JP2010230756A - Method of manufacturing liquid crystal display element, liquid crystal display element and negative type resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a liquid crystal display element, forming a column spacer and a projection for liquid crystal alignment having a height required for showing excellent display characteristic at the same time on a semi-transmission reflection type liquid crystal display element substrate. <P>SOLUTION: This method includes: a process 1 of coating a negative type resist composition on the semi-transmission reflection type liquid crystal display element substrate to form a resist film; a process 2 of applying active light beam to the resist film through a mask having openings of a pattern corresponding to the liquid crystal alignment projection forming part and the column spacer forming part; and a process 3 of developing the resist film already subjected to irradiation of the active light beam to form the column spacer and the projection for liquid crystal alignment at the same time. In the process 1, coating is performed so that the height of a lowest portion of the negative type resist composition coated between multi-gaps on the semi-transmission reflection type liquid crystal display element substrate is 0.6-0.9 times as large as the total of heights of the multi-gap and the negative type resist composition coated on the multi-gap. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention provides a liquid crystal display element capable of simultaneously forming a column spacer and a liquid crystal alignment protrusion having a height necessary for exhibiting excellent display characteristics on a transflective liquid crystal display element substrate. Regarding the method. Moreover, this invention relates to the liquid crystal display element manufactured using the manufacturing method of this liquid crystal display element. Furthermore, it is related with the negative resist composition used for the manufacturing method of this liquid crystal display element.

In order to improve the viewing angle of a liquid crystal display device, a method of forming arch-shaped protrusions on a transparent electrode and dividing and aligning liquid crystals in multiple directions within one pixel is used.
As a negative resist composition that can be used in the process of forming projections for dividing and aligning liquid crystals on a transparent electrode in the manufacturing process of a liquid crystal display device, for example, Patent Document 1 discloses an alkali-soluble resin, photopolymerization. A negative resist composition having an initiator and a photopolymerizable monomer as main components is disclosed. Patent Document 2 discloses a negative resist composition mainly composed of an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin.
By using these negative resist compositions, liquid crystal alignment protrusions and column spacers can be formed at the same time, and the manufacture of the liquid crystal display device can be simplified.

Conventionally, when a negative resist composition is applied onto a flat substrate to form the liquid crystal alignment protrusions and the column spacers at the same time, the negative resist composition is formed in order to flatten the surface of the applied negative resist composition. A leveling agent was added to the mold resist composition.

A transflective liquid crystal display device capable of improving the color developability in the reflective display portion and the transmissive display portion and optimizing the retardation has been put into practical use by a known technique (Patent Document 3). In general, as a method of manufacturing this apparatus, after forming a step portion called a multi-gap on a color filter using a resist composition, in order to maintain the thickness of the liquid crystal layer, the same process is performed on the multi-gap or between the multi-gap. A column spacer is formed on the color filter using a negative resist composition. Further, in the case of the vertical alignment type, a protrusion structure for liquid crystal alignment is formed on the multi-gap or between the multi-gap using the resist composition in the same manner.
On the other hand, in order to simplify the manufacturing process, a method of simultaneously forming a columnar structure (column spacer) and a protruding structure (liquid crystal alignment protrusion) in one process is conceivable. However, in general, a leveling agent is added to the resist composition for the purpose of improving the thickness uniformity of the resin film, so that protrusions and column spacers of any height necessary for exhibiting excellent display characteristics are provided. There is a problem that it is difficult to form simultaneously on or between the multi-gap. Therefore, the liquid crystal alignment protrusions and the column spacers have to be formed on a reflective liquid crystal display element substrate having a multi-gap separately by dividing each process.

JP-A-7-92689 JP 2003-330011 A Japanese Patent Laying-Open No. 2005-077941

The present invention provides a liquid crystal display element capable of simultaneously forming a column spacer and a liquid crystal alignment protrusion having a height necessary for exhibiting excellent display characteristics on a transflective liquid crystal display element substrate. It aims to provide a method. Moreover, an object of this invention is to provide the liquid crystal display element manufactured using the manufacturing method of this liquid crystal display element.

The present invention relates to a method for producing a liquid crystal display device, wherein a liquid crystal alignment protrusion and a column spacer are simultaneously formed on a transflective liquid crystal display device substrate using a negative resist composition, the negative resist composition Step 1 for forming a resist film by coating the object on the transflective liquid crystal display element substrate, and forming an opening of a pattern corresponding to the liquid crystal alignment protrusion forming portion and the column spacer forming portion in the resist film A step 2 of irradiating actinic rays through the mask, and a step 3 of simultaneously forming column spacers and protrusions for liquid crystal alignment by developing the resist film after irradiating the actinic rays, The negative resist composition in which the height of the lowest part of the negative resist composition applied between the multi-gap in step 1 is applied to the multi-gap and the multi-gap. It is a manufacturing method of the liquid crystal display device which is applied to a 0.6 to 0.9 times the total height of the object.
The present invention is described in detail below.

The inventors have determined that the height of the lowest portion of the negative resist composition applied between the multi-gap relative to the sum of the heights of the multi-gap and the negative resist composition applied over the multi-gap. By applying a negative resist composition so that the ratio falls within a specific range, a column spacer on the multi-gap and a liquid crystal alignment protrusion having a height necessary for exhibiting excellent display characteristics can be simultaneously formed. The inventors have found that it can be formed, and have completed the present invention.

In the method for producing a liquid crystal display element of the present invention, a projection for liquid crystal alignment and a column spacer are simultaneously formed using a negative resist composition.

In the method for producing a liquid crystal display element of the present invention, first, the negative resist composition is applied to a transflective liquid crystal display element substrate to form a resist film.
In the step 1, the negative resist composition is a negative resist composition in which the height of the lowest part of the negative resist composition applied between the multi-gap is applied on the multi-gap and the multi-gap. It coats so that it may become 0.6 to 0.9 times the sum total of height.
The height of the lowest part of the negative resist composition applied between the multi-gap is 0.6 times the total height of the multi-gap and the negative resist composition applied on the multi-gap. If it is less than the range, the obtained protrusions for liquid crystal alignment become too low, and the alignment cannot be controlled sufficiently. The height of the lowest part of the negative resist composition applied between the multi-gap is 0.9 times the total height of the multi-gap and the negative resist composition applied on the multi-gap. If it exceeds 1, the obtained protrusion for liquid crystal alignment becomes too high, resulting in a decrease in contrast or light leakage.
FIG. 1 shows a schematic diagram of a cross section of a transflective liquid crystal display element substrate coated with a negative resist composition.

Examples of the negative resist composition include those containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a leveling agent.
Negative type coated between multiple gaps using a general coating method such as spin coating by specifying the viscosity of the negative resist composition and the structure and content of the leveling agent contained The height of the lowest part of the resist composition can be within the above-described range.

In the above negative resist composition, the preferred lower limit of the viscosity measured at 25 ° C. and 30 rpm using an E-type viscometer is 4.5 mPa · s, and the preferred upper limit is 10.0 mPa · s. When the viscosity of the negative resist composition is less than 4.5 mPa · s, the film thickness when applied may be insufficient. If the viscosity of the negative resist composition exceeds 10.0 mPa · s, the resulting liquid crystal alignment protrusions may become too high, resulting in a decrease in contrast or light leakage. The more preferable lower limit of the viscosity of the negative resist composition is 5.0 mPa · s, and the more preferable upper limit is 9.5 mPa · s.

The leveling agent is not particularly limited, but preferably has a fluoro group. Since the leveling agent has a fluoro group, the coated surface when the obtained negative resist composition is coated can be appropriately formed into a concavo-convex shape along a multi-gap, and exhibits excellent display characteristics. The liquid crystal alignment protrusions having a height required for the above can be formed.

The weight average molecular weight of the leveling agent is not particularly limited, but a preferred lower limit is 3000. When the weight average molecular weight of the leveling agent is less than 3000, the leveling agent volatilizes in the pre-baking step of volatilizing the solvent of the resist material, and sufficient film uniformity may not be obtained. A more preferable lower limit of the weight average molecular weight of the leveling agent is 3500.

Examples of commercially available leveling agents include Megafac R-08 (manufactured by DIC) and PF-3320 (manufactured by Omninova).

Although the content of the leveling agent in the negative resist composition is not particularly limited, the preferable lower limit is 0.2 parts by weight and the preferable upper limit is 1.0 part by weight with respect to 100 parts by weight of the alkali-soluble resin described later. . When the content of the leveling agent is less than 0.2 parts by weight, a sufficient film leveling effect of the leveling agent may not be obtained. When the content of the leveling agent exceeds 1.0 part by weight, the obtained protrusion for liquid crystal alignment becomes too high, and the contrast may be lowered or light leakage may occur. The minimum with more preferable content of the said leveling agent is 0.25 weight part, and a more preferable upper limit is 0.9 weight part.

The alkali-soluble resin is not particularly limited, but those having a polymerizable double bond in the molecule are preferably used. Specific examples include alkali-soluble carboxyl group-containing polymer compounds such as copolymers obtained by copolymerizing a carboxyl group-containing monofunctional unsaturated compound and a monofunctional compound having an unsaturated double bond.

The said carboxyl group-containing monofunctional unsaturated compound is not specifically limited, For example, acrylic acid, methacrylic acid, etc. are mentioned.
The monofunctional compound having an unsaturated double bond is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl ( Examples include (meth) acrylic acid ester monomers of (meth) acrylate.
In the present specification, (meth) acrylate means acrylate or methacrylate.

The alkali-soluble carboxyl group-containing polymer compound contains other copolymer components derived from aromatic vinyl monomers, vinyl cyanide compounds, unsaturated dicarboxylic acid anhydrides, aromatic substituted maleimides, alkyl substituted maleimides, and the like. May be.
The aromatic vinyl monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene.
The vinyl cyanide compound is not particularly limited, and examples thereof include acrylonitrile and methacrylonitrile.
The unsaturated dicarboxylic acid anhydride is not particularly limited, and examples thereof include maleic anhydride.
The aromatic substituted maleimide is not particularly limited, and examples thereof include phenylmaleimide, benzylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide and the like.
The alkyl-substituted maleimide is not particularly limited, and examples thereof include methyl maleimide, ethyl maleimide, propyl maleimide, isopropyl maleimide and the like.

The alkali-soluble carboxyl group-containing polymer compound may contain other copolymer components derived from a monofunctional unsaturated compound having a hydroxyl group for the purpose of controlling solubility during development.
The monofunctional unsaturated compound having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl as monomers having one hydroxyl group in the molecule. Examples include methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the like.

The method for producing the alkali-soluble carboxyl group-containing polymer compound is not particularly limited, but the carboxyl group-containing monofunctional unsaturated compound, the monofunctional compound having an unsaturated double bond, and others added as necessary The copolymer component is copolymerized by a conventionally known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a dispersion polymerization method, an emulsion polymerization method using a radical polymerization initiator and a molecular weight regulator as necessary. And the like. Of these, the solution polymerization method is preferable.

Examples of the solvent for producing the alkali-soluble carboxyl group-containing polymer compound by the solution polymerization method include aliphatic alcohols such as methanol, ethanol, isopropanol and glycol, cellosolves such as cellosolve and butylcellosolve, Carbitols such as Tol and butyl carbitol, esters such as cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, ethers such as diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran, cyclohexanone, methyl ethyl ketone, methyl isobutyl Ketones such as ketones and polar organic solvents such as dimethyl sulfoxide and dimethylformamide can be used.

In addition, as a medium for producing the alkali-soluble carboxyl group-containing polymer compound by non-aqueous dispersion polymerization such as suspension polymerization, dispersion polymerization, emulsion polymerization, etc., for example, liquid such as benzene, toluene, hexane, cyclohexane, etc. Hydrocarbons and other nonpolar organic solvents can be used.

As said radical polymerization initiator, conventionally well-known radical polymerization initiators, such as a peroxide and an azo initiator, can be used, for example. Moreover, as said molecular weight regulator, (alpha) -methylstyrene dimer, a mercaptan-type chain transfer agent, etc. can be used, for example.

In the negative resist composition, the alkali-soluble resin is preferably an alkali-soluble (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain. When an alkali-soluble (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain is selected as the alkali-soluble resin, the negative resist composition has high sensitivity, and The liquid crystal alignment protrusion formed by curing the negative resist composition is excellent in resolution and adhesion to the substrate. The reason for this is considered to be that peeling of the pattern is suppressed as a result of the acrylic group in the side chain of the alkali-soluble resin reacting during exposure and the alkali-soluble resin itself being taken into the crosslinked structure.
The alkali-soluble (meth) acrylic copolymer has excellent compatibility with the other components of the negative resist composition because the polarity of the segments is low. As a result, problems such as development unevenness do not occur in the development process during the production of the liquid crystal alignment protrusions.

As the alkali-soluble (meth) acrylic copolymer, a copolymer composed of structural units represented by the following formulas (1a), (1b), (1c), (1d), and (1e) is preferable. is there.

In formulas (1a), (1b), (1c), (1d), and (1e), A ¹ and A ² are hydrogen, the following formulas (2a), (2b), (2c), or ( 2d), and when either A ¹ or A ² is hydrogen, the other is any of the following formulas (2a), (2b), (2c), or (2d). R ¹ represents hydrogen or a methyl group, R ² represents an alkyl group, a phenyl group, a phenyl group containing an alkyl group or an alkoxy group, a hydroxyalkyl group, or an alicyclic hydrocarbon, and R ³ represents a nitrile R ⁴ represents an alkyl group, a hydroxyalkyl group, or a radically polymerizable group-containing aliphatic hydrocarbon. Moreover, a, b, c, d, and e represent the molar ratio (%) of each component, and when a + b + c + d + e = 100, a, b, and d are 0-90, and c is 5-50. , E is 5-60.

The weight average molecular weight of the alkali-soluble (meth) acrylic copolymer is not particularly limited, but a preferable lower limit is 3000 and a preferable upper limit is 100,000. When the weight average molecular weight of the alkali-soluble (meth) acrylic copolymer is less than 3000, the adhesion of the liquid crystal alignment protrusions using the alkali-soluble (meth) acrylic copolymer may be reduced. If it exceeds 10,000, the resolution may decrease. The minimum with a more preferable weight average molecular weight of the said alkali-soluble (meth) acryl copolymer is 5000, and a more preferable upper limit is 50,000.
In addition, in this specification, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

The method for producing the alkali-soluble (meth) acrylic copolymer is not particularly limited. For example, ring-opening addition of an alicyclic epoxy group-containing unsaturated compound to a (meth) acrylic copolymer having a carboxyl group in the side chain. Examples include a method in which a part of the carboxyl group is modified by polymerization, and further, an isocyanate compound, an epoxy compound, a lactone compound, an alcohol compound, or the like is reacted with a hydroxyl group generated by modification and / or a part of the remaining carboxyl group. It is done.

The production method of the (meth) acrylic copolymer having a carboxyl group in the side chain is not particularly limited. For example, radical polymerization of a carboxyl group-containing monofunctional unsaturated compound and a (meth) acrylic acid ester monomer. Examples thereof include a method of copolymerization by a conventionally known method such as bulk polymerization, solution polymerization method, suspension polymerization method, dispersion polymerization method, emulsion polymerization method, using an initiator and, if necessary, a molecular weight adjusting agent.

Although it does not specifically limit as said alicyclic epoxy group containing unsaturated compound, For example, 3, 4- epoxy cyclohexyl (meth) acrylate etc. are used suitably.

Although it does not specifically limit as said isocyanate compound, For example, C2-C18 alkyl isocyanate and polymeric group containing isocyanate are used suitably. When the polymerizable group-containing isocyanate is used, the sensitivity during photocuring is increased, and various physical properties such as heat resistance, chemical resistance, and tack-free property are further improved.
Although the said polymerizable group containing isocyanate is not specifically limited, For example, it is preferable to use what the (meth) acryloyl group couple | bonded with the isocyanate group through the C2-C6 alkylene group. Specific examples include 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate, 2-acryloylethyl isocyanate, and the like. 2-methacryloylethyl isocyanate and 2-acryloylethyl isocyanate are, respectively, Karenz MOI and Karenz AOI (all manufactured by Showa Denko KK).

The method of reacting the isocyanate compound with a (meth) acrylic copolymer having a hydroxyl group and / or a carboxyl group in the side chain generated by the modification is not particularly limited, and the isocyanate compound is modified in the presence of a small amount of catalyst. The method of dripping or mixing in the solution of the (meth) acrylic copolymer which has a hydroxyl group and / or a carboxyl group in the side chain produced by this is mentioned.
The catalyst used in this case is not particularly limited, and examples thereof include lauric acid and dibutyltin.
If necessary, a polymerization inhibitor such as p-methoxyphenol, hydroquinone, methylhydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl-p-cresol may be used.
Furthermore, for the purpose of suppressing thickening and the like, treatment with an alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol or the like may be performed.

When the isocyanate compound is reacted with a (meth) acrylic copolymer having a hydroxyl group and a carboxyl group in the side chain generated by the modification according to the production method, a structural unit represented by the formula (2b) is formed. The

The said epoxy compound is not specifically limited, For example, a C2-C18 alkyl epoxy compound, a C2-C18 alkoxy epoxy compound, and a polymeric group containing epoxy compound are mentioned.

When the polymerizable group-containing epoxy compound is used as the epoxy compound, it is possible to realize improvement in various physical properties such as an increase in sensitivity during photocuring, heat resistance, chemical resistance, and tack-free property.
Although the said polymeric group containing epoxy compound is not specifically limited, For example, what the (meth) acryloyl group couple | bonded with the epoxy group via the C2-C6 alkylene group is preferable. Specifically, glycidyl (meth) acrylate etc. are mentioned, for example.

The method of reacting the epoxy compound with a (meth) acrylic copolymer having a hydroxyl group and / or a carboxyl group in the side chain produced by the modification is not particularly limited, and the epoxy compound is modified in the presence of a small amount of catalyst. The method of dripping or mixing in the solution of the (meth) acrylic copolymer which has a hydroxyl group and / or a carboxyl group in the side chain produced by this is mentioned.
The catalyst used in this case is not particularly limited. For example, triethylamine, tripromylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylcetylammonium bromide, tetrabutylammonium bromide, triphenylphosphine, trimethylbutyl Examples thereof include phosphonium bromide and tetrabutylphosphonium bromide.
If necessary, a polymerization inhibitor such as p-methoxyphenol, methylhydroquinone, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl-p-cresol may be used.

When the epoxy compound is reacted with a (meth) acrylic copolymer having a hydroxyl group and / or a carboxyl group in the side chain generated by the modification according to the above production method, it is represented by the formulas (2c) and (2d). A structural unit is formed.

When the isocyanate compound, the epoxy compound, the lactone compound, the alcohol compound, or the like is reacted with the (meth) acrylic copolymer having a hydroxyl group and / or a carboxyl group in the side chain generated by the modification, the above ( Among the hydroxyl groups contained in the (meth) acrylic copolymer, an amount corresponding to 0 to 100 mol% can be reacted.

In addition, when the isocyanate compound, the epoxy compound, the lactone compound, the alcohol compound, or the like is reacted with a (meth) acrylic copolymer having a hydroxyl group and / or a carboxyl group in a side chain generated by modification, the above ( Among the carboxyl groups contained in the (meth) acrylic copolymer, an amount corresponding to 0 to 90 mol% can be reacted. When the amount exceeding 90 mol% of the carboxyl group contained in the (meth) acrylic copolymer is reacted, the amount of the remaining carboxyl group becomes too small, so that alkali solubility is impaired and developability is lowered. There is.

In the above formulas (1a), (1b), (1c), (1d), and (1e), a, b, c, d, and e represent the molar ratio of each component, and a + b + c + d + e = 100 Then, the lower limit of a, b, and d is 0, and the upper limit is 90.
Further, when a + b + c + d + e = 100, the lower limit of c is 5 and the upper limit is 50. When c is less than 5, that is, when the molar ratio of the carboxyl group-containing structural unit is less than 5%, it becomes difficult to impart alkali solubility. When c exceeds 50, the swelling during development is remarkable and it becomes difficult to form a pattern.
Further, when a + b + c + d + e = 100, the lower limit of e is 5 and the upper limit is 60. When e is less than 5, the incorporation of the alkali-soluble resin into the crosslinked structure is insufficient and the crosslinking density is lowered. As a result, the shift in the development process becomes too large, and the height of the liquid crystal alignment protrusions varies. . When e exceeds 60, the crosslinking density of the crosslinked structure becomes too high, and it becomes difficult to stably form an arched shape.

Moreover, it is preferable that the said alkali-soluble resin contains the copolymerization component which has an aromatic ring in a molecule | numerator. By containing a copolymer component having an aromatic ring in the molecule, burn-in of a liquid crystal display device using the resulting negative resist composition can be suitably prevented.
The alkali-soluble resin having an aromatic ring is not particularly limited, but a benzyl (meth) acrylate copolymer is preferable because of good adhesion and developability.

The minimum with a preferable acid value of the said alkali-soluble resin is 50 mgKOH / g. When the acid value of the alkali-soluble resin is less than 50 mgKOH / g, the resolution of the negative resist is lowered, and arch-shaped liquid crystal alignment protrusions may not be stably formed. Although it does not specifically limit as an upper limit of the acid value of the said alkali-soluble resin, A preferable upper limit is 150 mgKOH / g. If the acid value of the alkali-soluble resin exceeds 150 mgKOH / g, the adhesion of the liquid crystal alignment protrusions using the negative resist to the substrate may be lowered. The more preferable lower limit of the acid value of the alkali-soluble resin is 60 mgKOH / g, and the more preferable upper limit is 140 mgKOH / g.
In the present specification, the acid value of the alkali-soluble resin is the number of mg of potassium hydroxide required for neutralization when 1 g of the alkali-soluble resin is dissolved in an organic solvent and titrated with potassium hydroxide using phenolphthalein as an indicator. Indicated by

Although content of the said alkali-soluble resin in the said negative resist composition is not specifically limited, A preferable minimum is 20 weight% with respect to the total solid, and a preferable upper limit is 80 weight%. When the content of the alkali-soluble resin is less than 20% by weight, the heat resistance and the development dissolution rate may be lowered. If the content of the alkali-soluble resin exceeds 80% by weight, the sensitivity may be lowered, or the reproducibility of the image cross-sectional shape may be poor. The minimum with more preferable content of the said alkali-soluble resin is 25 weight%, and a more preferable upper limit is 75 weight%.

The polymerizable monomer means a compound having one or more ethylenically unsaturated bonds in the molecule.
The compound having one ethylenically unsaturated bond in the molecule is not particularly limited, and examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyls thereof. Examples include ester, (meth) acrylonitrile, (meth) acrylamide, styrene and the like.

The compound having two ethylenically unsaturated bonds in the molecule is not particularly limited. For example, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl- 2-ethyl-1,3-propanediol di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, diethylene glycol (meth) acrylate, Polyethylene glycol (meth) acrylates such as triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, nonaethylene glycol (meth) acrylate, di Polyethylene glycol di (meth) such as tylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate ) Acrylate and the like.

The compound having three or more ethylenically unsaturated bonds in the molecule is not particularly limited. For example, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Multifunctional (meth) acrylate compounds such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate Etc. A compound having 3 or more of these ethylenically unsaturated bonds in the molecule is particularly suitable because the polymerization reaction proceeds rapidly and the exposure sensitivity is easily improved.

The polymerizable monomer preferably has a novolak skeleton in the unit structure.
The polymerizable monomer having the novolak skeleton is not particularly limited, and examples thereof include phenol novolac epoxy (meth) acrylate, o-cresol novolac epoxy (meth) acrylate, m-cresol novolac epoxy (meth) acrylate, and p-cresol novolak. Examples thereof include novolak epoxy (meth) acrylates such as epoxy (meth) acrylate, naphthol-modified novolak epoxy (meth) acrylate, and halogenated phenol novolac epoxy (meth) acrylate.
The general formula representing the novolak epoxy (meth) acrylate is shown in the following formula (3).

In formula (3), R ⁵ and R ⁶ represent hydrogen or a methyl group, and m represents 0 or a positive integer.

The novolac epoxy (meth) acrylate can be obtained, for example, by an esterification reaction between a novolac epoxy resin and an unsaturated monobasic acid.
Examples of the novolac epoxy resin include phenol novolac epoxy resin, o-cresol novolac epoxy resin, m-cresol novolac epoxy resin, p-cresol novolac epoxy resin, naphthol-modified novolac epoxy resin, and halogenated phenol novolac epoxy resin. .

As said unsaturated monobasic acid, the compound which has an ethylenic double bond and a carboxyl group from a reactive surface is preferable. Specific examples include (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid and the like. Of these, (meth) acrylic acid is preferred.

The method for the esterification reaction is not particularly limited. For example, in the presence of a stabilizer such as an epoxy esterification catalyst, a polymerization inhibitor, and an antioxidant, the novolak epoxy resin and the above are at a temperature of 30 to 150 ° C. Examples thereof include a method of reacting with an unsaturated monobasic acid.
The esterification catalyst is not particularly limited, and examples thereof include tertiary amines, imidazole compounds, phosphorus compounds, and organic metals.
The said polymerization inhibitor is not specifically limited, For example, hydroquinone, methyl hydroquinone, 4-methoxyphenol, etc. are mentioned.
The antioxidant is not particularly limited, and examples thereof include phosphites, phosphites, phosphites and the like.

The modification rate of the (meth) acrylate is not particularly limited, and a part of the novolac epoxy resin may be (meth) acrylate-modified, or the whole may be (meth) acrylate-modified.

The novolac epoxy (meth) acrylate preferably has an alkali-soluble functional group. When the novolac epoxy (meth) acrylate has the alkali-soluble functional group, the developability of the obtained negative resist is improved. The alkali-soluble functional group can be introduced by reacting a polybasic acid anhydride with a hydroxyl group contained in novolak epoxy (meth) acrylate. As the reaction method, for example, a method of continuing the reaction under the same conditions as the esterification reaction can be used.
A general formula representing the novolak epoxy (meth) acrylate having the alkali-soluble functional group is shown in the following formula (4).

In Formula (4), R ⁷ and R ⁸ represent hydrogen or a methyl group, and R ⁹ represents an atomic group derived from a polybasic acid anhydride and having a carboxyl group. M and n represent 0 or a positive integer.

The polybasic acid anhydride is not particularly limited. For example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, pyromellitic anhydride, trimellitic anhydride Etc. Of these, succinic anhydride or phthalic anhydride is preferred in terms of reactivity.

When the said novolak epoxy (meth) acrylate has an alkali-soluble functional group, the upper limit with preferable oxidation of the said novolak epoxy (meth) acrylate is 250 mgKOH / g. When the oxidation of the novolak epoxy (meth) acrylate having an alkali-soluble functional group exceeds 250 mgKOH / g, the adhesion may be lowered. The upper limit with more preferable oxidation of the novolak epoxy (meth) acrylate which has the said alkali-soluble functional group is 200 mgKOH / g.

The novolak epoxy (meth) acrylate has a preferable lower limit of 600 and a preferable upper limit of 2000 for the weight average molecular weight. If the weight average molecular weight of the novolak epoxy (meth) acrylate is less than 600, the amount of unreacted low molecular weight compound in the resin increases, and the remaining low molecular weight compound elutes in the liquid crystal, resulting in poor panel display. May cause. If the weight average molecular weight of the novolak epoxy (meth) acrylate exceeds 2000, a residue may be generated during development, or the resulting protrusion may not be arched. The more preferable lower limit of the weight average molecular weight of the novolak epoxy (meth) acrylate is 800, and the more preferable upper limit is 1800.

Commercially available products of the novolak epoxy (meth) acrylate are not particularly limited. For example, EA-1020, EA-1025, EA-1026, EA-1028, EA-6320, EA-6340 (all of these are Shin-Nakamura Chemical Ebecryl 150, Ebecryl 1150 (all are manufactured by Daicel Cytec), M-208, M-210 (all are manufactured by Toa Gosei Co., Ltd.), PNA-161H, CNA-142H, PCR-1169H , CCR-1159H (all are manufactured by Nippon Kayaku Co., Ltd.), Epicron N-695, Epicron N-775 (all are manufactured by DIC), PR-300, PR-310, PR-320, HRM-1004 , HRM-1005, HRM-1011, HRM-1013, HRM-2019, HR M-2021, HRM-2027, HRM-2031 (all of which are manufactured by Showa Polymer Co., Ltd.) and the like.

Although the content of the polymerizable monomer in the negative resist composition is not particularly limited, the preferable lower limit is 20% by weight and the preferable upper limit is 80% by weight with respect to the total solid content. When the content of the polymerizable monomer is less than 20% by weight, it tends to cause a decrease in sensitivity and a poor reproducibility of the image cross-sectional shape. When the content of the polymerizable monomer exceeds 80% by weight, the heat resistance and the development dissolution rate are likely to be reduced. The minimum with more preferable content of the said polymerizable monomer is 25 weight%, and a more preferable upper limit is 75 weight%.

The photopolymerization initiator is not particularly limited, and examples thereof include those conventionally known. For example, a compound capable of generating a radical that polymerizes an ethylenically unsaturated group by ultraviolet rays, a compound that generates an acid by ultraviolet rays, and the like Is mentioned.

The photopolymerization initiator is not particularly limited. For example, halomethylated triazine derivatives, halomethylated oxadiazole derivatives, imidazole derivatives, benzoin alkyl ethers, anthraquinone derivatives, benzanthrone derivatives, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoic acid Examples include acid ester derivatives, acridine derivatives, phenazine derivatives, titanocene derivatives, α-aminoalkylphenone compounds, and oxime derivatives.
The halomethylated triazine derivative is not particularly limited. For example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) ) -S-triazine and the like.
The imidazole derivative is not particularly limited, and examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) Examples include -4,5-diphenylimidazole dimer.
The benzoin alkyl ethers are not particularly limited, and examples thereof include benzoin methyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
The anthraquinone derivative is not particularly limited, and examples thereof include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
The benzophenone derivative is not particularly limited, and examples thereof include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and the like.
The acetophenone derivative is not particularly limited. For example, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1- Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone 1,1,1, -trichloromethyl- (p-butylphenyl) ketone and the like.
The thioxanthone derivative is not particularly limited, and examples thereof include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. Can be mentioned.
The benzoic acid ester derivative is not particularly limited, and examples thereof include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
The acridine derivative is not particularly limited, and examples thereof include 9-phenylacridine, 9- (p-methoxyphenyl) acridine and the like.
The phenazine derivative is not particularly limited, and examples thereof include 9,10-dimethylbenzphenazine.
The titanocene derivative is not particularly limited. For example, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2, 3,4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl- Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2 , 4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl- i-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl) -phen-1-yl, etc. Is mentioned.
The α-aminoalkylphenone compound is not particularly limited. For example, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylamino) Benzoyl) coumarin, 4- (diethylamino) Rukon, and the like.
The oxime derivative is not particularly limited. For example, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.
These photoinitiators may be used independently and 2 or more types may be used together.

In the negative resist composition, the content of the photopolymerization initiator is not particularly limited, but the preferable lower limit is 0.1 parts by weight, preferably 100 parts by weight in total of the alkali-soluble resin and the polymerizable monomer. The upper limit is 20 parts by weight. If the content of the photopolymerization initiator is less than 0.1 parts by weight, photocuring may be insufficient, and the adhesion of the liquid crystal alignment protrusions to the substrate may be reduced. When the content of the photopolymerization initiator exceeds 20 parts by weight, the photocuring reaction proceeds so much that a development residue is generated, or the shape of the obtained liquid crystal alignment protrusion is close to that of the column spacer, resulting in liquid crystal alignment abnormality. It may be a cause. The minimum with more preferable content of the said photoinitiator is 0.2 weight part, and a more preferable upper limit is 15 weight part. The more preferable lower limit of the content of the photopolymerization initiator is 0.5 parts by weight, and the more preferable upper limit is 10 parts by weight.

The negative resist composition may contain a reaction aid in order to reduce reaction disturbance due to oxygen. By using such a reaction aid and a hydrogen abstraction type photopolymerization initiator in combination, the curing rate when irradiated with light can be improved.

The reaction aid is not particularly limited, and examples thereof include amine-based, phosphine-based, and sulfonic acid-based reaction aids.
The amine-based reaction aid is not particularly limited, and examples thereof include n-butylamine, di-n-butylamine, triethylamine, triethylenetetramine, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like. .
The phosphine-based reaction aid is not particularly limited, and examples thereof include tri-n-butylphosphine.
The sulfonic acid-based reaction aid is not particularly limited, and examples thereof include s-benzylisothiouronium-p-toluenesulfinate. These reaction aids may be used alone or in combination of two or more.

The negative resist composition may contain a silane coupling agent as necessary.
The said silane coupling agent is not specifically limited, A conventionally well-known thing can be used. Especially, what has an acryloxy group or a methacryloxy group as a functional group is preferable. By containing a silane coupling agent having an acryloxy group or a methacryloxy group as a functional group, the adhesion of the negative resist composition to the substrate can be greatly improved.

The silane coupling agent having an acryloxy group is not particularly limited, and examples thereof include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.
The silane coupling agent having a methacryloxy group is not particularly limited. For example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Examples include triethoxysilane.
These silane coupling agents may be used independently and 2 or more types may be used together.

The negative resist composition usually uses an organic solvent so that the lower limit of the solid content concentration is 5% by weight and the upper limit is 50% by weight, preferably the lower limit is 10% by weight and the upper limit is 40% by weight. It is used after being prepared.
The organic solvent is not particularly limited as long as it can dissolve or disperse the above-described components and has excellent handleability. Specifically, for example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, lactic acid Examples include ethyl, methanol, ethanol, propanol, butanol and tetrahydrofuran.
Moreover, as said organic solvent, the thing of the range whose boiling point is 100-200 degreeC is used suitably, More preferably, the thing of the range whose boiling point is 120-180 degreeC is used.

The method for producing the negative resist composition is not particularly limited. For example, the alkali-soluble resin, the polymerizable monomer, the photopolymerization initiator, the leveling agent, the organic solvent, and any additive can be stirred. And mixing with a stirring blade or the like.

The coating method is not particularly limited, and conventionally known coating methods such as a spin coating method, a slit & spin coating method, a slit coating method, a spray coating method, a dip coating method, and a bar coating method can be used. . Of these, the spin coating method and the slit & spin coating method are preferable, and the slit & spin coating method is more preferable.
In the spin coating method and the slit & spin coating method, the height of the resist film can be adjusted by the number of spin rotations, and a column pacer with the required height can be formed. It can be carried out. Since the resist film obtained becomes thicker as the rotational speed is smaller, a high column spacer can be formed.

On the other hand, by satisfying the following items (1) and (2) as the composition of the negative resist, the height of the liquid crystal alignment protrusion is set to 0.6 to 0. 0, which is the sum of the height of the multi-gap and the column spacer. It can be set to 9 times.
(1) It contains an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a leveling agent having a fluoro group, and the content of the leveling agent having a fluoro group is based on 100 parts by weight of the alkali-soluble resin. 0.2 to 1.0 part by weight.
(2) Using an E-type viscometer, the viscosity when measured under the conditions of 25 ° C. and 30 rpm is 4.5 to 10 mPa · s.

Regarding the above item (1), a leveling agent having a fluoro group is preferred as the leveling agent because of its high leveling properties.
Moreover, since the effect of leveling property is small as content of the said leveling agent is less than 0.2 weight part with respect to 100 weight part of alkali-soluble resin, total height will be less than 0.6 times. When the content of the leveling agent exceeds 1.0 part by weight with respect to 100 parts by weight of the alkali-soluble resin, the height of the obtained liquid crystal alignment protrusion is 0.9 times the sum of the height of the multi-gap and the column spacer. It will be a larger value.

Regarding the above item (2), if the viscosity is less than 4.5 Pa · s, the spin cannot be rotated at a speed sufficient to satisfy the film uniformity. Can not form. When the viscosity exceeds 10 mPa · s, the height of the liquid crystal alignment protrusions obtained becomes a value larger than 0.9 times the total height of the multi-gap and the column spacer.

In the method for manufacturing a liquid crystal display element of the present invention, next, actinic rays are irradiated through a mask in which openings of patterns corresponding to the liquid crystal alignment protrusion forming portions and the column spacer forming portions of the resist film are formed. I do. By this step 2, the polymerizable monomer contained in the negative resist composition is cured in the light irradiation part.

The actinic rays are not particularly limited, and examples thereof include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Of these, ultraviolet rays are preferred.
The actinic ray exposure method is not particularly limited, but a proximity exposure method is generally used.

The preferable lower limit of the irradiation amount of the active light is 50 mJ / cm ² , and the preferable upper limit is 1000 mJ / cm ² . When the irradiation amount of the actinic ray is less than 50 mJ / cm ² , photocuring is insufficient, and a pattern may flow in the development process. When the irradiation amount of the active light exceeds 1000 mJ / cm ² , a development residue is likely to occur. The more preferable lower limit of the irradiation amount of the active light is 100 mJ / cm ² , and the more preferable upper limit is 500 mJ / cm ² .

In the method for producing a liquid crystal display element of the present invention, step 3 is then performed in which the resist film after irradiation with the actinic ray is developed to simultaneously form column spacers and liquid crystal alignment protrusions.
The solvent for the development is not particularly limited as long as it is a solvent capable of dissolving the uncured portion of the coating film. For example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate Alkali development consisting of an aqueous solution containing inorganic alkali compounds such as potassium silicate, sodium hydroxide and potassium hydroxide, and organic alkali compounds such as diethanolamine, triethylamine, triethanolamine, tetraalkylammonium hydroxide and tetramethylammonium hydroxide Liquid.

If necessary, the alkali developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, or the like. In particular, surfactants are preferably added because many surfactants have an improving effect on developability, resolution, background stains, and the like.

The surfactant used in the alkali developer is not particularly limited. For example, an anionic surfactant having a sodium naphthalenesulfonate group or a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, tetra And cationic surfactants having an alkylammonium group.

The development method is not particularly limited, but is usually performed at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C., by a method such as dip development, spray development, paddle development, brush development, or ultrasonic development.

After the development, it is preferable to sufficiently dry it in a drying oven or the like.
The drying temperature is preferably 220 ° C. or less, and the drying time is preferably 30 minutes or less. If the drying temperature exceeds 220 ° C and the drying time exceeds 30 minutes, the liquid crystal alignment protrusions and column spacers are formed on the color filter, resulting in damage to the color pigments or dyes in the openings, resulting in poor display quality. There is a fear.

In the liquid crystal display device manufactured using the method for manufacturing a liquid crystal display device of the present invention, the height of the liquid crystal alignment protrusion is 0.6 to 0.9 times the total height of the multi-gap and the column spacer. It is preferable. Such a liquid crystal display element is also one aspect of the present invention.
When the height of the liquid crystal alignment protrusion is less than 0.6 times the total height of the multigap and the column spacer, alignment control may not be sufficiently performed. When the height of the liquid crystal alignment protrusion exceeds 0.9 times the total height of the multi-gap and the column spacer, the contrast may be lowered or light leakage may occur. The height of the liquid crystal alignment protrusion is more preferably 0.65 to 0.85 times the total height of the multi-gap and the column spacer.
FIG. 2 is a schematic cross-sectional view of a transflective liquid crystal display element substrate on which liquid crystal alignment protrusions and column spacers are formed.

According to the present invention, a liquid crystal display element capable of simultaneously forming a column spacer and a liquid crystal alignment protrusion having a height necessary for exhibiting excellent display characteristics on a transflective liquid crystal display element substrate. The manufacturing method of can be provided. Moreover, according to this invention, the liquid crystal display element manufactured using the manufacturing method of this liquid crystal display element can be provided.

It is a schematic diagram of the cross section of the transflective liquid crystal display element substrate which applied the negative resist composition. It is a schematic diagram of a cross section of a transflective liquid crystal display element substrate on which liquid crystal alignment protrusions and column spacers are formed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Synthetic stirrer of alkali-soluble resin, dropping funnel, condenser, thermometer, 150 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was put in a flask equipped with a gas introduction tube, and stirred at 110 ° C. while purging with nitrogen. The temperature rose.
Next, a monomer mixture composed of 16, 4 parts by weight (0.19 mol) of methacrylic acid, 36.9 parts by weight (0.36 mol) of methyl methacrylate, and 12.3 parts by weight (0.12) of 2-ethylhexyl methacrylate was prepared. In addition, 3.6 parts by weight of t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, “Perbutyl O”) as a radical polymerization initiator was dropped into the flask over 2 hours from the dropping funnel, The reaction was continued with stirring at 110 ° C. for 3 hours. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin solution (solid content: 30% by weight) having an acid value of 100 mgKOH / g and a weight average molecular weight of 15000 was obtained.

(2) Preparation of negative resist composition 100 parts by weight of the obtained alkali-soluble resin, and 60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “EA-1020”) as a polymerizable monomer 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (manufactured by Ciba Specialty Chemicals, “OXE-01”) as a photopolymerization initiator And 5 parts by weight of 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-5103”) as a silane coupling agent, and MegaFac R-08 (manufactured by DIC) as a leveling agent having a fluoro group , 0.5 parts by weight, and PGMEA as a solvent in a total of 750 parts by weight. The Narubutsu was prepared.

(3) Formation of projections for liquid crystal alignment and column spacers The obtained negative resist composition was spin-coated at 500 rpm on a color filter substrate with ITO having a multi-gap of 1.5 μm thickness, and then at 80 ° C. for 2 minutes. A resist film was obtained by drying. As a part for forming a liquid crystal alignment protrusion by a proximity exposure method (print gap 100 μm) on the obtained resist film, a part for forming a circular opening and a column spacer having an i-line transmittance of 50% and a mask diameter of 10 μm. Ultraviolet rays of 100 mJ / cm ^{2 in} terms of i-line were irradiated using high-pressure mercury or the like through a mask having a rectangular opening with an i-line transmittance of 100% and a mask diameter of 15 × 25 μm. Thereafter, the resist film after ultraviolet irradiation was developed with a 0.1% aqueous sodium carbonate solution for 60 seconds and washed with pure water for 30 seconds. Next, a baking process was performed at 230 ° C. for 60 minutes to obtain a substrate on which protrusions for liquid crystal alignment and column spacers were formed.

(Example 2)
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 600 parts by weight.

Example 3
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 550 parts by weight.

Example 4
A substrate on which protrusions for liquid crystal alignment and column spacers were formed was obtained in the same manner as in Example 1 except that the content of Megafac R-08 in the negative resist composition was 0.25 parts by weight.

(Example 5)
Protrusion for aligning liquid crystal and column spacer in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 600 parts by weight and the content of Megafac R-08 was 0.25 parts by weight. A substrate on which was formed was obtained.

(Example 6)
Protrusions for aligning liquid crystal and column spacers in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 550 parts by weight and the content of Megafac R-08 was 0.25 parts by weight A substrate on which was formed was obtained.

(Example 7)
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of Megafac R-08 in the negative resist composition was 0.9 parts by weight.

(Example 8)
Protrusion for aligning liquid crystal and column spacer in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 600 parts by weight and the content of Megafac R-08 was 0.9 parts by weight A substrate on which was formed was obtained.

Example 9
Protrusions for liquid crystal alignment and column spacers in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 550 parts by weight and the content of Megafac R-08 was 0.9 parts by weight A substrate on which was formed was obtained.

(Example 10)
The PGMEA content in the negative resist composition is 600 parts by weight, and 0.5 parts by weight of PF-3320 (Omnova Co., Ltd.) 0.5 weights instead of 0.5 parts by weight of MegaFac R-08 as a leveling agent having a fluoro group A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the portion was used.

(Comparative Example 1)
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 850 parts by weight.

(Comparative Example 2)
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 500 parts by weight.

(Comparative Example 3)
Protrusions for aligning liquid crystal and column spacers in the same manner as in Example 1 except that the content of PGMEA in the negative resist composition was 600 parts by weight and the content of Megafac R-08 was 0.10 parts by weight. A substrate on which was formed was obtained.

(Comparative Example 4)
A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of Megafac R-08 in the negative resist composition was 1.50 parts by weight.

(Comparative Example 5)
In place of 0.5 parts by weight of MegaFac R-08, 0.5 parts by weight of DOW CORNING 11 ADDITIVE (manufactured by Toray Dow Corning) was used as a leveling agent having no fluoro group, and in the negative resist composition A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content of PGMEA was 600 parts by weight.

(Comparative Example 6)
In place of 0.5 part by weight of Megafax R-08, 0.5 part by weight of DISPERLON UVX-270 (manufactured by Enomoto Kasei Co., Ltd.) was used as a leveling agent having no fluoro group, and PGMEA in the negative resist composition was A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content was 600 parts by weight.

(Comparative Example 7)
Using 0.5 parts by weight of TA-411 (manufactured by NOF Corporation) as a leveling agent having no fluoro group instead of 0.5 parts by weight of Megafac R-08, the inclusion of PGMEA in the negative resist composition A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the amount was 600 parts by weight.

(Comparative Example 8)
Instead of 0.5 parts by weight of MegaFac R-08, 0.5 parts by weight of Riquemar P-100 (manufactured by Riken Vitamin Co., Ltd.) was used as a leveling agent having no fluoro group, and PGMEA in the negative resist composition was used. A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content was 600 parts by weight.

(Comparative Example 9)
Instead of 0.5 part by weight of Megafac R-08, 0.5 part by weight of Sorbone S-20 (manufactured by Toho Chemical Co., Ltd.) was used as a leveling agent having no fluoro group, and PGMEA in the negative resist composition was used. A substrate on which liquid crystal alignment protrusions and column spacers were formed was obtained in the same manner as in Example 1 except that the content was 600 parts by weight.

<Evaluation>
The following evaluation was performed about the negative resist composition obtained by the Example and the comparative example, and the board | substrate with which the protrusion for liquid crystal aligning and the column spacer were formed. The results are shown in Tables 1-4.
In Comparative Example 2, since the viscosity of the obtained negative resist composition was too low, film thickness measurement and pattern height evaluation could not be performed.

(1) Measurement of viscosity The viscosity of the obtained negative resist composition was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., “DVM-E”) at 25 ° C. and 30 rpm.

(2) Film thickness measurement The film thickness at the time when a resist was applied to a color filter substrate with ITO having a multi-gap was measured using a fine shape measuring apparatus (“P-16 +” manufactured by KLA-Tencor). .

(3) Pattern Height The height of the obtained column spacer and liquid crystal alignment protrusion was measured with a laser microscope (manufactured by KEYENCE, "VK-9500").

According to the present invention, a liquid crystal display element capable of simultaneously forming a column spacer and a liquid crystal alignment protrusion having a height necessary for exhibiting excellent display characteristics on a transflective liquid crystal display element substrate. The manufacturing method of can be provided. Moreover, according to this invention, the liquid crystal display element manufactured using the manufacturing method of this liquid crystal display element can be provided.

1 Multi-gap 2 Negative resist composition 3 Total height of multi-gap and negative resist composition coated on multi-gap 4 Lowest part of negative resist composition applied between multi-gap Height 5 Liquid crystal alignment protrusion 6 Column spacer 7 Total height of multi-gap and column spacer 8 Height of liquid crystal alignment protrusion

Claims (3)

A method of manufacturing a liquid crystal display element, wherein a liquid crystal alignment protrusion and a column spacer are simultaneously formed on a transflective liquid crystal display element substrate using a negative resist composition,
Step 1 of applying the negative resist composition to the transflective liquid crystal display element substrate to form a resist film;
Irradiating the resist film with actinic rays through a mask in which openings of a pattern corresponding to the liquid crystal alignment protrusion forming portion and the column spacer forming portion are formed; and
And developing the resist film after irradiating the actinic ray, thereby simultaneously forming a column spacer and a liquid crystal alignment protrusion,
The negative type in which the height of the lowest part of the negative resist composition applied between the multi-gap on the transflective liquid crystal display element substrate in the step 1 is applied to the multi-gap and the multi-gap. A method for producing a liquid crystal display element, wherein coating is performed so that the total height of the resist composition and the resist composition is 0.6 to 0.9 times. The liquid crystal display device manufactured by the manufacturing method according to claim 1, wherein the height of the liquid crystal alignment protrusion is 0.6 to 0.9 times the total height of the multi-gap and the column spacer. A characteristic liquid crystal display element. A negative resist composition for use in a method for manufacturing a liquid crystal display element, wherein a liquid crystal alignment protrusion and a column spacer are simultaneously formed on a transflective liquid crystal display element substrate using a negative resist composition,
The negative resist composition includes an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a leveling agent having a fluoro group, and the content of the leveling agent having the fluoro group is the alkali-soluble resin. The viscosity is 4.5 to 10 mPa · s when measured under the conditions of 25 ° C. and 30 rpm using an E-type viscometer with respect to 100 parts by weight. A negative resist composition characterized by the above.

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