KR101021717B1 - Protrusion of Vertically Aligned Liquid Crystal Display Device, Spacer of Vertically Aligned Liquid Crystal Display Device, and Process for Forming the Same - Google Patents

Abstract

The present invention is a vertically oriented photoresist that is capable of forming protrusions and / or spacers that are excellent in resolution and residual film ratio, and also excellent in pattern shape, heat resistance, solvent resistance, transparency, etc., and also excellent in orientation, voltage retention, and the like. The radiation sensitive resin composition which can provide a liquid crystal display element is provided. This resin composition contains (a) alkali-soluble resin, (b) 1,2-quinonediazide compound, and (c) the specific melamine compound and / or the compound which has 2 or more epoxy groups in a molecule | numerator.

Photoresist, spacer, alkali-soluble resin, 1,2-quinonediazide compound, melamine compound

Description

Protrusion of Vertically Aligned Liquid Crystal Display Device, Spacer of Vertically Aligned Liquid Crystal Display Device, and Process for Forming the Same}

1 is an example of the schematic diagram of the cross-sectional shape of a processus | protrusion and a spacer.

It is an example of the schematic diagram which illustrates the cross-sectional shape of the vertically-aligned liquid crystal display element which has a processus | protrusion and a spacer.

<Brief description of the parts of the main parts of the drawings>

1: spacer

2: turning

3: liquid crystal

4: liquid crystal aligning film

5: color filter

6: glass substrate

The present invention provides a radiation-sensitive resin composition for forming projections and / or spacers for vertically aligned liquid crystal display elements, and projections and spacers for projections and / or spacers for vertically aligned liquid crystal display elements formed therefrom. One vertically oriented liquid crystal display element, and a method of forming the projection and / or the spacer.

Liquid crystal display devices are the most widely used among flat panel displays, and the display quality of TFT (thin film transistor) type liquid crystal displays (TFT-LCDs) has been widely used in recent years by OA devices such as personal computers and word processors, liquid crystal televisions, and the like. The demand for performance is becoming increasingly stringent.

The most commonly used method among TFT-LCDs is TN (Twisted Nematic) type LCD, which has an orientation direction of 90 on both outer sides of a substrate having two transparent electrodes (hereinafter referred to as a "transparent electrode substrate"). Another polarizing film is arrange | positioned, the alignment film is arrange | positioned inside two transparent electrode substrates, and a nematic type liquid crystal is arrange | positioned between both alignment films, and the orientation direction of a liquid crystal is the other electrode side from one electrode side. It is twisted 90 degrees over. When light of unpolarized light enters in this state, linearly polarized light transmitted through one polarizing plate can pass through the other polarizing plate in order to transmit the liquid crystal in the polarization direction, so that it becomes bright. Next, when a liquid crystal molecule is made upright by applying a voltage to both electrodes, in order to transmit the linearly polarized light which reached the liquid crystal as it is, it cannot penetrate the other polarizing plate, and it becomes a dark state. After that, if the voltage is not applied again, the state returns to the bright state.

In recent years, such TN-type LCDs have the same contrast and color reproducibility on the front side as the CRTs. However, the TN type LCD has a big problem that the viewing angle is narrow.

As a solution to this problem, MVA (Multi-domain Vertically Aligned) type LCD (vertical alignment liquid crystal display) has been developed.

This MVA type LCD is not the beneficiation mode of the TN type LCD, as described in "Liquid Crystal" (Vol. 3, No. 2, p. 117 (1999)) and Japanese Patent Laid-Open No. 11-258605. The birefringence mode is a combination of a negative liquid crystal having a dielectric anisotropy and an alignment film in a vertical direction, and the alignment direction of the liquid crystal in a position close to the alignment film remains almost vertical even when no voltage is applied. It is excellent also in the manufacturing process surface, such as not having to perform the rubbing process for orientating a liquid crystal.

In the MVA type LCD, as the domain regulating means for allowing the liquid crystal to have a plurality of alignment directions in one pixel region, the electrode on the display side has a slit in one pixel region, and the light on the incident side electrode substrate In the same pixel region, projections having slopes at positions different from the slits of the electrodes, for example, triangular abstractions, semi-convex lens shapes, and the like are formed.

In general, in order to maintain a constant cell gap between two transparent electrode substrates, a spherical or rod-shaped spacer such as resin or ceramic is used as a conventional liquid crystal display. When the two transparent electrode substrates are bonded together, the spacers are scattered on one of the substrates, and the cell gap is defined by the diameter of the spacers.                         

Further, in order to avoid defects such as nonuniformity of the cell gap due to nonuniformity of the diameter of the spacer, Japanese Patent Laid-Open No. 2001-201750 discloses a method of forming protrusions and spacers using a photoresist. This method has the advantage that fine processing is possible and the shape can be easily controlled. However, Japanese Unexamined Patent Application Publication No. 2001-201750 does not specifically describe the composition of the photoresist, and the performance of the formed protrusions and spacers is also not clear.

As the performance required for the photoresist used for the formation of the projections and the spacers for the vertical alignment liquid crystal display element, the cross-sectional shape is appropriate, and the resistance to the solvent used in the subsequent alignment film forming step is applied in the alignment film forming step. Loss of heat resistance, transparency, resolution, and the residual film ratio is high performance. Moreover, what is excellent in the orientation, voltage retention, etc. is calculated | required by the obtained vertical alignment type liquid crystal display element.

Applicant has already described a copolymer of [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) unsaturated compounds other than these, [B] unsaturated polymerization A radiation-sensitive resin composition for simultaneously forming a projection and a spacer containing an acidic compound and a [C] radiation-sensitive polymerization initiator, a projection and a spacer formed therefrom, and a liquid crystal display device including the projection and the spacer are proposed. (See Japanese Patent Laid-Open No. 2003-29405).

However, development of radiation-sensitive resin compositions useful for the formation of projections and spacers in vertically oriented liquid crystal display devices has only just begun, and projections having excellent performance in response to the rapid spread of TFT-LCDs and increasingly stringent demanded performance and The development of new radiation-sensitive resin compositions capable of forming spacers has become an important technical problem.

An object of the present invention is to provide a radiation-sensitive resin composition for forming a projection and / or a spacer for a vertical alignment liquid crystal display element.

Another object of the present invention is to provide a photoresist that is capable of forming protrusions and spacers having excellent resolution and residual film ratio, and excellent pattern shape, heat resistance, solvent resistance, transparency, and the like, and also having excellent orientation, voltage retention and the like. It is providing the radiation sensitive resin composition which can provide a liquid crystal display element.

Still another object of the present invention is to provide a method for forming a projection and / or a spacer for a vertically aligned liquid crystal display device using the radiation-sensitive resin composition of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above object and advantages of the present invention are first, (a) alkali-soluble resin, (b) 1,2-quinonediazide compound and (c) a compound represented by the following formula (1) and / or an epoxy group It is achieved by the radiation sensitive resin composition characterized by containing the compound which has two or more in inside.                         

Wherein, R ¹ to R ⁶ independently represent a hydrogen atom or a group -CH ₂ OR, R represents a linear or branched alkyl group having 1 to 6 carbon atoms or a hydrogen atom.

According to this invention, the said objective and advantage of this invention are 2nd achieved by the processus | protrusion for vertically-aligned liquid crystal display elements formed from the radiation sensitive resin composition of this invention.

According to this invention, the said objective and advantage of this invention are 3rd achieved by the spacer for the vertical alignment type liquid crystal display element formed from the radiation sensitive resin composition of this invention.

Further, according to the present invention, the above object and advantages of the present invention are achieved by the vertically aligned liquid crystal display device having the protrusions and / or spacers of the present invention.

Finally, according to the present invention, the above object and advantages of the present invention are the fifth step of forming a film of the radiation-sensitive resin composition of the present invention on a substrate, a step of exposing radiation to the film through a photomask, the film after exposure It is achieved by the method of forming the processus | protrusion and / or spacer for a vertically-aligned liquid crystal display element characterized by including the process of image development by alkali developing solution, and the process of exposing radiation to this pattern.

Hereinafter, each component of the radiation sensitive resin composition of this invention is demonstrated in detail.

(a) alkali-soluble resin

"Alkali solubility" which is used about alkali-soluble resin used for this invention means the film of the radiation sensitive resin composition in this invention formed on the board | substrate by exposing the below-mentioned processus | protrusion and / or a spacer, and exposing it. Then, when developing this film after exposure with alkali developing solution, it means the property which can substantially melt | dissolve and remove all the exposure part of the said film after exposure.

Alkali-soluble resin in this invention is not specifically limited as long as it has the said property. Preferred alkali-soluble resins are novolak resins obtained by polycondensing phenols and aldehydes in the presence of an acidic catalyst.

As phenols used for manufacture of the said novolak resin, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2 , 6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4 -Ethyl resorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl catechol, pyrogallol, fluoroglycinol, thymol, isothymol and the like.

Among these phenols, phenol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2 , 3,5-trimethylphenol and the like are preferable.

The said phenols can be used individually or in mixture of 2 or more types. In addition, in this invention, as a preferable combination in the case of using 2 or more types of phenols, m-cresol / p-cresol, m-cresol / 2, 3- dimethyl phenol, m-cresol / 2, 4- Dimethylphenol, m-cresol / 2,5-dimethylphenol, m-cresol / 2,3,5-trimethylphenol, phenol / 2,3-dimethylphenol / 3,4-dimethylphenol, m-cresol / 2,3 -Dimethylphenol / 2,4-dimethylphenol, m-cresol / 2,3-dimethylphenol / 3,4-dimethylphenol, m-cresol / 2,4-dimethylphenol / 2,5-dimethylphenol, m-cresol / 2,5-dimethylphenol / 3,4-dimethylphenol, m-cresol / 2,3-dimethylphenol / 2,3,5-trimethylphenol, m-cresol / p-cresol / 2,3-dimethylphenol, Examples include m-cresol / p-cresol / 2,4-dimethylphenol, m-cresol / p-cresol / 2,5-dimethylphenol and m-cresol / p-cresol / 2,3,5-trimethylphenol. There is a number.

Moreover, as aldehydes polycondensed with phenols, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o- Hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, etc. I can lift it.                     

Among these aldehydes, formaldehyde, o-hydroxybenzaldehyde and the like are preferable.

The said aldehydes can be used individually or in mixture of 2 or more types. The usage-amount of aldehydes becomes like this. Preferably it is 0.4-2.0 mol with respect to 1 mol of phenols, More preferably, it is 0.6-1.5 mol.

As an acidic catalyst used for polycondensation of phenols and aldehydes, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. are mentioned, for example.

These acidic catalysts can be used individually or in mixture of 2 or more types. The usage-amount of an acidic catalyst is 1 * 10 <^{-5> -5} * 10 <^-1> mol normally with respect to 1 mol of phenols.

The polycondensation reaction is carried out in the absence of solvent or in a solvent.

As said solvent, For example, Alcohol, such as methanol, ethanol, n-propanol, i-propanol, n-butanol; Ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether; Ketones, such as ethyl methyl ketone, methyl isobutyl ketone, and 2-heptanone, etc. are mentioned.

These solvent can be used individually or in mixture of 2 or more types.

The amount of the solvent used is usually 20 to 1,000 parts by weight, preferably 50 to 800 parts by weight based on 100 parts by weight of the reaction raw material.

Although the temperature of a polycondensation reaction can be adjusted suitably according to the reactivity of a reaction raw material, it is 10-200 degreeC normally.

As the operation for carrying out the polycondensation reaction, (A) a method in which phenols, aldehydes, acidic catalysts and the like are put into the reaction vessel collectively, (B) an acidic catalyst is previously added to the reaction vessel, and phenols, aldehydes and the like are present in the presence thereof. The method of adding at the same time as the reaction proceeds can be appropriately employed.

As a method for recovering the novolak resin after the end of the polycondensation reaction, for example, (c) a method of raising the temperature in the reaction system to 130 to 230 ° C, removing volatile matter under reduced pressure, and recovering the novolak resin, ( D) The produced novolak resin is ethylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, 3-methoxy propionate methyl, 2-hydroxypropionate ethyl, propylene glycol monomethyl ether, methyl isobutyl ketone, 2-hep After dissolving in good solvents such as tanone, dioxane, methanol, and ethyl acetate, poor solvents such as water, n-hexane, n-heptane, etc. are mixed and precipitated, and the precipitated resin is then separated to obtain high novolak resin. The method of recovering a molecular weight fraction, etc. are mentioned.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC) of the novolak resin obtained in this way is workability | operativity at the time of apply | coating a radiation sensitive resin composition to a base material, and a resist From the standpoint of developability, sensitivity and heat resistance, the temperature is preferably 2,000 to 20,000, more preferably 3,000 to 15,000.

In addition, in this invention, when alkali-soluble resin has a carbon-carbon unsaturated bond, you may hydrogenate and use a part of this unsaturated bond.                     

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

(b) 1,2-quinonediazide compounds

As a 1, 2- quinone diazide compound used for this invention, the compound which produces | generates a carboxylic acid by exposure of radiation, for example, 1, 2- benzoquinone diazide- 4-sulfonic acid ester, 1, 2- benzo Quinonediazide-5-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,2-benzoquinone diazide-4- Sulfonic acid amide, 1,2-benzoquinone diazide-5-sulfonic acid amide, 1,2-naphthoquinone diazide-4-sulfonic acid amide, 1,2-naphthoquinone diazide-5-sulfonic acid amide, etc. are preferable. And more preferably 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5-sulfonic acid ester.

Specific examples of 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5-sulfonic acid ester include 2,3,4-trihydroxybenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1, 1,2 of trihydroxy benzophenones such as 2-naphthoquinone diazide-4-sulfonic acid ester and 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester Naphthoquinone diazide sulfonic acid esters;

2,2 ', 4,4'-tetrahydroxyphenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1, 2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,3 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4- Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methyl Benzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5- Sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydrate Roxy-3'-methoxybenzophenone-1,2-na Diazide-5-sulfonic acid ester, such as tetra-hydroxy-benzophenone 1,2-naphthoquinonediazide sulfonic acid esters;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenone, such as -1, 2- naphthoquinone diazide-5- sulfonic acid ester;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5 ' Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Hexahydroxy benzophene, such as a diazide-4- sulfonic acid ester and a 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester Discussion 1,2-naphthoquinone diazide sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonedia Zide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonedia Zide-5-sulfonic acid ester, 2,2,2-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,2-tri (p-hydroxy Phenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester,

Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naph Toquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis ( 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3 -Phenyl propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naph Toquinonediazide-5-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone Diazide-5-sulfonic acid ester,

Bis (2,5-dimethyl-4-hydroxyphenyl) (2-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxy Phenyl) (2-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3'3'-tetramethyl-1,1'-spirobiindene-5,6 , 7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiin Den-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfon acid ester, 2,2,4-trimethyl-7,2 ', 4 '-Trihydroxyflavane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-naph Toquinonediazide-5-sulfonic acid ester, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman-1,2-naphthoquinone di Diazide-5-sulfonic acid ester,

2- [bis (5-i-propyl-4-hydroxy-2-methylphenyl) methyl] phenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2- [bis (5-i-propyl- 4-hydroxy-2-methylphenyl) methyl] phenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1- [1- {3- (1- [4-hydroxyphenyl] -1-methyl Ethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydrate Hydroxyphenyl} -1-methylethyl] benzene-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl } -1-methylethyl] benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3- Dihydroxybenzene-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene -1,2-naphthoquinonediazide-5-sul The poly (hydroxyphenyl) such esters can be exemplified such as 1,2-naphthoquinonediazide sulfonic acid esters of alkane.

In addition to these compounds, J. Kosar et al., "Light-Sensitive Systems" (John Wiley & Sons, published in 1965) p. 339 and W. S. De Fores, Photoresist (McGraw-Hill, 1975) p. And 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5-sulfonic acid ester as described in [50] can be used.

Among these 1,2-naphthoquinone diazide-4-sulfonic acid esters and 1,2-naphthoquinone diazide-5-sulfonic acid esters, 1,2-naphthoquinone diazide-5-sulfonic acid ester is preferable, Especially 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 4 , 4'-4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5- Sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,2-tri (p- Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- Hydroxychroman-1,2-naphthoquinonedi Diazide-5-sulfonic acid ester such as, (a) it is preferred in view of the dissolution inhibiting effect in an alkali developing solution of the alkali-soluble resin.

The said 1,2-quinonediazide compound can be used individually or in mixture of 2 or more types.

The amount of the 1,2-quinonediazide compound used is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin. In this case, when the usage-amount of a 1, 2- quinonediazide compound is less than 5 weight part, the amount of carboxylic acid produced | generated by exposure will become small, and pattern formation will become difficult, and when it exceeds 50 weight part, exposure of a short time will be carried out. It is difficult to decompose all the added 1,2-quinonediazide compounds, and there exists a possibility that image development by alkaline developing solution may become difficult.

(c) component

The component (c) used in the present invention is a compound represented by the above formula (hereinafter referred to as "compound (c1)") and / or a compound having two or more epoxy groups in a molecule (hereinafter referred to as "compound (c2) It is said. "

Hereinafter, these compounds are demonstrated.

Compound (c1)-

As the compound (c1), for example, hexamethylolmelamine, hexabutylolmelamine, partially methylolated melamine or hydrogen atoms of at least some hydroxyl groups in these compounds may be substituted with linear or branched alkyl groups having 1 to 6 carbon atoms. Substituted compound etc. are mentioned.

Moreover, as a commercial item of a compound (c1), for example, cymel 202, copper 238, copper 266, copper 267, copper 272, copper 300, copper 301, copper 303, copper 325, copper 327, copper 370, copper 701, copper 1141, East 1156, East 1158 (above, Mitsui Cyanamid Co., Ltd.), Nikarak Mx-31, East 40, East 45, East 032, East 706, East 708, East 750, Nikarak Ms-11, Copper 001, Nikarak Mw-22, copper 30 (above, Sanwa Chemical Co., Ltd.), etc. are mentioned.

The said compound (c1) can be used individually or in mixture of 2 or more types.

When using a compound (c1), addition amount becomes like this. Preferably it is 1-50 weight part, More preferably, it is 5-40 weight part with respect to 100 weight part of (a) alkali-soluble resin. By using a compound (c1) in the quantity of this range, the protrusion and spacer of a favorable shape can be formed, and the radiation sensitive resin composition which shows moderate solubility with respect to an alkaline developing solution can be obtained.

Compound (c2)

Examples of the compound (c2) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cyclic aliphatic polyglycidyl ethers, and aliphatic polyglycidyl ethers. And glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, and the like.

Among these compounds (c2), bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic polyglycidyl ethers are alkali developments of radiation-sensitive resin compositions. It is preferable from the viewpoint of shape control of the resulting protrusions and spacers.

In addition, as a commercial item of a compound (c2), it is Epicoat 828, copper 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010 (above, Yuca-shell epoxy ( Note) production); Epicoat 807 (manufactured by Eucashell Epoxy Co., Ltd.) as a bisphenol F type epoxy resin; Epicoat 152, copper 154 (above, manufactured by Eucashell Epoxy), EPPN 201, copper 202 (above, manufactured by Nippon Kayaku Co., Ltd.), and the like as the phenol novolak type epoxy resin; EOCN-102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180 S 75 (Yukaka Epoxy Co., Ltd.) ) Etc; As cyclic aliphatic polyglycidyl ethers, CY-175, copper 177, copper 179 (above, manufactured by Ciba-Geigy Co., Ltd.), ERL-4206, copper 4221, copper 4234, copper 4299 (above, manufactured by UCC Corporation), Shodine 509 (manufactured by Showa Denko Co., Ltd.), Aldarite CY-182, Copper 184, Copper 192 (above, manufactured by Shiba-Kaiyi Co., Ltd.), Epiclone 200, Copper 400 (above, manufactured by Dainippon Ink, Inc.), Epicoat 871, Copper 872 (above, manufactured by Eucashell Epoxy Co., Ltd.), ED-5661, Copper 5662 (above, manufactured by Seranise Co., Ltd.), etc .; Examples of the aliphatic polyglycidyl ethers include epolite 100 MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Yushi Co., Ltd.), and the like. The said compound (c2) can be used individually or in mixture of 2 or more types.

The addition amount at the time of using a compound (c2) is 1-50 weight part with respect to 100 weight part of (a) alkali-soluble resin, More preferably, it is 5-30 weight part. By using the compound (c2) in an amount within this range, protrusions and spacers excellent in heat resistance and rubbing resistance can be formed. Moreover, when the usage-amount of a compound (c2) is less than 1 weight part, (b) reaction with the carboxylic acid produced | generated by exposure to a 1, 2- quinonediazide compound does not fully advance, and the heat resistance of the processus | protrusion and spacer formed In addition, there is a possibility that solvent resistance becomes insufficient. On the other hand, if it exceeds 50 parts by weight, the softening point of the formed protrusions and spacers decreases, making it difficult to maintain the shape during the heat treatment in the forming process.

Other additives

The following other additive can be added to the radiation sensitive resin composition of this invention as needed.

-Sensitizer-

A sensitizer is a component which has an effect which further improves the sensitivity of a radiation sensitive resin composition.

Examples of such sensitizers include 2H-pyrido (3,2-b) -1,4-oxazine-3 (4H)-warms and 10H-pyrido (3,2-b)-(1,4 ) -Benzothiazines, urazoles, hydantoins, barbiturates, glycine anhydrides, 1-hydroxybenzotriazoles, aloxanes, maleimides, flavones, dibenzalacetones, dibenzalcyclohexanes, Carcones, xanthenes, thioxanthenes, porphyrins, phthalocyanines, acridines, anthracenes, benzophenones, acetophenones, coumarins having a substituent at the 3-position and / or 7-position, and the like. Can be.

These sensitizers can be used individually or in mixture of 2 or more types. The addition amount of a sensitizer is 30 weight part or less normally with respect to 100 weight part of (a) alkali-soluble resin, Preferably it is 0-20 weight part.

-Trihalomethyl group containing -s-triazine-

Trihalomethyl group containing -s-triazine consists of a compound represented by following formula (2).

In the formula, X represents a halogen atom, A represents a group represented by -CX ₃ or the following formulas 3 to 8, B, D and E independently of each other a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, Hydroxyl group, straight or branched alkyl group of 1 to 10 carbon atoms, aryl group of 6 to 12 carbon atoms, straight or branched alkoxyl group of 1 to 10 carbon atoms, straight or branched alkyl tea of 1 to 10 carbon atoms Or a secondary amino group having an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched keto having 1 to 10 carbon atoms An alkyl group, a ketoaryl group having 6 to 12 carbon atoms, a straight or branched alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear or branched alkylcarbonyloxy group having 2 to 20 carbon atoms, and m is 1 to 5 The number.

Examples of the trihalomethyl group-containing s-triazine include 2,4,6-tris (trichloromethyl) -s-triazine and 2-phenyl-4,6-bis (trichloromethyl) -s- Triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (2-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (3-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (2-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methoxy-β-styryl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-tri Methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (3-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methoxynaph Tyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, etc. are mentioned. .

Among these compounds, 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.

The said trihalomethyl group containing -s-triazine can be used individually or in mixture of 2 or more types.

The addition amount of the trihalomethyl group-containing s-triazine is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the (a) alkali-soluble resin.

Low molecular weight compounds containing other phenolic hydroxyl groups

As another phenolic hydroxyl group containing low molecular weight compound, for example, 1, 1-bis (2, 5- dimethyl- 4-hydroxyphenyl) acetone, 1, 1-bis (2, 4- dihydroxyphenyl) acetone, 1 , 1-bis (2,6-dimethyl-4-hydroxyphenyl) acetone, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxy-2-methylbenzene etc. are mentioned.

These other phenolic hydroxyl group containing low molecular weight compounds can be used individually or in mixture of 2 or more types.

The addition amount of another phenolic hydroxyl group containing low molecular weight compound becomes like this. Preferably it is 50 weight part or less, More preferably, it is 45 weight part or less with respect to 100 weight part of (a) alkali-soluble resin.

Onium salt compound

An onium salt compound consists of a compound represented by following formula (9).

(A) _n Z ⁺ Y ^-

Wherein, A is the same meaning as A in the formula 2, n is 2 or 3, Z ⁺ denotes the S ⁺ or I ^+, Y ^- is _{^{BF 4 -, PF 6 -,}} SbF 6 -, AsF ₆ ^-, p- toluenesulfonic represents a sulfonic acid anion, acetate anion of methane sulfonic acid anion or trifluoroacetate trifluoroacetic.

As an onium salt compound, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium trifluoro, for example Methanesulfonate, diphenyl iodonium trifluoroacetate, diphenyl iodonium p-toluenesulfonate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, 4-methoxyphenylphenyl iodonium hexafluoro Rophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate , 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophospho Nate, bis (4-t-butylphenyl) iodonium hexaple Luoro arsenate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl Diaryl iodonium salts such as iodonium p-toluenesulfonate;

Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroacenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate , Triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium Hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfo Nitrate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4- Phenyl Triarylsulfonium salts such as thiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and 4-phenylthiophenyldiphenylsulfonium p-toluenesulfonate. Can be.

Among these onium salt compounds, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl Iodonium trifluoroacetate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldi Phenyl sulfonium trifluoro acetate, 4-phenylthio phenyl diphenyl sulfonium trifluoro methane sulfonate, 4-phenylthio phenyl diphenyl sulfonium trifluoro acetate, etc. are preferable.

The onium salt compounds may be used alone or in combination of two or more thereof.

The addition amount of the onium salt compound is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.

-Surfactants-                     

Surfactant is a component which has the effect | action which improves coatability (for example, striation) and alkali developability of the exposed part after film formation.

As such surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactants, such as polyethyleneglycol dialkyl ester, such as polyethyleneglycol dilaurate and polyethyleneglycol distearate, and are brand name F-top EF 301, copper 303, copper 352 (above, Shinsegae Kasei Co., Ltd.) Megapack F 171, Copper 172, Copper 173 (above, manufactured by Dainippon Ink, Inc.), Florad FC 430, Copper 431 (above, manufactured by Sumitomo 3M, Inc.), Asahi Guard AG 710, Sufron Fluorine-based surfactants such as S-382, Supron SC-101, 102, 94, 103, 104, 105 and 106 (above, manufactured by Asahi Glass Co., Ltd.); KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow No. 57, 95 (above, Kyoisha Chemical Co., Ltd. make), etc. are mentioned.

The said surfactant can be used individually or in mixture of 2 or more types. The addition amount of surfactant is 0.5 weight part or less normally, Preferably it is 0.2 weight part or less with respect to the total solid of a radiation sensitive resin composition.

The radiation-sensitive resin composition of the present invention is particularly useful for forming spacers for other liquid crystal display elements, in addition to being preferable for forming projections and / or spacers for vertically aligned liquid crystal display elements.

Composition solution

It is preferable to use the radiation sensitive resin composition in this invention as a solution (henceforth a "composition solution") melt | dissolved in the suitable solvent.

As a solvent used for a composition solution, it is preferable to melt | dissolve each component of a radiation sensitive resin composition, and to have a suitable vapor pressure, without reacting with each component.

As such a solvent, For example, Ethylene glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol-n-propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, 2-heptanone, methyl isobutyl ketone and cyclohexanone; Ethyl acetate, n-butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl hydroxyacetate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate, methyl lactate, ethyl lactate, 2- Ethyl hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 2-hydroxy-3- And other esters such as methyl methyl butyrate and 3-methyl-3-methoxybutyl butylate.

These solvents can be used individually or in mixture of 2 or more types.

Moreover, as needed, with the said solvent, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, acetonyl acetone, isophorone, capro Acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate And high boiling point solvents such as carbitol acetate.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Solid content concentration is adjusted to 20-40 weight%, for example, and the composition solution in this invention can also be used, for example, filtering by the filter of about 0.2 micrometer of pore diameters as needed.

Method of forming protrusions and / or spacers

Next, using the radiation-sensitive resin composition in the present invention, the projections for the vertically-aligned liquid crystal display elements and / or the spacers for the vertically-aligned liquid crystal display elements, preferably the vertically-aligned liquid crystal display elements, on the substrate. Only the processus | protrusion of a dragon or the method of forming this processus | protrusion and the spacer for vertically-aligned liquid crystal display elements are demonstrated.

First, after apply | coating a composition solution to a board | substrate, a solvent is removed by prebaking and a film is formed.

As said board | substrate, what consists of glass, quartz, silicone, a transparent resin, etc. can be used, for example.

As a coating method of a composition solution, various methods, such as the spraying method, the roll coating method, the rotation coating method, can be used, for example.

In addition, although the conditions of prebaking differ according to the kind, compounding ratio, etc. of each component, the conditions for about 1 to 15 minutes are suitable at 70-90 degreeC.

Subsequently, after irradiating a film with radiation, such as an ultraviolet-ray, it develops with alkaline developing solution, and removes an unnecessary part and forms a predetermined pattern.

As a pattern mask and exposure operation used at the time of exposure, (1) the method of exposing once using one kind of photomask which has both patterns of a projection part and a spacer part, and (2) the photomask and spacer which have only a projection part Any of two methods of exposure using two types of photomask which have only a part may be sufficient. Moreover, as a pattern mask used for the method of (1), what has a transmittance | permeability with which a projection part and a spacer part differ can also be used.

In the present invention, however, only one of the protrusions and the spacer may be formed on the substrate in some cases, and in this case, (3) one-time exposure using either the photomask having only the protrusion and the photomask having only the spacer portion. Method is employed. In this case, the remaining protrusions or spacers required for the vertically aligned liquid crystal display element are formed by a conventionally known method.

As radiation used for exposure, although visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays, etc. can be used, ultraviolet-ray is preferable.

As said alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alkanolamines, such as dimethylethanolamine, methyl diethanolamine, and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Cyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Aqueous solutions, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the alkaline developer.

The developing method may be any of paddle method, dipping method, shower method and the like, and the developing time is usually 30 to 180 seconds.

After the alkali development, for example, running water washing is performed for 30 to 90 seconds, and the pattern is formed by drying with compressed air or compressed nitrogen, for example.

Subsequently, after exposing radiation again to the pattern after alkali development, Preferably it is a predetermined time, for example, a hotplate at predetermined temperature, for example, 150-250 degreeC with a heating apparatus, such as a hotplate and oven, for example. Prebaking and / or spacer can be formed by post-baking for 5 to 30 minutes in an oven and 30 to 90 minutes in an oven. However, a photomask may or may not be used for exposure in this process.

The height of the projections thus formed is usually 0.1 to 3.0 µm, preferably 0.5 to 2.0 µm, particularly preferably 1.0 to 1.5 µm, and the height of the spacer is usually 1 to 10 µm, preferably 2 to 8 µm, particularly Preferably it is 3-5 micrometers.

According to the method of forming the protrusions and / or spacers, the fine protrusions and spacers can be finely processed, the shape and size (height or bottom dimension) can be easily controlled, and the pattern shape, heat resistance, solvent resistance, and transparency are excellent. Can be formed stably and with good productivity, and can provide a vertically-aligned liquid crystal display device excellent in orientation, voltage retention and the like.

<Examples>

Hereinafter, although embodiment of this invention is described concretely by an Example, this invention is not restrict | limited to these Examples at all.

Synthesis Example 1

In a flask equipped with a cooling tube, a stirrer and a thermometer, 64.8 g (0.6 mol) of m-cresol, 43.2 g (0.4 mol) of p-cresol, 75.4 g of a 37% by weight aqueous formaldehyde solution (0.93 mol of formaldehyde), oxalic acid dihydrate After adding 0.63 g (0.005 mol), the flask was immersed in an oil bath and polycondensed under stirring while refluxing the reaction solution for 4 hours. Then, after raising the temperature of the oil bath to 200 degreeC over 3 hours, the pressure in a flask was decompressed to 30-50 mmHg, volatile matter was removed, and the melted resin was cooled to room temperature, and it collect | recovered. Then, this resin was melt | dissolved in ethyl acetate so that resin concentration might be 30 weight%, 1.3 times of methanol and 0.9 times of water of this solution weight were added, stirred, and left to stand. Then, the lower layer separated into two layers was taken out, the solvent was removed and the novolak resin of Mw = 8.000 was obtained. This novolak resin is called resin (a-1).

Synthesis Example 2

In a flask equipped with a cooling tube, a stirrer and a thermometer, 64.8 g (0.6 mol) of m-cresol, 43.2 g (0.4 mol) of p-cresol, 75.4 g of a 37% by weight aqueous formaldehyde solution (0.93 mol of formaldehyde), oxalic acid dihydrate After adding 0.63 g (0.005 mol) and 270 g of methyl isobutyl ketones, polycondensation was carried out for 8 hours, stirring and keeping internal temperature at 90-100 degreeC. Thereafter, the reaction solution was washed twice with 500 g of ion-exchanged water to obtain a resin solution. Thereafter, ethyl acetate was added to the resin solution, and the resin concentration was diluted to 30% by weight. Then, 1.3 times the amount of methanol and 0.9 times the amount of water of the solution was added, stirred, and left to stand. Then, the lower layer separated into two layers was taken out, the solvent was removed and the novolak resin of Mw = 8,500 was obtained. This novolak resin is called resin (a-2).

&Lt; Synthesis Example 3 &

In a flask equipped with a cooling tube, a stirrer and a thermometer, 108.1 g (1.0 mol) of m-cresol, 75.4 g (0.93 mol of formaldehyde) in a 37% by weight aqueous formaldehyde solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, methylisobutyl After putting 270 g of ketones, polycondensation was carried out for 8 hours with stirring while maintaining the internal temperature at 90 to 100 ° C. Thereafter, the reaction solution was washed twice with 500 g of ion-exchanged water to obtain a resin solution. Thereafter, ethyl acetate was added to the resin solution, and the resin concentration was diluted to 30% by weight. Then, 1.3 times the amount of methanol and 0.9 times the amount of water of the solution was added, stirred, and left to stand. Then, the lower layer separated into two layers was taken out, the solvent was removed, and the novolak resin of Mw = 9,000 was obtained. This novolak resin is called resin (a-3).

&Lt; Synthesis Example 4 &

In a flask equipped with a cooling tube, a stirrer and a thermometer, 108.1 g (1.0 mol) of m-cresol, 75.4 g (0.93 mol of formaldehyde) in a 37% by weight aqueous formaldehyde solution, 0.63 g (0.005 mol) of oxalic acid dihydrate, methylisobutyl After putting 270 g of ketones, polycondensation was carried out for 8 hours with stirring while maintaining the internal temperature at 90 to 100 ° C. Thereafter, the reaction solution was washed twice with 500 g of ion-exchanged water to obtain a resin solution. Thereafter, ethyl acetate was added to the resin solution, and the resin concentration was diluted to 30% by weight. Then, 1.3 times the amount of methanol and 0.9 times the amount of water of the solution was added, stirred, and left to stand. Then, the lower layer separated into two layers was taken out, the solvent was removed and the novolak resin of Mw = 9,500 was obtained. This novolak resin is called resin (a-4).

&Lt; Example 1 >

100 parts by weight of the resin (a-1) as the component (a), and 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethyl as the component (b) 4,4 '-[1- {4- (1- [4-hydroxyphenyl]-consisting of a condensate of 1.0 mole of lidene] bisphenol and 2.0 mole of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 30 parts by weight of 1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, (c) 20 parts by weight of cymel 300 as a component, and Megapack F as a surfactant 0.01 parts by weight of 172 was mixed, diluted and dissolved with diethylene glycol ethyl methyl ether so that the total solid concentration was 25% by weight, and then filtered with a membrane filter having a pore diameter of 0.2 μm to prepare a composition solution (S-1). It was.

Subsequently, protrusions and spacers were formed in the following order, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3 below.

(1-1) Formation of protrusions and spacers

After apply | coating composition solution (S-1) on a glass substrate using the spinner, it prebaked for 2 minutes on the 90 degreeC hotplate, and formed the film of 4.0 micrometers in film thicknesses. Subsequently, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a residual pattern of 5 µm width corresponding to the protrusion and a residual pattern of 30 µm dots corresponding to the spacer portion. It was. Then, after developing at 25 degreeC for 60 second with 2.38 weight% tetramethylammonium hydroxide aqueous solution, it wash | cleaned with pure water for 1 minute. Thereafter, ultraviolet light having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 30 seconds, followed by post-baking at 220 ° C. for 60 minutes in an oven to form protrusions and spacers.

(1-2) Formation of Projections and Spacers

After apply | coating composition solution (S-1) on a glass substrate using the spinner, it prebaked for 2 minutes on the 90 degreeC hotplate, and formed the film of 4.0 micrometers in film thicknesses. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a 5 μm wide residual pattern corresponding to the protrusion. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a residual pattern of 30 μm dots corresponding to the spacer portion. Then, after developing at 25 degreeC for 60 second with 2.38 weight% tetramethylammonium hydroxide aqueous solution, it wash | cleaned with pure water for 1 minute. Subsequently, after exposing an ultraviolet-ray having an intensity of 100 W / m ² at a wavelength of 365 nm for 30 seconds, post-baking was performed at 220 ° C. for 60 minutes in an oven to form protrusions and spacers.

(2) evaluation of resolution

When a pattern was formed by the procedure of said (1-1) and (1-2), the case where the pattern was resolved was "good" and the case where it was not resolved was "defect".

(3) Evaluation of residual film rate

When forming the projections and the spacers using the radiation-sensitive resin composition, as described in Japanese Patent Laid-Open No. 2001-201750, when the exposure energy amount (exposure time) is changed, the change in the film reduction amount during alkali development is changed. It is preferable to have a moderate and high residual film ratio. Therefore, the residual film rate when the ultraviolet ray having an intensity of 100 W / m ² at the wavelength of 365 nm was exposed for 4 seconds, 5 seconds, or 6 seconds was measured, respectively. The case where it exists in 90 to 110% of range with respect to the residual film rate in the case of exposure for 5 second was made "good | favorableness."

(4-1) Evaluation of cross-sectional shape of protrusion

When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed by a scanning electron microscope, and the case of A or B is "good" and the case of C is "bad". It was. Cross-sectional shapes A, B, and C of the projections are typically as illustrated in FIG. 1.

A: When the dimension of the bottom part exceeds 5 micrometers and is 7 micrometers or less,

B: when the dimension of the bottom part exceeds 7 micrometers,

C: Trapezoidal shape regardless of the bottom dimension.

(4-2) Evaluation of Cross-sectional Shape of Spacer

When the cross-sectional shapes A, B and C of the spacer were defined as follows, the cross-sectional shapes of the formed spacers were observed by a scanning electron microscope, and the case of A or C was "good" and the case of B was "bad". It was. Cross-sectional shape A, B, and C of a spacer is typically as showing in FIG.

A: When the dimension of a bottom part exceeds 30 micrometers and is 36 micrometers or less,

B: when the dimension of the bottom part exceeds 36 micrometers,

C: Trapezoidal shape regardless of the bottom dimension.

(5) Evaluation of heat resistance

After apply | coating composition solution (S-1) using a spinner on a silicon substrate, it pre-baked for 2 minutes on a 90 degreeC hotplate, and after forming a film of 4.0 micrometers in thickness, Canon Ltd. to the obtained film Ultraviolet light with an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds using a manufactured PLA-501 F exposure machine (ultra high pressure mercury lamp). Then, this board | substrate was baked after 1 hour at 220 degreeC in the clean oven, the cured film was formed, and the film thickness T1 was measured. Furthermore, after carrying out the post-baking of the board | substrate which formed this cured film in a clean oven at 240 degreeC for 1 hour further, the film thickness (T2) of a cured film was measured, and the film thickness change rate (| T2-T1 | / T1) x 100 (%) was calculated and evaluated. When the value is 5% or less, it can be said that heat resistance is favorable.

(6) Evaluation of solvent resistance

In the same manner as in the above (5), the film thickness (T2) of the cured film was measured. Thereafter, the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide held at 70 ° C. for 20 minutes, and then the film thickness t2 of the cured film was measured, and the film thickness change rate (| t2-T2 | / T2) by immersion was measured. ) X 100 (%) was calculated and evaluated. When the value is 5% or less, it can be said that solvent resistance is favorable.

(7) evaluation of transparency

A cured film was formed on the glass substrate in the same manner as in the above (5) except that a glass substrate "Corning 7059" (manufactured by Corning Corporation) was used instead of the silicon substrate. Then, the light transmittance of the wavelength range of 400-800 nm was measured and evaluated about this board | substrate using the spectrophotometer "150-20 type double beam" (made by Hitachi, Ltd.). When the value is 93% or more, it can be said that transparency is favorable.

(8) Evaluation of orientation and voltage retention

Protrusions and spacers were formed in the same manner as in the above (1-1) on the electrode surface of the glass substrate having the ITO (indium oxide doped tin) film as the electrode using the composition solution (S-1). Then, after apply | coating AL1H659 (brand name, JSR Co., Ltd. product) to the glass substrate which formed the processus | protrusion and the spacer by the printing machine for liquid crystal aligning film application | coating as a liquid crystal aligning agent, it dried at 180 degreeC for 1 hour, and a film | membrane A film having a thickness of 0.05 mu m was formed.

Moreover, AL1H659 was apply | coated to the electrode surface of the other glass substrate which has an ITO film | membrane as a liquid crystal aligning agent by the printing machine for liquid crystal aligning film application, and it dried at 180 degreeC for 1 hour, and formed the film of 0.05 micrometer in thickness.

Subsequently, an epoxy resin adhesive containing glass fibers having a diameter of 5 µm was applied to the outer surface of each of the obtained liquid crystal alignment films of both substrates by screen printing, and both substrates were pressed so that the liquid crystal alignment film surfaces faced each other, and then pressed. The adhesive was cured. Thereafter, between the liquid crystal injection holes, the liquid crystal injection port manufactured by Merck Corporation MLC-6608 (brand name) was filled and the liquid crystal injection hole was sealed with an epoxy adhesive, and then the polarizing plates were bonded to the outer surfaces of both substrates so that their deflection directions were perpendicular to each other. To produce a vertically aligned liquid crystal display device. The longitudinal cross section of the obtained vertically-aligned liquid crystal display element is typically shown in FIG. In FIG. 2, 1 is a spacer, 2 is a protrusion, 3 is a liquid crystal, 4 is a liquid crystal aligning film, 5 is a color filter, 6 is a glass substrate.

Then, the orientation and voltage retention of the obtained vertically-aligned liquid crystal display element were evaluated as follows.

In evaluation of orientation, the case where abnormal domain was formed in a liquid crystal cell when voltage was turned on / off was observed with the polarization microscope, and the case where an abnormal domain was not confirmed was called "good".

In the evaluation of the voltage retention, after applying a voltage of 5 V to the liquid crystal display element, the circuit is opened, the holding voltage after 16.7 milliseconds is measured, and the ratio to the applied voltage (5 V) is calculated. The case where the value was 98% or more was "good" and the case below 98% was "bad".

<Examples 2 to 12 and Comparative Examples 1 to 2>

Except having used each component shown in following Table 1, it carried out similarly to Example 1, the composition solution was produced, the protrusion and the spacer were formed, and various evaluation was performed. The evaluation results are shown in Tables 2 and 3.

(B) component, (c1) component, and (c2) component in Table 1 are as follows.

b-1: 1.0 mol of 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol and 1,2-naphthoquinone diazide- Condensate with 2.0 moles of 5-sulfonic acid chloride

b-2: Condensate of 1.0 mol of 2,3,4-trihydroxybenzophenone and 2.6 mol of 1,2-naphthoquinone diazide-5-sulfonic acid chloride

b-3: Condensate of 1.0 mol of 2,3,4,4'-tetrahydroxybenzophenone and 2.5 mol of 1,2-naphthoquinone diazide-5-sulfonic acid chloride

b-4: 1.0 mol of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and 1.9 mol of 1,2-naphthoquinone diazide-5-sulfonic acid chloride Condensate

b-5: 1.0 mol of 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman and 1,2-naphthoquinone diazide- Condensate with 3.0 moles of 5-sulfonic acid chloride

c1-1: Cymel 300

c1-2: cymel 272

c1-3: Nikarak Ms-11

c2-1: epicoat 828

c2-2: epolite 100 MF                     

Example 13

Using the composition solution (S-1) prepared in Example 1, the composition solution (S-1) was applied by a spinner on a glass substrate, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a film thickness. A 4.0 micrometer film was formed. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a 5 μm wide residual pattern corresponding to the protruding portion. Thereafter, the solution was developed at 25 ° C. for 60 seconds with a 2.38% by weight tetramethylammonium hydroxide aqueous solution, and then washed with pure water for 1 minute. Then, after exposing the ultraviolet-ray whose intensity | strength is 100 W / m <^2> at wavelength 365nm for 30 second, it post-baked for 60 minutes at 220 degreeC in oven, and formed protrusion.

It was A as a result of observing and evaluating the cross-sectional shape with the scanning electron microscope in the procedure of said (4-1) about the obtained processus | protrusion.

As described above, the radiation-sensitive resin composition for forming the projections and / or spacers for the vertically-aligned liquid crystal display device of the present invention is excellent in resolution and residual film ratio, and has a pattern shape, heat resistance, solvent resistance, and transparency. It is possible to provide a vertically aligned liquid crystal display device having excellent projections and / or spacers and the like, and excellent in orientation, voltage retention and the like.

Further, the method for forming the projections and / or spacers for the vertically aligned liquid crystal display element of the present invention can be finely processed, and the shape and size (such as height and bottom dimension) can be easily controlled, and the pattern shape and heat resistance The micro projections and spacers excellent in solvent resistance, transparency, and the like can be stably formed with good productivity, and a vertically aligned liquid crystal display device excellent in orientation, voltage retention and the like can be provided.

Claims (7)

(1) (a) alkali-soluble resin containing novolak resin, (b) 1,2-quinonediazide compound, and (c) a compound having two or more compounds or epoxy groups represented by the following formula (1) in a molecule or Forming a film on a substrate using a radiation-sensitive resin composition containing both of these, and (2) radiation once using one kind of photomask having both patterns of protrusions and spacers on the film. A process of exposing, (3) developing the coating film with an alkaline developer after exposure, and (4) exposing radiation to the formed pattern again. Formation method of the spacer for type liquid crystal display elements. <Formula 1>

Wherein, R ¹ to R ⁶ is a hydrogen atom or a group -CH ₂ OR as independent of each other, R represents a linear or branched alkyl group having 1 to 6 carbon atoms or a hydrogen atom. delete The projection for a vertical alignment liquid crystal display element and the spacer for a vertical alignment liquid crystal display element formed simultaneously by the formation method of Claim 1. delete The vertical alignment liquid crystal display element provided with the protrusion for the vertical alignment liquid crystal display element of Claim 3, and the spacer for a vertical alignment liquid crystal display element. delete delete

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