JPH1115154A - Photosensitive resin composition and display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the negative photosensitive resin composition well balanced among sensitivity, resolution (hole pattern), transparency, heat resistance, and resistance to chemicals and the display device using this. SOLUTION: This photosensitive resin composition contains (A) an alkali- soluble resin obtained by copolymerizing an unsaturated carboxylic acid (a-1) with a radically polymerizable compound (a-2) represented by the formula in which each of R1 -R3 is, independently, an H atom or a 1-5C alkyl or alkoxy group; and (m) is an integer of 1-5, (B) a compound having at least one ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The display device using this resin composition is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a TFT (Thin Fil) having not only excellent sensitivity and resolution but also good heat resistance.
m Transistor) and a negative photosensitive resin composition suitably used as a transparent insulating film formed between a transparent electrode and the like, a liquid crystal display device using the same, a plasma display panel, an LED luminous body, and the like. Display element.

[0002]

2. Description of the Related Art In recent years, the development of a liquid crystal display (LCD) has been remarkable, and it has been regarded as a favorite of a next-generation display device replacing a CRT (CRT).
Among them, an active matrix type liquid crystal display in which a thin film transistor (TFT) is incorporated in each pixel of the liquid crystal display has excellent characteristics such as high-speed response, high quality, and a wide viewing angle, and has been particularly attracting attention. .
And development of high aperture ratio, enlargement of a display screen, etc. are still being actively carried out.

In such an active matrix type liquid crystal display, for example, a TFT type liquid crystal display, the following various approaches have conventionally been taken in order to widen the aperture ratio which is a problem.

[0004] The characteristics of the TFT are improved and the area is reduced by improving the film quality of the semiconductor film and the gate insulating film. The parasitic capacitance is reduced by employing a self-aligned (self-aligned) TFT structure, and the TFT and the auxiliary capacitance are reduced. -The transistor section is arranged on the gate wiring.・ Improve the voltage holding characteristics of the liquid crystal and reduce the auxiliary capacitance.・ Overlap the storage capacitor on the gate wiring.・ Auxiliary capacitance is made of transparent electrodes. -Reduce the wiring width by using low resistance wiring material. -By sandwiching an insulating film between the pixel electrode and the gate / source wiring, the gap between them is narrowed. -A light-shielding film is provided on the TFT substrate side to reduce the bonding margin with the counter substrate.

[0005] Among the above approaches, a method of narrowing a gap between a pixel electrode and a gate / source wiring by sandwiching an insulating film between the pixel electrode and the gate / source wiring has been particularly promising in recent years.

[0006]

However, the insulating film used in such a promising method has characteristics such as high sensitivity, high resolution (hole pattern), transparency, heat resistance and chemical resistance. However, there is a problem that no conventional photosensitive resin having such characteristics is present. In addition, a positive photoresist containing a novolak resin and a naphthoquinonediazide compound, which has been conventionally used for manufacturing semiconductors, also has excellent sensitivity and resolution, but has transparency, heat resistance, chemical resistance and the like. In view of this, it is not satisfactory. For this reason, the appearance of a photosensitive resin having all the characteristics such as high sensitivity, high resolution (hole pattern), transparency, heat resistance, and chemical resistance has been desired. Further, the above-mentioned problems and demands are caused not only by the liquid crystal display element but also by the plasma display panel (PDP) and the LE.
It is common to display elements such as D light emitters.

The present invention has been made in view of the above-mentioned problems of the prior art, and aims at balancing sensitivity, resolution (hole pattern), transparency, heat resistance, and chemical resistance. An object of the present invention is to provide a negative photosensitive resin composition and various display elements using the same.

[0008]

As a result of various studies to solve the above problems, the present inventors have found that [A] an alkali-soluble resin obtained by copolymerizing an unsaturated carboxylic acid and a predetermined radically polymerizable compound, [B] The compound having at least one ethylenically unsaturated double bond, and [C] the photosensitive resin composition containing a photopolymerization initiator, the ultraviolet ray and further heat, the above-mentioned predetermined radical polymerizable compound The inventors have found that the double bond of the cyclohexene ring and the component [B] are chemically bonded (crosslinked), and that the above-mentioned object can be achieved by a film formed using this photosensitive resin composition, and the present invention has been completed. I came to.

That is, the photosensitive resin composition of the present invention comprises:
[A] Unsaturated carboxylic acid (a-1) and the following general formula (1)

Embedded image (In the formula, R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₄ is a hydrogen atom or 1 carbon atom.
5 to 5 alkyl groups or alkoxy groups, m is 1 to 5
Indicates an integer. )) (A)
And (B) a compound having at least one ethylenically unsaturated double bond, and [C] a photopolymerization initiator. .

Further, a liquid crystal display element of the present invention is characterized by using the above-mentioned photosensitive resin composition, and in this case, this photosensitive resin composition is formed between a TFT and a transparent electrode. It is preferably used as at least one of a transparent insulating film, a transparent insulating film formed between an alignment film and a transparent electrode, and a protective film formed on a color filter.

Further, the plasma display of the present invention
A panel is a plasma display panel using the above-described photosensitive resin composition, wherein the photosensitive resin composition is used as a transparent insulating film or a protective film.

Furthermore, an LED luminous body of the present invention is an LED luminous body using the above-mentioned photosensitive resin composition, wherein the above-mentioned photosensitive resin composition is used as a protective film. I do.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the alkali-soluble resin [A] used in the photosensitive resin composition of the present invention comprises an unsaturated carboxylic acid (a-1) and the following general formula (1)

Embedded image (In the formula, R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₄ is a hydrogen atom or 1 carbon atom.
5 to 5 alkyl groups or alkoxy groups, m is 1 to 5
Indicates an integer. )) (A)
-2).

Here, specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like (hereinafter, (meth) refers to both cases with and without meta). Is contained. ]. These may be used in combination of two or more. Specific examples of the radical polymerizable compound represented by the general formula (1) include (2-cyclohexenyl) methyl (meth) acrylate, (2-cyclohexenyl) ethyl (meth) acrylate, and (3-cyclohexenyl)
Examples thereof include methyl (meth) acrylate and (3-cyclohexenyl) ethyl (meth) acrylate, and these may be used in combination of two or more.

The above alkali-soluble resin [A]
Is an unsaturated carboxylic acid and the radical polymerizable compound,
Other radical polymerizable compounds (a-
It may be a copolymer with 3). Specific examples of such other radical polymerizable compounds include styrene, methylstyrene, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate,
Unsaturated carboxylic acid alkyl esters such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate; and unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Mixtures are mentioned.

As described above, the alkali-soluble resin [A]
Is a copolymer component of each of the above compounds, and the content thereof can be appropriately selected according to the characteristics of the photosensitive resin composition to be obtained, but the unsaturated carboxylic acid (a-1) component is usually 10 to 10. 70% by weight, preferably 30 to 60% by weight, and the radical polymerizable compound (a-2) component is usually 5 to 80% by weight, preferably 20 to 60% by weight. The other radically polymerizable compound (a-3) is contained as an optional component, but may be contained in the alkali-soluble resin [A] in an amount of less than 70% by weight, preferably less than 50% by weight.

If the content of the unsaturated carboxylic acid (a-1) component is less than 10% by weight, the solubility in an aqueous alkali solution is reduced, so that the developability is deteriorated and the sensitivity is lowered. There is. On the other hand, if it exceeds 70% by weight, the solubility in an aqueous alkali solution becomes too large, and the residual film ratio after development may decrease or the coating film surface may be roughened. When the content of the radically polymerizable compound (a-2) is less than 5% by weight, the crosslinking density decreases,
In some cases, the residual film ratio after development may decrease, or the heat resistance may deteriorate. On the other hand, when the content exceeds 80% by weight, the solubility in an aqueous alkali solution is reduced, so that the developability may be deteriorated or the sensitivity may be reduced.

Further, in the present invention, the ratio differs depending on the ratio of the unsaturated carboxylic acid (a-1) component, the radical polymerizable compound (a-2) component and the other radical polymerizable compound (a-3). Has an average molecular weight (Mw) in terms of polystyrene of usually 1, as an alkali-soluble resin [A].
000-100,000, preferably 5,000-5
It is desirable to use those having a molecular weight of 0000. When the average molecular weight (Mw) in terms of polystyrene of the alkali-soluble resin [A] is less than 1,000, the residual film ratio after development may be reduced, or the heat resistance may be deteriorated. On the other hand, 10
If it exceeds 000, developability and sensitivity may be reduced, or residue may remain after development.

The above-mentioned alkali-soluble resin [A] can be obtained by a conventionally known polymerization method. Alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, N-methyl-2 -In a solvent such as an aprotic polar solvent such as pyrrolidone, in the presence of a catalyst (polymerization initiator) such as an azo compound such as 2,2'-azobisisobutyronitrile and an organic peroxide, It is preferably obtained by copolymerizing each component.

Next, as the compound [B] having at least one ethylenically unsaturated double bond, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth)
(Meth) acrylic acid derivatives such as acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate;
Hydroxyalkyl esters such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; ω-carboxypolycaprolactone mono (meth) acrylate; monohydroxyethyl phthalate (meth) Monofunctional (meth) acrylate compounds such as acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, trimethylolpropane tri ( Meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyldi (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di (meth) acrylate, hydroxypropyl di (meth) acrylate, diethylene glycol bishydroxypropyl (meth) acrylate, and monohydroxypentaerythritol tri Examples include polyfunctional (meth) acrylate compounds such as (meth) acrylate.

As these compounds, commercially available monofunctional or polyfunctional (meth) acrylate compounds can be used as they are. Specifically, Aronix M-54
00, M-5700, M-215, M-220,
M-245, M-305, M-309, M-3
15, the same M-400, the same M-450, the same M-8060,
M-8560 (manufactured by Toagosei Chemical Industry Co., Ltd.), VISCOAT 295, 300, 360, and 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD TMPTA, PET-30, DPHA, DPCA -60 (manufactured by Nippon Kayaku Co., Ltd.).

In the present invention, among the above-mentioned compounds, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Aronix M- 305, M-400, M-450, Viscoat 300, 400, KAYARAD TMPTA, D
Trifunctional or higher polyfunctional (meth) acrylates such as PHA and PET-30 are preferably used. In addition, these compounds can be used alone or in combination of two or more.

Next, as the photopolymerization initiator [C], thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, and benzophenones such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone; , 2-diethoxyacetophenone,
2,2-dimethoxy-2-phenylacetophenone, 2
-Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-
Acetophenones such as 1-one, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl)
Halogen compounds such as -s-triazine, 2,4,6-
Acylphosphine oxides such as trimethylbenzoyldiphenylphosphine oxide and 3,3 ′,
4,4'-tetra (t-butylperoxycarbonyl)
Peroxides such as benzophenone;

As the above compound, a commercially available photopolymerization initiator can be used as it is.
ACURE651, 184, 500, 907, 369, 261 (manufactured by Ciba-Geigy), KAYAR
AD-DETX (Nippon Kayaku Co., Ltd.), Lucirin
TPO (manufactured by BASF Japan Ltd.) and the like can be mentioned.

As described above, the photosensitive resin composition of the present invention contains the above-mentioned components [A], [B] and [C], and the content ratio of the components [A] to [C]. Is 20 to 150 parts by weight, preferably 40 to 100 parts by weight of the compound [B] having at least one ethylenically unsaturated double bond, based on 100 parts by weight of the alkali-soluble resin [A].
And 0.1 to 50 parts by weight, preferably 1 to 25 parts by weight, of the photopolymerization initiator [C], and 100 parts by weight of a compound having at least one or more total ethylenically unsaturated double bonds. The content of the polyfunctional (meth) acrylate compound having at least three ethylenically unsaturated double bonds is preferably at least 50 parts by weight.

When the amount of the compound [B] having at least one ethylenically unsaturated double bond is less than 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin [A], curing of the photosensitive resin by light is unsatisfactory. In some cases, the solubility in a developer is increased, and the surface of the coating film after development may be roughened. On the other hand, when the amount exceeds 150 parts by weight, the tack on the surface of the coating film becomes too large, and the coating film obtained after curing may be roughened. Further, the photopolymerization initiator [C] was added in an amount of 0.1 to 100 parts by weight of the alkali-soluble resin [A].
If the amount is less than 1 part by weight, the crosslinking (curing) reaction of the compound having at least one ethylenically unsaturated double bond may not proceed sufficiently, while if it exceeds 50 parts by weight, the developability is reduced. May be.

The photosensitive resin composition of the present invention may contain components other than the above components, if necessary, as long as the object of the present invention is not impaired. Such other components include a sensitizer, a coupling agent, a surfactant and the like.

The sensitizer is used for improving the sensitivity of the photosensitive resin composition.
It is used by adding 1 to 20 parts by weight based on parts by weight. As the sensitizer, naphthothiazolines, benzothiazolines and the like which are hardly colored by heating are preferably used.
Specifically, 1-methyl-2-benzoylmethylene-β
-Naphthothiazoline, 2- (β-naphthoylmethylene)
And -3-methylbenzothiazoline.

The coupling agent is used for improving the adhesion to the substrate, and the remaining components (hereinafter abbreviated as "solid content") of the photosensitive resin composition except for the solvent are 100. It is used by adding 10 parts by weight or less based on parts by weight. As the coupling agent, silane-based, aluminum-based and titanate-based compounds are used. Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltrimethoxysilane, and aluminum-based such as acetoalkoxyaluminum diisopropylate And titanate compounds such as tetraisopropylbis (dioctylphosphite) titanate.

The surfactant is used for improving the wettability, leveling property and coating property on the underlying substrate, and is used in an amount of 0.01 to 100 parts by weight of the photosensitive resin composition.
１1 part by weight is used. As a surfactant,
Silicon-based surfactants, acrylic surfactants, fluorine-based surfactants, and the like are used. Specifically, Byk-3
00, Byk-306, Byk-335, Byk-31
0, Byk-341, Byk-344, Byk-370
(By trade name, manufactured by Big Chemie Co., Ltd.), such as Byk-354, Byk-358, Byk-36
Acrylics such as No. 1 (trade name, manufactured by Big Chemie Co., Ltd.), SC-101 (manufactured by Asahi Glass Co., Ltd.), EF-35
1, Fluorosurfactants such as EF-352 (trade name, manufactured by Tochem Products Co., Ltd.).

The photosensitive resin composition of the present invention is usually used in the form of a solution after being dissolved in an appropriate solvent. This solution is obtained by adding an alkali-soluble resin [A] into a solvent and completely dissolving the solution, and then compounding a compound [B] having at least one ethylenically unsaturated double bond in the solution and a photopolymerization initiator. [C] and, if necessary, a sensitizer, a coupling agent,
A surfactant and the like are mixed at a predetermined ratio, and the solid content concentration is 2
It is prepared by adjusting the amount to be 0 to 40% by weight and then stirring to completely dissolve.

Examples of the solvent used here include alcohols such as methoxydiethanol, ethoxyethanol, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; esters such as methyl cellosolve acetate, ethyl cellosolve acetate and ethyl lactate. , Diethylene glycol dimethyl ether, N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide and the like can be mentioned.
A mixture of more than one species can be used.

When the photosensitive resin composition prepared as described above is applied to the surface of a substrate and the solvent is removed by heating, a coating film can be formed. The application of the photosensitive resin composition to the substrate surface can be performed by a conventionally known method such as a spin coating method, a roll coating method, and a dipping method. Then, this coating is a hot plate,
Heat in an oven etc. (hereinafter abbreviated as "pre-bake")
Is done. The prebaking conditions vary depending on the type and blending ratio of each component, but are usually 70 to 110 ° C, 1 to 5 minutes for a hot plate, and 5 to 15 minutes for an oven.

Thereafter, the prebaked coating film is irradiated with ultraviolet rays or the like via a mask having a predetermined pattern, and then developed with a developing solution to remove unnecessary portions to form a coating film having a predetermined pattern. Examples of the developer include aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydroxide and potassium hydroxide, and organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, a surfactant or the like can be added to the above-mentioned alkaline aqueous solution. The development method may be any of dipping method, shower method, spray method and the like, and the development time is usually 30 to 240 seconds. After development, the pattern can be formed by rinsing with running water and drying. .

Thereafter, the pattern is transferred to a hot plate,
By heating in an oven or the like (hereinafter abbreviated as “post-baking”), the unreacted components of the compound having at least one ethylenically unsaturated double bond are further crosslinked, and the solvent is completely removed, A predetermined coating pattern can be obtained. Post-baking conditions vary depending on the type and blending ratio of each component, but are usually 180 to 22.
At 0 ° C., 5-30 minutes for a hot plate and 30-90 minutes for an oven.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Synthesis example 1 of alkali-soluble resin) (3-cyclohexenyl) methyl methacrylate 50
g, 50 g of methacrylic acid, 1.5 g of 2,2′-azobisisobutyronitrile, and 280 g of methanol were charged into a stirrer, a cooling tube, a nitrogen introducing tube, and a flask equipped with a thermometer.
After purging with nitrogen for 0 minutes, the flask was immersed in an oil bath to carry out a polymerization reaction at an internal temperature of 65 ° C. for 5.5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was diluted with 2800 g of ethyl acetate.
And 1400 g of cyclohexane, and the resulting precipitate was dried under reduced pressure to obtain a polystyrene-equivalent average molecular weight of 33.
90 g of an alkali-soluble resin of 000 were obtained.

(Synthesis Example 2 of Alkali-Soluble Resin) (3-Cyclohexenyl) methyl methacrylate 25
g, styrene 25 g, methacrylic acid 50 g, 2,2′-
0.5 g of azobisisobutyronitrile and 200 g of tetrahydrofuran were charged into a stirrer, a cooling tube, a nitrogen inlet tube and a flask equipped with a thermometer, and purged with nitrogen for 30 minutes. The polymerization reaction was performed for 5 hours. Thereafter, the flask was cooled to room temperature, and the reaction solution was mixed with 1500 g of ethyl acetate and 1500 g of cyclohexane.
And the resulting precipitate was dried under reduced pressure to obtain 70 g of an alkali-soluble resin having an average molecular weight of 15,600 in terms of polystyrene.

(Synthesis example 3 of alkali-soluble resin) 50 g of styrene, 50 g of methacrylic acid, 0.1 g of 2,2'-azobisisobutyronitrile, 200 g of tetrahydrofuran
Was charged into a flask equipped with a stirrer, cooling tube, nitrogen inlet tube and thermometer. After purging with nitrogen for 30 minutes, the flask was immersed in an oil bath to carry out a polymerization reaction at an internal temperature of 74 ° C. for 5.5 hours. Thereafter, the flask was cooled to room temperature, the reaction solution was added dropwise to a mixed solution of 1500 g of ethyl acetate and 1500 g of cyclohexane, and the resulting precipitate was dried under reduced pressure to obtain 70 g of an alkali-soluble resin having an average molecular weight of 26,500 in terms of polystyrene.

Example 1 160 g of N, N-dimethylacetamide, 40 g of butyl cellosolve, and 44 g of the alkali-soluble resin obtained in the above Synthesis Example 1 were charged into a nitrogen-separated 500 ml separable flask equipped with stirring blades, and stirred. After dissolving uniformly, Aronix M305
(Product name: Toa Gosei Chemical Industry Co., Ltd.) 26.4 g, I
rgacure907 (trade name: CIBA-GEIGY)
4.4 g, 2- (β-naphthoylmethylene) -3
-0.22 g of methylbenzothiazoline was added and uniformly dissolved, and then Byk-344 (manufactured by BYK Chemie Co., Ltd.)
0.14 g was added, and the mixture was stirred at room temperature for 1 hour.
The solution was filtered through a 2 μm membrane filter to obtain a solution of the photosensitive resin composition. Next, the photosensitive resin composition solution obtained as described above was evaluated by forming a pattern as described below. This evaluation method is common to Example 2 and Comparative Example 1 described later.

[Evaluation of Photosensitive Resin Composition] Pattern forming method: The solution of the photosensitive resin composition obtained in each of Examples and Comparative Examples was spin-coated on a glass substrate and then heated at 80 ° C. in an oven. Pre-baking was performed for 10 minutes to form a coating film. Then, after exposing (all lines, no filter) by changing the exposure time with a PLA-501F mask aligner (trade name, manufactured by Canon), 0.02 wt%
Using an aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 1 minute for Example 1 and Comparative Example 1,
Example 2 was spray developed for 90 seconds. Then, it was rinsed with pure water and dried. And 2 in the oven
By heating at 00 ° C. for 30 minutes, the cross-linking of the unreacted components of the compound having at least one ethylenically unsaturated double bond in the coating film is further promoted, and at the same time, the solvent is completely removed. A film was formed. The coating film thus obtained was evaluated for the following properties with respect to sensitivity, resolution, residual film ratio, transparency, heat resistance, and chemical resistance. Table 1 shows the results of these evaluations.

[Evaluation Method] Sensitivity: Exposure was performed through a mask as shown in FIG.
In the obtained pattern, an exposure amount (“appropriate exposure amount” or “sensitivity”) at which the size of the bottom portion of the hole pattern obtained by the mask pattern of 10 μm was 10 μm was obtained. Resolution: The size of the bottom of the minimum hole pattern resolved at an appropriate exposure was measured by a scanning electron microscope. -Remaining film ratio: (film thickness after development / film thickness after prebaking) x 1
00 was determined, and 90% or more was evaluated as ○, and less than 90% was evaluated as ×. -Transparency: In the obtained patterned glass substrate,
The transmittance of the coating film alone at 400 to 800 nm was measured with a spectrophotometer (trade name: U-3210, manufactured by Hitachi, Ltd.). At this time, the minimum transmittance (that is, the wavelength 400
(transmittance in nm) is 95% or more, and ○ is less than 95%. Heat resistance: 220 ° C of the obtained patterned glass substrate
After reheating for 1 hour, the remaining film ratio after heating and the transmittance after heating (the transmittance at a wavelength of 400 nm) with respect to the thickness before heating (the thickness after post-baking) were measured. The case where the residual film ratio after heating was 95% or more was evaluated as ○, and the case where it was less than 95% was evaluated as ×. ○, 95% when transmittance after heating is 95% or more
The case of less than was evaluated as x. -Chemical resistance: 2 w on the obtained patterned glass substrate
immersion treatment at 40 ° C. for 15 minutes in an aqueous solution of t% sodium hydroxide (hereinafter abbreviated as NaOH treatment), immersion treatment at 40 ° C. for 30 minutes in an aqueous solution of 10 wt% hydrochloric acid (hereinafter abbreviated as HCl treatment), 30 ° C at 40 ° C
After a separate immersion treatment (hereinafter abbreviated as NMP treatment) and an immersion treatment in isopropyl alcohol at 40 ° C. for 30 minutes (hereinafter abbreviated as IPA treatment), the rate of change in film thickness before and after each treatment The change in the transmittance before and after each treatment was measured, and the change in the coating film surface was observed. The case where the change rate of the film thickness before and after each treatment was less than 1% was evaluated as ○, and the case where it was 1% or more was evaluated as x. The case where the rate of change of the transmittance before and after each treatment was less than 1% was evaluated as ○, and the case where it was 1% or more was evaluated as x. Observation of the surface of the coating film was evaluated as ○ when there was no change, and as X when there was a change such as film roughness.

Example 2 N, N-dimethylacetamide (160 g), butyl cellosolve (40 g), and the alkali-soluble resin (44 g) obtained in Synthesis Example 2 were charged into a nitrogen-purged 500 ml separable flask equipped with stirring blades and stirred. After dissolving uniformly, Aronix M305
(Product name: Toa Gosei Chemical Industry Co., Ltd.) 26.4 g, I
rgacure907 (trade name: CIBA-GEIGY)
8.8 g, 2- (β-naphthoylmethylene) -3
-0.22 g of methylbenzothiazoline was added and uniformly dissolved, and then Byk-344 (manufactured by BYK Chemie Co., Ltd.)
0.14 g was added, and the mixture was stirred at room temperature for 1 hour.
The solution was filtered through a 2 μm membrane filter to obtain a solution of the photosensitive resin composition. Thereafter, a pattern was formed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 1 N, N-dimethylacetamide (160 g), butyl cellosolve (40 g), and the alkali-soluble resin (44 g) obtained in Synthesis Example 3 were charged into a nitrogen-purged 500 ml separable flask equipped with stirring blades and stirred. After dissolving uniformly, Aronix M305
(Product name: Toa Gosei Chemical Industry Co., Ltd.) 26.4 g, I
rgacure907 (trade name: CIBA-GEIGY)
8.8 g, 2- (β-naphthoylmethylene) -3
-0.22 g of methylbenzothiazoline was added and uniformly dissolved, and then Byk-344 (manufactured by BYK Chemie Co., Ltd.)
0.14 g was added, and the mixture was stirred at room temperature for 1 hour.
The solution was filtered through a 2 μm membrane filter to obtain a solution of the photosensitive resin composition. Thereafter, a pattern was formed and evaluated in the same manner as in Examples 1 and 2. Table 1 shows the evaluation results.

[0044]

[Table 1]

As shown in Table 1, the alkali-soluble resin [A] containing the radically polymerizable compound (a-2) component represented by the general formula (1) of Examples 1 and 2 belonging to the scope of the present invention. And at least one ethylenically unsaturated double bond
The photosensitive resin composition containing the compound [B] having at least one and the photopolymerization initiator [C] has at least one alkali-soluble resin [A] and at least one ethylenically unsaturated double bond by ultraviolet light and heat. Since the compound [B] has a chemical bond (crosslinking), the alkali-soluble resin [A] containing no radically polymerizable compound (a-2) represented by the general formula (1) of Comparative Example 1 [A] ], The difference in the dissolution rate of the exposed part and the unexposed part with respect to the alkali developing solution becomes larger, and it can be seen that a pattern film having excellent residual film ratio, sensitivity and resolution after development is obtained. .

Further, it is excellent in transparency, heat resistance and chemical resistance, and has no practical problems.
Particularly useful as a transparent insulating film disposed between the TFT and the transparent electrode, a transparent insulating film disposed between the alignment film and the transparent electrode, and a protective film disposed on the color filter Is also clear. Furthermore, it is clear from the above characteristics that the photosensitive resin composition of the present invention can be suitably used as a transparent insulating film or a protective film in a PDP or a protective film in an LED luminous body.

[0047]

As described above, according to the present invention, a predetermined alkali-soluble resin, a compound having at least one ethylenically unsaturated double bond, and a photopolymerization initiator are blended. It is possible to provide a negative photosensitive resin composition balanced in sensitivity, resolution (hole pattern), transparency, heat resistance and chemical resistance, and various display elements using the same. That is, with the photosensitive resin composition of the present invention, it is possible to form a film pattern excellent in sensitivity, resolution, transparency, heat resistance, chemical resistance and the like, and such a film pattern constitutes a liquid crystal display device. It can be suitably used as a transparent insulating film formed between a TFT and a transparent electrode, a transparent insulating film formed between an alignment film and a transparent electrode, and a protective film formed on a color filter. Is also applicable.

[Brief description of the drawings]

FIG. 1 is a plan view showing a mask pattern used for evaluating characteristics of a photosensitive resin composition.

Claims (6)

[Claims] [A] An unsaturated carboxylic acid (a-1) and the following general formula (1): (In the formula, R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₄ is a hydrogen atom or 1 carbon atom.
5 to 5 alkyl groups or alkoxy groups, m is 1 to 5
Indicates an integer. )) (A)
And (B) a compound having at least one ethylenically unsaturated double bond, and [C] a photopolymerization initiator. Photosensitive resin composition. 2. A method comprising adding another radical polymerizable compound (a-3) copolymerizable with the unsaturated carboxylic acid (a-1) and / or the radical polymerizable compound (a-2). The photosensitive resin composition according to claim 1, wherein 3. A liquid crystal display device comprising the photosensitive resin composition according to claim 1 or 2. 4. A transparent insulating film formed between the TFT and the transparent electrode, a transparent insulating film formed between the alignment film and the transparent electrode, and protection formed on the color filter, wherein the photosensitive resin composition is formed. 4. The liquid crystal display device according to claim 3, wherein the device is used as at least one of the films. 5. A plasma display panel using the photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition is used as a transparent insulating film or a protective film. A plasma display panel characterized by the above. 6. An LED luminous body using the photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition is used as a protective film. body.