 30 weight part or less with respect to 100 weight part of alkali-soluble resin.

When forming a resist pattern whose cross section is an inverse taper shape or an overhang shape, the usage-amount of a component (C) can be suitably determined according to the film thickness of a resist composition, the kind of component (C), etc., but it is generally thick In this case, since light is difficult to transmit, the light may be reduced. The component (C) is usually used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.

4. Other additives

Surfactant can be added to a resist composition for the purpose of the improvement of the dispersibility of each component of a resist composition, etc. As surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonyl phenol ether; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and ethylene glycol distearate; F-top EF301, EF303, EF352 (made by Shin-Kita Chemical Co., Ltd.), megafax F171, F172, F173, F177 (made by Dainippon Ink), Florid FC430, FC431 (made by Sumitomo 3M Corporation), Asahi Guard AG710, company Fluorine surfactants such as Pron S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (manufactured by Asahi Glass Co., Ltd.); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Acrylic acid type or methacrylic acid type (co) polymer Polyflow Nos. 75 and No. 95 (manufactured by Kyoeisa Oil Chemical Co., Ltd.) are mentioned. The compounding quantity of these surfactant is 2 weight part or less normally per 100 weight part of solid content of a composition, Preferably it is 1 weight part or less.

5. Organic Solvent

Although the resist composition of this invention may be used as powder as needed, normally, each component is melt | dissolved in the organic solvent, it filters, and is used as a resist solution. An organic solvent is used in an amount sufficient to dissolve or disperse each component uniformly. Solid content concentration in a resist solution is 5-50 weight% normally, Preferably it is about 10-40 weight%.

As an organic solvent, For example, Alcohol, such as n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, cyclohexyl alcohol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; Esters such as propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, ethyl ethoxypropionate and ethyl pyruvate Ryu; Cyclic ethers such as tetrahydrofuran and dioxane; Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Cellosolve acetates such as ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; Alcohol ethers such as ethylene glycol diemel ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, and propylene glycol monobutyl ether; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl glycol dimethyl ether and diethylene glycol diethyl ether; lactones such as γ-butyrolactone; Halogenated hydrocarbons such as trichloroethylene; Aromatic hydrocarbons such as toluene and xylene; Polar organic solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide; 2 or more types of these mixed solvents are mentioned.

6. Method of forming resist pattern

The resist composition of the present invention can form a resist pattern on a substrate using photolithography techniques. Specifically, the resist composition of the present invention is uniformly applied onto the substrate by spin coating or the like, and the solvent is dried to remove the resist film. Although it does not restrict | limit especially as a board | substrate, A silicon substrate, a glass substrate, an ITO film formation board | substrate, a chromium film formation board | substrate, a resin substrate, etc. are mentioned.

The resist film is usually heat treated (prebaked) for about 10 to 200 seconds at a temperature of about 80 to 110 ° C. In this way, a resist film having a thickness of about 0.5 to 5 m is obtained. Subsequently, the pattern shape is exposed on a resist film using a desired light source. When the resist composition of the present invention is a chemically amplified resist containing a photoacid generator and an acid crosslinkable component as a crosslinking component (B), it is usually 10 at a temperature of about 100 to 130 ° C after exposure for the purpose of promoting the crosslinking reaction. Post exposure baking (PEB) is performed for about 200 seconds.

Examples of the actinic rays used for exposure include ultraviolet rays, far ultraviolet rays, KrF excimer laser light, X-rays, electron beams, and the like. As a specific example of the light source to expose, the bright spectrum of mercury, such as 436 nm, 405 nm, 365 nm, and 254 nm, the KrF excimer laser light source of 248 nm, etc. are mentioned.

In the resist composition of the present invention, since the exposed portion is insolubilized with respect to the alkaline developer by the action of the crosslinking component (B) and acts negatively, the resist film starts to remain after the development when the exposure amount is a certain amount or more. The exposure energy at this time is called "Eth". In order to form the resist pattern of a reverse taper shape or an overhang shape in a cross section, it exposes with the exposure amount about 2 times or less of Eth or more normally. When the exposure amount is increased, the cross-sectional shape of the resist pattern immediately becomes a rectangular to pure tapered shape.

The resist composition of the present invention can be developed with an alkaline developer. As alkaline developing solution, alkaline aqueous solution is used normally. As an alkali, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia; Primary amines such as ethylamine and propylamine; Secondary amines such as diethylamine and dipropylamine; Tertiary amines such as trimethylamine and triethylamine; Alcohol amines such as diethyl ethanol amine and triethanol amine; Quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and the like. In addition, water-soluble organic solvents such as methyl alcohol, ethyl alcohol, propyl alcohol and ethylene glycol, surfactants, and dissolution inhibitors of resins may be added to the aqueous alkali solution, if necessary.

When used in the lift-off method, the resist pattern obtained by the development forms various films such as a metal deposition film on the entire surface of the substrate therefrom. Thereafter, the resist pattern is removed together with the film formed thereon, leaving only a film such as a metal deposition film formed on the substrate. In this case, the cross-sectional shape of a resist pattern is made into a reverse taper shape or an overhang shape.

When producing an organic EL display panel, organic electroluminescent material is vapor-deposited on the resist pattern of the reverse taper shape or overhang shape obtained by image development, and metals, such as aluminum, are vapor-deposited (FIG. 1). In this case, the resist pattern is left as an electrically insulating partition without being removed. This electrically insulating partition wall can give a function as a black matrix.

In the case where the resist pattern is used as the insulating layer of the organic EL display panel (Fig. 2), the cross-sectional shape is rectangular or inverse taper shape, preferably rectangular. In this case as well, the resist pattern is left as an insulating layer without removing the resist pattern. In FIG. 2, in order to form the resist pattern 24 whose cross section is reverse tapered, in the resist composition of this invention, the black pigment of the component (C) absorbs actinic rays, such as an azo dye, (a Japanese publication) It is preferable to use a resist composition instead of JP-A 5-165218, because a resist pattern excellent in heat resistance can be formed. In addition, in order to form the resist pattern 24 whose cross section is an inverse taper shape, you may use the resist composition of this invention with a small content of a component (C).

If ultraviolet rays are irradiated while heating the resist pattern formed on the substrate before the deposition step of the organic EL material or the metal, the heat resistance of the resist pattern can be further improved. Specifically, ultraviolet rays are irradiated at an irradiation dose of about 5 to 1000 mW while the whole substrate is placed on a hot plate and heated to a temperature of about 70 to 120 ° C. The irradiation time of ultraviolet rays is usually about 20 to 40 seconds.

In light shielding films, such as a black matrix, it is preferable that the optical density (OPTICAL DENCITY; OD value) measured using the white light source exists in the range of 2.5-4.5 in 1.0 micrometer of film thicknesses. More specifically, when the intensity of light before entering the object is set to I ₀ and the intensity of light after entering and being absorbed by the object is set to I, the OD value is expressed as log (I ₀ / I). Moreover, it is preferable that the resist composition for light shielding films contains a comparatively large amount of black pigment, and is high in resolution.

When the resist composition of the present invention containing a relatively large amount of black pigment is used, a light shielding film exhibiting a high OD value can be obtained. In order to give a desired OD value and good resolution, a method of baking the resist pattern is effective. Specifically, a resist pattern is formed using a resist composition having a black pigment, and after exposure bake (PEB), if necessary, usually 150 to 400 ° C, preferably 200 to 350 ° C, more preferably 250 It is -350 degreeC, Usually, it is heated for 1 to 10 minutes, Preferably it is baked for 1 to 5 minutes. By baking, the resin component of a resist composition becomes black and OD value becomes high.

By using a black pigment as a component (C), the resist composition of this invention can be applied suitably for the use of light shielding films, such as a color filter of a liquid crystal display panel, and a black matrix in an organic electroluminescent display panel. For example, in the color filter of a liquid crystal display panel, light is formed between pixels by forming a black matrix between pixels such as red (R), green (G), and blue (B) using the resist composition of the present invention. The fall of contrast and color purity by the leakage of can be prevented. Also in an organic EL display panel, it is used as a black matrix in order to raise contrast and to improve visibility, In this case, it can combine the function as a black matrix, and an electrically insulating partition or an insulating layer.

By using the resist composition of the present invention, it is possible to easily form a light shielding film patterned using a photolithography technique. In particular, in the chemically amplified resist composition using a combination of a photoacid generator and an acid crosslinkable component as the crosslinking component (B), even if the content of the black pigment is high, the curing reaction by crosslinking proceeds close to the substrate. This excellent light shielding film can be obtained. Moreover, this light shielding film (resist pattern) is excellent in heat resistance and peeling resistance. Further, by adjusting all the conditions such as the kind and the amount of the black pigment used, the kind and amount of the other components, the irradiation conditions, and the like, the cross-sectional shape of the resist pattern can be arbitrarily controlled, such as an inverse taper shape, an overhang shape, a rectangle, and the like.

An Example and a comparative example are given to the following, and this invention is demonstrated to it further more concretely. The measuring method of physical property is as follows.

(1) heat resistance

The board | substrate with which the resist pattern was formed was put on the hotplate for 300 second, and the temperature which can maintain the reverse taper-shaped resist pattern was measured. Specifically, heating was performed for every 110 seconds to 5 ° C for 300 seconds, and the shape of the resist pattern was observed with a scanning electron microscope to measure the temperature (heat resistance temperature) at the time when the top of the resist pattern was stretched and rounded.

(2) peeling resistance

After image development, whether or not a resist pattern was formed on the substrate was visually observed to evaluate the evaluation that the peeling resistance was poor (×) and the peeling resistance was good (○).

(3) optical density (OD value)

The optical density of the resist film with a film thickness of 1.0 micrometer was measured using the white light source.

(4) resolution

It is the value which observed and measured the dimension of the resist pattern which the line & space (L / S) formed by the method as described in Example was 1/1 with a scanning electron microscope (SEM).

Example 1

90 parts by weight of poly p-vinylphenol having a weight average molecular weight of 6000 and 10 parts by weight of a novolak resin having a weight average molecular weight of 4000 obtained by dehydration of formaldehyde with formaldehyde at an injection ratio of 70/30 (weight ratio). 1 part by weight of a triazine-based photoacid generator [manufactured by Midori Chemical, TAZ106], and 3 parts by weight of melamine-based resin [substance: Mitsui Cytech, Cymel 303], and titanium black 60 weight part (titanium black pure powder) was dissolved in polyethyleneglycol monomethyl ether, and the resist solution of 34 weight% of solid content concentration was prepared.

Using a spin coater, this resist solution was applied onto the transparent glass substrate so that the dry film thickness was 1.0 mu m, and then heated on a hot plate at 100 DEG C for 90 seconds to form a resist film. Using Canon PLA501F as an exposure machine, it exposed to the resist film with the energy of 50mJ / cm <2> through the mask, and formed the latent image. Thereafter, post exposure bake (PEB) was performed at 110 ° C. for 60 seconds. Next, paddle development was performed for 65 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution.

After development, the glass substrate on which the resist pattern was formed was placed on a hot plate, heated at 150 ° C. for 30 seconds, and then heated up to 300 ° C. for 60 seconds, and held at 300 ° C. for 90 seconds to fire the resist pattern. The treatment was performed. In this way, a resist pattern was obtained in which the line & space (L / S) was 1/1. It was 5 micrometers when this resist pattern was observed with the scanning electron microscope and the resolution was measured. The heat resistance temperature of this resist pattern was 250 degreeC, and was excellent in heat resistance. Moreover, the peeling resistance of this resist pattern was favorable ((circle)).

On the other hand, in the same manner as above, a resist film was formed on another transparent glass substrate. Thereafter, heat treatment and firing treatment were performed in the same manner as described above except that exposure and development were not performed. It was 2.5 when the optical density (OD value) was measured about the resist film obtained in this way using the monochrome density measurement density meter (TD-932 by Sakatainkusu Co., Ltd.).

Example 2

90 parts by weight of poly p-vinylphenol having a weight average molecular weight of 6000 and 10 parts by weight of a novolak resin having a weight average molecular weight of 4000 obtained by dehydration of formaldehyde with formaldehyde at an injection ratio of 70/30 (weight ratio). 1 part by weight of a triazine-based photoacid generator [manufactured by Midori Chemical, TAZ106], and 3 parts by weight of melamine-based resin [substance: Mitsui Cytech, Cymel 303], and titanium black 90 weight part (titanium black pure powder) was dissolved in polyethyleneglycol monomethyl ether, and the resist solution of 34 weight% of solid content concentration was prepared.

Using a spin coater, this resist solution was applied onto the transparent glass substrate so that the dry film thickness was 1.0 mu m, and then heated on a hot plate at 100 DEG C for 90 seconds to form a resist film. After exposure to energy of 200mJ / cm <2> through the mask to the resist film using PLA501F by Canon Corporation as an exposure machine, 110 degreeC and the post-exposure bake (PEB) for 60 second were performed. Next, paddle development was performed for 65 seconds using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. After the development, the glass substrate on which the resist pattern was formed was placed on a hot plate and heated at 150 ° C. for 60 seconds.

The resist pattern formed in this way was 15 micrometers. The heat resistance temperature of this resist pattern was 250 degreeC, and was excellent in heat resistance. The peeling resistance of this resist pattern was favorable ((circle)). In addition, the resist film was formed in the other transparent glass substrate by the same method, and the optical density (OD value) measured after heat processing was 3.0.

Example 3

In Example 1, except that 1 part by weight of the triazine-based photoacid generator was changed to 3 parts by weight and 3 parts by weight of the melamine resin crosslinker, respectively, to 25 parts by weight, a resist solution was prepared in the same manner as in Example 1 to form a resist pattern. It formed and baked the resist pattern. As a result, the heat resistance temperature of the obtained resist pattern rose from 250 degreeC of Example 1 to 300 degreeC. The other characteristic of this resist pattern was the same as that of Example 1.

Example 4

In Example 2, a resist solution was prepared in the same manner as in Example 2 except that 1 part by weight of the triazine-based photoacid generator was changed to 3 parts by weight and 3 parts by weight of the melamine-based resin crosslinking agent, respectively. Formed. As a result, the heat resistance temperature of the obtained resist pattern rose from 250 degreeC of Example 2 to 300 degreeC. The other characteristics of this resist pattern were the same as in Example 2.                 

Comparative Example 1

In Example 2, a resist pattern was formed on a transparent glass substrate in the same manner as in Example 2, except that polyp-vinylphenol having a weight average molecular weight of 6000 was used alone as the alkali-soluble resin. The peeling resistance of this resist pattern was inferior (x).

Comparative Example 2

Example 2 WHEREIN: Except having independently used the novolak resin of the weight average molecular weight 4000 obtained by dehydrating condensation of formaldehyde with formaldehyde at the injection ratio of 70/30 (weight ratio) as alkali-soluble resin independently. In the same manner as in Example 2, a resist pattern was formed on the transparent glass substrate. The heat resistance temperature of this resist pattern was 120 degreeC, and heat resistance was inadequate.

ADVANTAGE OF THE INVENTION According to this invention, the resist pattern which is remarkably excellent in heat resistance and favorable adhesiveness with a board | substrate can be formed, and the black resist composition suitable for the use as a light shielding film, such as a black matrix, is provided. Moreover, according to this invention, the method of forming resist patterns, such as a patterned light shielding film, using this resist composition is provided. The resist composition of this invention is especially suitable for the use of the black matrix of a color filter in a liquid crystal display panel, the black matrix, an electrically insulating partition, an insulating layer, etc. in an organic electroluminescent display panel.

Claims (15)

(A) Alkali-soluble resin containing 30 to 95 weight% of polyvinyl phenol and 5 to 70 weight% of novolak resin, (B) Irradiation of actinic light, or irradiation of actinic light, and crosslinking alkali-soluble resin by heat processing following it The resist composition containing the component and (C) black pigment. The resist composition according to claim 1, wherein the polyvinylphenol has a weight average molecular weight of 3000 to 20000. The resist composition according to claim 1, wherein the novolak resin is a condensation reaction of a mixed phenol of metacresol and paracresol with formaldehyde, formalin or paraformaldehyde. The resist composition according to claim 3, wherein the ratio of metacresol and paracresol used in the condensation reaction is 80:20 to 20:80. The resist composition according to claim 1, wherein the novolak resin has a weight average molecular weight of 1000 to 10,000. The compound according to claim 1, wherein the crosslinking component (B) is a combination of a compound (B1) which generates an acid by irradiation with actinic light and a compound (B2) which crosslinks an alkali-soluble resin using this acid as a catalyst. The resist composition whose (B1: B2) is 1: 1-1: 30. The resist composition according to claim 1, wherein the crosslinking component (B) is an alkoxymethylated amino resin. The resist composition according to claim 1, wherein the black pigment is 10 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin. The resist composition of claim 1, wherein the black pigment is an inorganic pigment. The resist composition of Claim 1 whose ratio of the inorganic pigment in a black pigment is 30 weight part or less with respect to 100 weight part of alkali-soluble resin. (A) Alkali-soluble resin containing 30 to 95 weight% of polyvinyl phenol and 5 to 70 weight% of novolak resin, (B) Irradiation of actinic light, or irradiation of actinic light, and crosslinking alkali-soluble resin by heat processing following it A resist pattern forming method of baking a resist pattern after forming a resist pattern on a substrate by exposing the resist film obtained by applying and drying the resist composition containing the component and (C) black pigment to a board | substrate, and developing with a developing solution. . The resist pattern forming method according to claim 11, wherein the exposure amount at the time of exposure is equal to or greater than the exposure energy amount Eth at which the resist film begins to remain after development, or less than twice the Eth. The resist pattern forming method according to claim 11, wherein the substrate is heated to 70 to 120 ° C. during exposure. The resist pattern forming method according to claim 11, wherein the firing is performed by heating at 150 to 400 DEG C for 1 to 10 minutes. The light shielding film obtained by the method of Claim 11.

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