JP2007304544A - Negative resist for forming protrusion for liquid crystal alignment, protrusion for liquid crystal alignment, color filter, liquid crystal display element and manufacturing method of liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist for forming a protrusion for liquid crystal alignment capable of forming the protrusion for liquid crystal alignment having excellent adhesiveness to a substrate even when a bottom area is minute and excellent height and shape stability, to provide the protrusion for liquid crystal alignment formed by using the negative resist for the protrusion for liquid crystal alignment, to provide a color filter, to provide a liquid crystal display element and to provide a manufacturing method of the liquid crystal display element. <P>SOLUTION: In the negative resist for forming the protrusion for liquid crystal alignment containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator and a silane coupling agent, the alkali-soluble resin has a double bond in its molecule and has ≥100 mg KOH/g acid value. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention provides a liquid crystal alignment projection forming negative type capable of forming a liquid crystal alignment projection having excellent adhesion to a substrate and excellent height and shape stability even when the bottom area is small. The present invention relates to a resist, a protrusion for liquid crystal alignment using the negative resist for forming a protrusion for liquid crystal alignment, a color filter, a liquid crystal display element, and a method for manufacturing a liquid crystal display element.

Generally, in a liquid crystal display device, liquid crystal aligned in a direction perpendicular or parallel to the substrate is injected between two substrates on which a color filter, a black matrix, a linear transparent electrode, an alignment film, and the like are formed. It has a structure. The liquid crystal injected between these two substrates is aligned in a vertical direction, a parallel direction, or the like with respect to the substrate in the state where no electric field is applied, but the alignment state is changed by the application of an electric field, and the liquid crystal is transmitted. The amount of transmitted light can be adjusted.

Such a liquid crystal display device has been put to practical use as a liquid crystal television used for a large-screen television in recent years because it is thinner and consumes less power than a conventional display device using a cathode ray tube. However, the liquid crystal display element has a problem that the viewing angle is narrower than that of a display device using a cathode ray tube, and with the widespread use of a large-screen liquid crystal television, an improvement in the viewing angle has been strongly demanded.

As a method for improving the viewing angle of a liquid crystal display device, conventionally, an arch-shaped protrusion is formed on a transparent electrode, and the liquid crystal is locally tilted by using the slope of the protrusion so that the liquid crystal can be oriented in multiple directions within one pixel. A method of dividing and aligning is known. Conventionally, the arch-shaped protrusion formed on such a transparent electrode is formed by forming a protrusion having a substantially rectangular cross section by a photolithographic technique using a positive resist, and then heating and reflowing the protrusion. It was arched. As such a positive resist, for example, Patent Document 1 discloses a resist containing a naphthoquinonediazide compound and a novolac resin.

However, the projections formed on the transparent substrate using the positive resist are heated and reflowed to form an arch shape. Therefore, depending on the bottom width of the pattern to be formed and the heating temperature, the height of the arch shape of the obtained projection, There is a problem in that the contact angle and the like differ, and liquid crystal alignment unevenness and display unevenness occur. In addition, the positive resist disclosed in Patent Document 1 has a problem in that the unreacted naphthoquinone diazite and the novolak resin undergo a coupling reaction by heating to cause the resist to turn red. In addition, the alkali-soluble carboxylic acid produced by photolysis of naphthoquinonediazide causes a difference in solubility in the alkaline developer between the exposed and unexposed areas. Compared to negative resists that generate a difference, the margin of development conditions is narrow, and it is affected by development deterioration due to oxygen in the air, so it is difficult to manage the development state. Further, the manufacturing process of the liquid crystal display device includes a step of using various resists in addition to the step of forming protrusions on the transparent electrode, but the resist used in the color filter step is usually a negative resist. For this reason, the use of a positive resist only in the process of forming protrusions on the color filter substrate has caused the manufacturing process to become complicated.

On the other hand, for example, Patent Document 2 discloses providing a protrusion on an electrode using a negative resist mainly composed of an alkali-soluble resin, a photopolymerization initiator, and a photopolymerizable monomer. However, this method has a problem that, when the bottom area of one of the liquid crystal alignment protrusions to be formed is small, the margin of the developing condition is narrow, and the adhesion of the protrusion to the substrate is reduced.

Furthermore, Patent Document 3 discloses a photosensitive resin composition mainly composed of an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin as a negative resist for forming projections for liquid crystal split alignment. . However, this photosensitive resin composition requires heating and melting at a high temperature of 230 ° C. in order to obtain a target shape, so that the resin itself is damaged and protrusions are formed on the color filter. In such a case, there is a problem that the color pigment or dye of the color filter is damaged and the display quality itself is deteriorated.
JP-A-7-92689 JP 2003-330011 A JP 2006-11359 A

The present invention provides a liquid crystal alignment projection forming negative type capable of forming a liquid crystal alignment projection having excellent adhesion to a substrate and excellent height and shape stability even when the bottom area is small. A method for producing a resist, a liquid crystal alignment protrusion, a color filter, a liquid crystal display element, and a liquid crystal display element using the negative resist for forming the liquid crystal alignment protrusion.

The present invention is a negative resist for liquid crystal alignment projection formation containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a silane coupling agent, and the alkali-soluble resin is polymerizable within the molecule. This is a negative resist for forming protrusions for liquid crystal alignment having a double bond and an acid value of 100 mgKOH / g or more.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have found that a negative resist for forming protrusions for liquid crystal alignment for splitting and aligning liquid crystals on a substrate surface such as a color filter, an alkali-soluble resin, a polymerizable monomer, and a photopolymerization start And a composition containing a silane coupling agent, and the alkali-soluble resin has a polymerizable double bond in the molecule and has an acid value of a specific value or more. By the method, for example, even when the bottom area is as small as 120 μm ² or less, it is possible to form an arch-shaped liquid crystal alignment protrusion having excellent adhesion to the substrate and excellent height and shape stability. As a result, the present invention has been completed.

The negative resist for forming liquid crystal alignment projections of the present invention (hereinafter also referred to as negative resist of the present invention) contains an alkali-soluble resin.
The alkali-soluble resin has a polymerizable double bond in the molecule. Such an alkali-soluble resin is not particularly limited, and for example, an alkali-soluble carboxyl group-containing copolymer such as a copolymer obtained by copolymerizing a carboxyl group-containing monofunctional unsaturated compound and a monofunctional compound having an unsaturated double bond. Examples include molecular compounds.

The carboxyl group-containing monofunctional unsaturated compound is not particularly limited, and examples thereof include acrylic acid and methacrylic acid.
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, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid dicyclopentanyloxyethyl, (meth) acrylic And (meth) acrylic acid ester monomers such as isobornyl acid, dicyclopentanyl (meth) acrylate, and benzyl (meth) acrylate. In addition, in this specification, (meth) acryl means acryl and / or methacryl.

The alkali-soluble carboxyl group-containing polymer compound includes aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Unsaturated maleic anhydrides such as maleic anhydride; aromatic substituted maleimides such as phenylmaleimide, benzylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide; alkyl-substituted maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, etc. You may contain the component which consists of.

Furthermore, the alkali-soluble carboxyl group-containing polymer compound may contain 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 of the monomer having one hydroxyl group in the molecule include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, Examples include 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate.

In the alkali-soluble carboxyl group-containing polymer compound, the preferred lower limit of the ratio of components attributable to the carboxyl group-containing monofunctional unsaturated compound is 5% by weight, and the preferred upper limit is 50% by weight. If it is less than 5% by weight, it is difficult to impart alkali solubility, and if it exceeds 50% by weight, swelling during development may be remarkably difficult to form a pattern. A more preferred lower limit is 10% by weight, and a more preferred upper limit is 40% by weight.

The method for copolymerizing the carboxyl group-containing monofunctional unsaturated compound and the monofunctional compound having an unsaturated double bond is not particularly limited. For example, using a radical polymerization initiator and, if necessary, a molecular weight regulator. And polymerizing by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, and emulsion polymerization. Of these, solution polymerization is preferred.

Solvents for producing the alkali-soluble carboxyl group-containing polymer compound by solution polymerization include, for example, aliphatic alcohols such as methanol, ethanol, isopropanol and glycol; cellosolvs such as cellosolve and butylcellosolve; carbitol and butyl Carbitols such as carbitol; esters such as cellosolve acetate, carbitol acetate and propylene glycol monomethyl ether acetate; ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran; ketones such as cyclohexanone, methyl ethyl ketone and methyl isobutyl ketone; A polar organic solvent such as dimethyl sulfoxide or 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.

It does not specifically limit as said radical polymerization initiator, For example, conventionally well-known radical polymerization initiators, such as a peroxide and an azo initiator, can be used. 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 of the present invention, the alkali-soluble resin is preferably an alkali-soluble (meth) acrylic copolymer having a (meth) acryl 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 of the present invention is cured for liquid crystal alignment. High sensitivity, resolution, and adhesion by the substrate can be obtained on the protrusions. This is because the alkali-soluble resin itself is taken into the cross-linked structure due to the reaction of the acrylic group in the side chain of the alkali-soluble resin during the exposure, so that development shift and pattern peeling are suppressed. It is done.
Moreover, since the said alkali-soluble (meth) acryl copolymer has the low polarity of a segment, it is excellent in the compatibility in the negative resist of this invention. 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.

In formulas (1a), (1b), (1c), (1d) and (1e), A ¹ and A ² represent hydrogen, the following formulas (2a), (2b), (2c) or (2d) , A ¹ or A ² is hydrogen, the other is any of the following formulas (2a), (2b), (2c) or (2d). R ¹ represents hydrogen and / 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 to 90, c is 5 to 50, and e is 5 ~ 60.

Although it does not specifically limit as a weight average molecular weight of the said alkali-soluble (meth) acryl copolymer, A preferable minimum is 3000 and a preferable upper limit is 100,000. If it is less than 3000, the adhesion of the liquid crystal alignment protrusions may be lowered, and if it exceeds 100,000, the resolution may be lowered. A more preferred lower limit is 5000, and a more preferred upper limit is 50,000.
In addition, in this specification, the said weight average molecular weight is a value calculated | required by polystyrene conversion, measuring with gel permeation chromatography.

Although it does not specifically limit as a manufacturing method of the said alkali-soluble (meth) acryl copolymer, For example, an alicyclic epoxy group containing unsaturated compound is ring-opened to the (meth) acryl copolymer which has a carboxyl group in a side chain. A method in which a part of the carboxyl group is modified by addition 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. Can be mentioned.

The method for producing the (meth) acrylic copolymer having a carboxyl group in the side chain is not particularly limited. For example, a carboxyl group-containing monofunctional unsaturated compound and a (meth) acrylic acid ester monomer are used as radicals. Examples thereof include a method of copolymerization by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization or emulsion polymerization using a polymerization 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 it does not specifically limit as said polymerizable group containing isocyanate, For example, it is preferable to use what the (meth) acryloyl group couple | bonded with the isocyanate group through the C2-C6 alkylene group. Specifically, for example, 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate, 2-acryloylethyl isocyanate and the like can be mentioned, and 2-methacryloylethyl isocyanate and 2-acryloylethyl isocyanate are respectively Karenz MOI, And it is marketed as Karenz AOI (all are made by Showa Denko KK).

The method of reacting the isocyanate compound with the (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 added in the presence of a small amount of the catalyst. The method of dripping or mixing in the solution of the (meth) acryl copolymer which has a hydroxyl group and / or a carboxyl group in the side chain produced by modification | denaturation 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, 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 an 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 above production method, a structural unit represented by the formula (2b) is formed. .

It does not specifically limit as said epoxy compound, 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 it does not specifically limit as said polymerizable group containing epoxy compound, For example, the (meth) acryloyl group couple | bonded with the epoxy group through the C2-C6 alkylene group is preferable. Specifically, glycidyl (meth) acrylate etc. are mentioned, for example.

The method for reacting the epoxy 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 epoxy compound is added in the presence of a small amount of catalyst. The method of dripping or mixing in the solution of the (meth) acryl copolymer which has a hydroxyl group and / or a carboxyl group in the side chain produced by modification | denaturation is mentioned.
The catalyst used in this case is not particularly limited. And butylphosphonium bromide.
If necessary, a polymerization inhibitor such as p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl-p-cresol may be used.

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

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

In the above formulas (1a), (1b), (1c), (1d) and (1e), 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 have a lower limit of 0% and an upper limit of 90%. The lower limit of c is 5%, and the upper limit is 50%. The lower limit of e is 5%, and the upper limit is 60%. The lower limit of c is 5%, and the upper limit is 50%. However, when the molar ratio of the carboxyl group-containing structural unit is less than 5%, it is difficult to impart alkali solubility. If it exceeds 50%, the swelling during development is remarkable and it becomes difficult to form a pattern. Further, the preferable lower limit of e is 5%, and the preferable upper limit is 60%. However, if it is less than 5%, the incorporation of the alkali-soluble resin into the crosslinked structure becomes insufficient and the crosslinking density is lowered. When the deviation becomes too large, the height of the liquid crystal alignment protrusions varies, and when it exceeds 60%, the crosslink density of the crosslink structure becomes too high, making it difficult to stably form the shape on the arch.

In the negative resist of the present invention, the alkali-soluble resin has a lower acid value of 100 mgKOH / g. If it is less than 100 mgKOH / g, the resolution of the negative resist of the present invention is lowered, and arch-shaped projections for liquid crystal alignment cannot be stably formed. Although it does not specifically limit as an upper limit of an acid value, A preferable upper limit is 150 mgKOH / g. If it exceeds 150 mgKOH / g, the adhesion of the liquid crystal alignment protrusions using the negative resist of the present invention to the substrate may be lowered. A more preferable lower limit is 110 mgKOH / g, and a more preferable upper limit is 140 mgKOH / g.
In the present specification, the acid value of the alkali-soluble resin is defined as 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 a number.

The content of the alkali-soluble resin in the negative resist of the present invention is usually 40% by weight or more, preferably 50% by weight or more, and usually 90% by weight or less, preferably 80% by weight with respect to the total solid content. % Or less. If the amount of the alkali-soluble resin is too small, it tends to cause a decrease in heat resistance and a development dissolution rate, and if it is too much, it tends to cause a decrease in sensitivity and poor reproducibility of the image cross-sectional shape.

The negative resist of the present invention contains a polymerizable monomer.
The polymerizable monomer means a compound having one or more ethylenically unsaturated bonds in the molecule, but the difference in the solubility of the developer between the exposed portion and the non-exposed portion due to the polymerizable property, the cross-linkability and the accompanying property. From the viewpoint of expansion, it is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is more preferably an acrylate compound derived from a (meth) acryloyloxy group.

Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 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, triethylene glycol Polyethylene glycol (meth) acrylates such as (meth) acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, nonaethylene glycol (meth) acrylate; Polyethylene glycol di (meth) acrylates such as cold di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate Etc.

Examples of the compound having three or more ethylenically unsaturated bonds in the molecule include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol. Multifunctional (meth) acrylate compounds such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. 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.
These polymerizable monomers may be used independently and 2 or more types may be used together.

Although it does not specifically limit as content of the polymerizable monomer in the negative resist of this invention, A preferable minimum is 10 weight% and a preferable upper limit is 50 weight% with respect to the total solid. If it is less than 10% by weight, it tends to cause a decrease in sensitivity and poor reproducibility of the image cross-sectional shape, and if it exceeds 50% by weight, it tends to cause a decrease in heat resistance and a decrease in development dissolution rate. A more preferred lower limit is 20% by weight, and a more preferred upper limit is 40% by weight or less.

In the negative resist of the present invention, the content of the alkali-soluble resin and the content of the polymerizable monomer are preferably in a specific ratio in order to stabilize the protrusion height and the shape in contact with the substrate. Specifically, the preferred lower limit of the weight ratio of (alkali-soluble resin content) / (polymerizable monomer content) is 1, the preferred upper limit is 3.5, and the more preferred lower limit is 1.5. A more preferred upper limit is 3.

The negative resist of the present invention contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited and includes conventionally known photopolymerization initiators, such as a compound capable of generating a radical that polymerizes an ethylenically unsaturated group by ultraviolet light, and a compound that generates an acid by ultraviolet light. Can be mentioned.

Specific examples of the photopolymerization initiator include, 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 other halomethylated triazine derivatives, halomethylated oxadiazole derivatives, 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- ( -Methoxyphenyl) -4,5-diphenylimidazole dimer, imidazole derivatives such as 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, Benzoin such as benzoin isopropyl ether, benzoin alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinone derivatives, benzanthrone derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone Benzene such as 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone Phenone derivative, 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, -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthio Thioxanthone derivatives such as Sandton, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine, 9,10- Phenazine derivatives such as dimethylbenzphenazine, 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-phenyl Luolophen-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-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro- Titanocene derivatives such as 3- (pyr-1-yl) -phen-1-yl, 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-dimethylaminoethylbenzo -To, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) Α-aminoalkylphenone compounds such as cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, 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 other oxime derivatives And the like. These photoinitiators may be used independently and 2 or more types may be used together.

In the negative resist of the present invention, the content of the photopolymerization initiator is not particularly limited, but when the total of the alkali-soluble resin and the polymerizable monomer is 100 parts by weight, the preferred lower limit is 0.1 weight. Parts, and the preferred upper limit is 15 parts by weight. If the amount is less than 0.1 parts by weight, the negative resist of the present invention may not be photocured. If the amount exceeds 15 parts by weight, alkali development may not be possible in photolithography. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 10 parts by weight.
As will be described later, when the liquid crystal alignment protrusion and the column spacer are formed at the same time using the negative resist of the present invention, the preferred lower limit of the content of the photopolymerization start is alkali-soluble resin and polymerization. 0.5 parts by weight with respect to a total of 100 parts by weight of the functional monomers, and the preferred upper limit is 10 parts by weight. If it is less than 0.5 part by weight, the photocuring becomes insufficient, and the adhesion of the column spacer and the liquid crystal alignment projection to the substrate may be lowered. If it exceeds 10 parts by weight, the photocuring reaction proceeds too much. The shape of the liquid crystal alignment protrusions produced through the steps described later is close to that of the column spacer, which may cause a liquid crystal alignment abnormality.

The negative resist of the present invention 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 photoreaction initiator in combination, the curing rate when irradiated with light can be improved.

Examples of the reaction aid include amines such as n-butylamine, di-n-butylamine, triethylamine, triethylenetetramine, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate; tri-n-butylphosphine, etc. Phosphinic compounds such as sulphonic acid such as s-benzylisothiouronium-p-toluenesulfinate can be used. These reaction aids may be used alone or in combination of two or more.

The negative resist of the present invention contains a silane coupling agent.
The silane coupling agent serves to improve the adhesion between the negative resist of the present invention and the substrate. Such a silane coupling agent is not particularly limited, and conventionally known ones 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-waiting methacryloxy group as a functional group, the adhesion of the negative resist of the present invention to the substrate can be greatly improved.

Examples of the silane coupling agent having an acryloxy group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.
Examples of the silane coupling agent having a methacryloxy group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltri An ethoxysilane etc. are mentioned.
These silane coupling agents may be used independently and 2 or more types may be used together.

In the negative resist of the present invention, the content of the silane coupling agent is not particularly limited, but when the total of the alkali-soluble resin and the polymerizable monomer is 100 parts by weight, the preferred lower limit is 0.1 weight. Parts, and the preferred upper limit is 15 parts by weight. If it is less than 0.1 part by weight, the adhesion to the substrate may be lowered, and if it exceeds 15 parts by weight, an alkali development residue may occur in photolithography. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 10 parts by weight.

In the negative resist of the present invention, the components constituting the negative resist of the present invention described above usually use an organic solvent, the lower limit of the solid content concentration is 5% by weight, the upper limit is 50% by weight, preferably the lower limit is It is used after being prepared so that the content is 10% by weight and the upper limit is in the range of 40% by weight.
The organic solvent is not particularly limited as long as it can dissolve and 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 (hereinafter abbreviated as “PGMAc”), methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, Examples include chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, methanol, ethanol, propanol, butanol, tetrahydrofuran and the like.
Moreover, as said organic solvent, 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.

Next, a method for manufacturing a liquid crystal alignment protrusion using the negative resist of the present invention will be described.
In order to produce the liquid crystal alignment protrusions using the negative resist of the present invention, first, the negative resist of the present invention is applied on a substrate to have a predetermined thickness to form a coating.
The coating method is not particularly limited, and for example, conventionally known coating methods such as spin coating, slit & spin, slit coating, spray coating, dip coating, and bar coating can be used.

Next, actinic rays such as ultraviolet rays are irradiated on the formed film through a mask on which a predetermined pattern is formed. Thereby, in the light irradiation part, the alkali-soluble resin, the polymerizable monomer, and the photopolymerization initiator contained in the negative resist of the present invention are reacted and photocured.
The irradiation wavelength of the active light is not particularly limited, but it is preferable to use ultraviolet rays having a wavelength of about 250 to 400 nm. The irradiation dose of an actinic ray, preferable lower limit is 50 mJ / cm ^2, a preferred upper limit is less than 200 mJ / cm ^2. If it is less than 50 mJ / cm ² , the photocuring is insufficient and the subsequent alkali treatment may dissolve the exposed area and a pattern may not be formed. When it is 200 mJ / cm ² or more, the photocuring of the surface portion of the film is sufficiently advanced, and the shape of the liquid crystal alignment protrusions to be manufactured becomes a trapezoidal shape, which may cause a liquid crystal alignment abnormality.

Next, the photocured product after photocuring is alkali-developed to form a liquid crystal alignment projection having a predetermined pattern made of the photocured product of the negative resist of the present invention on the substrate.
The solvent used in the alkali development treatment is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured part. For example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate An aqueous solution containing an inorganic alkali compound such as potassium silicate, sodium hydroxide or potassium hydroxide, or an organic alkali compound such as diethanolamine, triethylamine, triethanolamine, tetraalkylammonium hydroxide or tetramethylammonium hydroxide.

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, and the like. In particular, it is preferable to add a surfactant because many surfactants have an improving effect on developability, resolution, background stains, and the like.

Examples of the surfactant used in the alkali developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants having

Although it does not specifically limit as a method of an alkali image development process, Usually, it is carried out by methods, such as immersion development, spray development, brush development, ultrasonic development, at the development temperature of 10-50 degreeC, Preferably 15-45 degreeC.

Finally, it is thoroughly dried in a drying oven. The drying temperature is preferably 220 ° C. or less, and the drying time is preferably 30 minutes or less. When the temperature exceeds 220 ° C. and the drying time is longer than 30 minutes, when the liquid crystal alignment protrusion is formed on the color filter, the color pigment or dye in the opening is damaged and the display quality itself is deteriorated. There is a risk of letting you.

The negative resist of the present invention has excellent resolution since the contained alkali-soluble resin has a polymerizable double bond in the molecule and the acid value is 100 mgKOH / g or more. Even when the bottom area is as small as 120 μm ² or less, a liquid crystal alignment protrusion having excellent height and shape stability can be produced. Furthermore, since it consists of a composition containing the alkali-soluble resin, polymerizable monomer, photopolymerization initiator, and silane coupling agent described above, the liquid crystal alignment protrusions to be manufactured have excellent adhesion to the substrate. A projection for aligning a liquid crystal, which uses such a negative resist of the present invention and has a bottom area of 120 μm ² or less, is also one aspect of the present invention.

In addition, when the liquid crystal alignment protrusion of the present invention is provided on the color filter of the liquid crystal display element, the liquid crystal display element using the color filter has a wide viewing angle.
The negative resist for forming projections for liquid crystal alignment of the present invention or a color filter using the projection for liquid crystal alignment of the present invention is also one aspect of the present invention.
Further, a negative resist for forming a liquid crystal alignment protrusion of the present invention, a liquid crystal alignment protrusion of the present invention, or a liquid crystal display element using the color filter of the present invention is also one aspect of the present invention.

A method of manufacturing a liquid crystal display element using a negative resist for forming a projection for liquid crystal alignment according to the present invention, wherein the negative resist for forming a liquid crystal alignment protrusion is applied to a substrate to form a resist film (1 ), A step (2) of irradiating actinic rays through a mask having a predetermined pattern formed on the liquid crystal alignment protrusion forming portion and the column spacer forming portion of the resist film, and developing the resist film, When the manufacturing method of the liquid crystal display element having the step (3) of simultaneously forming the column spacer and the liquid crystal alignment protrusion is used, the liquid crystal alignment protrusion and the column spacer can be simultaneously formed, thereby shortening the manufacturing process and reducing the liquid crystal The productivity of the display element can be greatly improved. Such a liquid crystal display device manufacturing method is also one aspect of the present invention.

In the method for producing a liquid crystal display element of the present invention, first, a step (1) of forming a resist film by applying the liquid crystal alignment projection forming negative resist of the present invention to a substrate is performed.
The thickness of the resist film is adjusted to a desired thickness depending on the shape of column spacers and liquid crystal alignment protrusions described later. As a coating method, a conventionally known coating method can be used in the same manner as the method for producing the liquid crystal alignment protrusion using the negative resist of the present invention described above.

In the method for manufacturing a liquid crystal display element of the present invention, the step (2) of irradiating actinic rays through a mask in which a predetermined pattern is formed on the liquid crystal alignment protrusion forming portion and the column spacer forming portion of the resist film is then performed. Do. Thereby, in the light irradiation part, the alkali-soluble resin, the polymerizable monomer, and the photopolymerization initiator contained in the negative resist for forming a projection for liquid crystal alignment according to the present invention are reacted and photocured.

In the step (2), the liquid crystal alignment protrusion and the column spacer can be simultaneously formed by irradiating the liquid crystal alignment protrusion forming portion and the column spacer forming portion of the resist film with actinic rays having different irradiation amounts. It becomes.

In the step (2), it is preferable to use an ultraviolet ray having a wavelength of about 250 to 440 nm, and more preferably an ultraviolet ray having a wavelength of about 365 nm as the actinic ray.

When using ultraviolet rays as the active light, the preferable lower limit of the dose of ultraviolet rays to be irradiated to the liquid crystal alignment protrusions forming part of the resist film is 80 mJ / cm ^2, the upper limit is preferably 160 mJ / cm ^2. If it is less than 80 mJ / cm ² , the photo-curing may be insufficient and the liquid crystal alignment protrusions having a desired shape may not be formed when the alkali treatment is continued and the exposed portion is dissolved. When it exceeds 160 mJ / cm ² , the photocuring of the coating film surface portion is sufficiently advanced, and the shape of the obtained liquid crystal alignment protrusions may be close to that of the column spacer.

When ultraviolet rays are used as the actinic rays, the preferable lower limit of the amount of ultraviolet rays irradiated to the column spacer forming portion of the resist film is 200 mJ / cm ² , and the preferable upper limit is 400 mJ / cm ² . If it is less than 200 mJ / cm ² , the shape of the obtained column spacer becomes a protrusion shape, and the uniformity of the cell gap may be lowered. If it exceeds 400 mJ / cm ² , the cumulative irradiation time of ultraviolet rays becomes longer. The productivity of the liquid crystal display element may be reduced.

As described above, as a method of irradiating the resist film with actinic rays having different irradiation doses, for example, using a halftone mask, simultaneously exposing the liquid crystal alignment protrusion formation portion and the column spacer formation portion, The method of performing exposure to the liquid crystal alignment protrusion forming portion and the column spacer forming portion multiple times by changing the irradiation amount, etc., can be used, but when the method using the halftone mask is used, the manufacturing process is reduced. It is preferable because it becomes possible.
The halftone mask refers to a mask having a plurality of regions having different actinic ray transmittances. By using such a halftone mask, irradiation with an actinic ray is performed on an arbitrary pattern during exposure. Exposure can be performed by adjusting the amount.

In the method for manufacturing a liquid crystal display device of the present invention, when a halftone mask is used, the actinic light transmittance in the pattern portion of the liquid crystal alignment protrusion of the halftone mask is the active light transmittance of the column spacer pattern portion. When 100% is set, the preferable lower limit is 20% and the preferable upper limit is 60%. If it is less than 20%, a desired liquid crystal alignment protrusion may not be formed. If it exceeds 60%, the shape of the liquid crystal alignment protrusion may be close to that of a column spacer.

In the method for manufacturing a liquid crystal display element of the present invention, the step (3) of simultaneously forming column spacers and liquid crystal alignment protrusions is then performed by developing the resist film.
In the step (3), a developer used for developing the resist film, a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound, etc., contained as needed in the developer. For the above, the same method as the method for producing the liquid crystal alignment protrusions using the negative resist of the present invention described above can be used.
Also, with respect to the development processing method and the drying method, a method similar to the method for producing the liquid crystal alignment protrusions using the negative resist of the present invention described above can be used.

According to the present invention, even when the bottom area is small, the liquid crystal alignment projection forming negative capable of forming the liquid crystal alignment projection having excellent adhesion to the substrate and excellent in height and shape stability. A liquid crystal alignment protrusion, a color filter, a liquid crystal display device, and a method of manufacturing a liquid crystal display element using the negative resist for forming a liquid crystal alignment protrusion can be provided.

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) Synthesis of alkali-soluble resin (P-1) A flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube was charged with 150 parts by weight of PGMAc, stirred while purging with nitrogen, and heated to 110 ° C. .
Next, to a monomer mixture consisting of 32.6 parts by weight (0.38 mol) of methacrylic acid and 31.1 parts by weight (0.31 mol) of methyl methacrylate, t-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl O ) 3.6 parts by weight of the dropping funnel was dropped into the flask over 2 hours, and further stirred at 110 ° C. for 3 hours for aging.
Next, 36.4 parts by weight (0.20 mol) of 3,4-epoxycyclohexyl methacrylate, 0.36 parts by weight of triphenylphosphine and 0.15 parts by weight of methylhydroquinone were added, and the mixture was heated at 100 ° C. for 10 hours. Reacted. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin (P-1) (solid content 40%) having an acid value of 100 mgKOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 500, and a weight average molecular weight of 15000 was obtained. .

(2) Preparation of negative resist for forming liquid crystal alignment protrusions 200 parts by weight of the alkali-soluble resin (P-1) solution obtained in (1), 40 parts by weight of dipentaerythritol hexaacrylate (DPHA), photoinitiator 5 parts by weight of OXE-01 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, and as a solvent A negative resist for forming protrusions for liquid crystal alignment was prepared by mixing 100 parts by weight of PGMAc.

(Example 2)
(1) Synthesis of alkali-soluble resin (P-2) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction pipe was charged with 150 parts by weight of PGMAc, stirred while purging with nitrogen, and heated to 110 ° C. .
Next, a monomer mixture composed of 35.6 parts by weight (0.41 mol) of methacrylic acid and 28.0 parts by weight (0.28 mol) of methyl methacrylate was added to t-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl O ) 3.6 parts by weight of the dropping funnel was dropped into the flask over 2 hours, and further stirred at 110 ° C. for 3 hours for aging.
Next, 36.4 parts by weight (0.20 mol) of 3,4-epoxycyclohexyl methacrylate, 0.36 parts by weight of triphenylphosphine and 0.15 parts by weight of methylhydroquinone were added, and the mixture was heated at 100 ° C. for 10 hours. Reacted. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin (P-2) (solid content 40%) having an acid value of 120 mgKOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 500, and a weight average molecular weight of 15000 was obtained. .

(2) Preparation of negative resist for forming liquid crystal alignment projections 200 parts by weight of the alkali-soluble resin (P-2) solution obtained in (1), 40 parts by weight of dipentaerythritol hexaacrylate, OXE- as a photoinitiator 5 parts by weight of 01 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, and 100 parts by weight of PGMac as a solvent Were mixed to prepare a negative resist for forming projections for liquid crystal alignment.

(Example 3)
In the preparation of the negative resist for forming liquid crystal alignment protrusions, instead of 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, a methacryloxy group was used. A negative resist for forming protrusions for liquid crystal alignment was prepared in the same manner as in Example 2 except that 10 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. Prepared.

Example 4
In the preparation of the negative resist for forming liquid crystal alignment protrusions, instead of 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, a methacryloxy group was used. Negative resist for forming protrusions for liquid crystal alignment in the same manner as in Example 2 except that 10 parts by weight of 3-methacryloxypropyltriethoxysilane (KBE-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. Was prepared.

(Comparative Example 1)
(1) Synthesis of alkali-soluble resin (P-3) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube was charged with 150 parts by weight of PGMAc, stirred while purging with nitrogen, and heated to 110 ° C. .
Next, a monomer mixture consisting of 15.4 parts by weight (0.18 mole) of methacrylic acid and 84.7 parts by weight (0.85 mole) of methyl methacrylate was added to t-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl O ) 3.6 parts by weight of the dropping funnel was dropped into the flask over 2 hours, and the mixture was further stirred at 110 ° C. for 4 hours to be reacted. As a result, an alkali-soluble resin (P-3) (solid content 40%) having an acid value of 100 mgKOH / g and a weight average molecular weight of 15000 was obtained.

(2) Preparation of negative resist for forming liquid crystal alignment projections 200 parts by weight of the alkali-soluble resin (P-3) solution obtained in (1), 40 parts by weight of dipentaerythritol hexaacrylate, OXE- as a photoinitiator 5 parts by weight of 01 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, and 100 parts by weight of PGMac as a solvent Were mixed to prepare a negative resist for forming projections for liquid crystal alignment.

(Comparative Example 2)
(1) Synthesis of alkali-soluble resin (P-4) A flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube was charged with 150 parts by weight of PGMAc, stirred while purging with nitrogen, and heated to 110 ° C. .
Next, a monomer mixture consisting of 29.5 parts by weight (0.34 mol) of methacrylic acid and 34.5 parts by weight (0.35 mol) of methyl methacrylate was added to t-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl O ) 3.6 parts by weight of the dropping funnel was dropped into the flask over 2 hours, and further stirred at 110 ° C. for 3 hours for aging.
Next, 36.4 parts by weight (0.20 mol) of 3,4-epoxycyclohexyl methacrylate, 0.36 parts by weight of triphenylphosphine and 0.15 parts by weight of methylhydroquinone were added, and the mixture was heated at 100 ° C. for 10 hours. Reacted. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin (P-4) (solid content 40%) having an acid value of 80 mgKOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 500, and a weight average molecular weight of 15000 was obtained. .

(2) Preparation of negative resist for forming liquid crystal alignment projections 200 parts by weight of the alkali-soluble resin (P-4) solution obtained in (1), 40 parts by weight of dipentaerythritol hexaacrylate, OXE- as a photoinitiator 5 parts by weight of 01 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, and 100 parts by weight of PGMac as a solvent Were mixed to prepare a negative resist for forming projections for liquid crystal alignment.

(Comparative Example 3)
A negative resist for forming liquid crystal alignment protrusions was prepared in the same manner as in Example 2 except that the silane coupling agent having an acryloxy group was not added.

(Reference Example 1)
Instead of 10 parts by weight of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having an acryloxy group, 3-glycidoxypropyltrisilane as a silane coupling agent having an epoxy group A negative resist for forming liquid crystal alignment protrusions was prepared in the same manner as in Example 2 except that 10 parts by weight of methoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

(Evaluation)
For the negative resists for forming liquid crystal alignment protrusions obtained in Examples 1 to 4, Comparative Examples 1 to 3, and Reference Example 1, the liquid crystal alignment protrusions were formed and evaluated by the following methods. The results are shown in Table 1.
The results are shown in Table 1.

(Creation of liquid crystal alignment protrusions)
On a glass substrate on which a transparent conductive film has been formed, the negative resist for forming liquid crystal alignment projections obtained in each of the Examples, Comparative Examples, and Reference Examples is applied by spin coating, and dried at 80 ° C. for 2 minutes. A membrane was obtained. The obtained coating film was irradiated with 100 mJ / cm ² ultraviolet rays through an 8 μm square dot pattern mask, developed with a 0.1% aqueous sodium carbonate solution for 60 seconds, and washed with pure water for 30 seconds. Thereafter, after baking at 200 ° C. for 30 minutes, a liquid crystal alignment projection pattern was obtained.

(Evaluation of protrusion shape)
Whether the protrusion shape was a dome shape was observed with an optical microscope and SEM, and evaluated according to the following criteria.
○: Overall, it has a gentle dome shape, and there is no flat area at the tip of the protrusion. In addition, no snoring is seen.
X: A flat region or a sliding can be confirmed at the tip of the protrusion.

(Evaluation of pattern bottom area and adhesion)
The relationship between the bottom area of the liquid crystal alignment protrusions and the adhesiveness was observed with an optical microscope and SEM, and evaluated according to the following criteria.
Evaluation of adhesion ○: No peeling during development when the bottom area of the liquid crystal alignment protrusion is 120 μm ² or less ×: There is peeling during development when the bottom area of the liquid crystal alignment protrusion is 120 μm ² or less

(Example 5)
On the glass substrate on which the transparent conductive film was formed, the negative resist for forming liquid crystal alignment protrusions obtained in Example 1 was applied by spin coating, and dried at 80 ° C. for 2 minutes to obtain a coating film.
On the obtained coating film, an 8 μm square halftone mask having a UV light transmission region in the pattern shape of the liquid crystal alignment protrusion and the column spacer (40% UV transmittance of the pattern portion of the liquid crystal alignment protrusion, UV transmittance of 100%) through the, 120 mJ / cm ² to the liquid crystal alignment protrusions formed part was irradiated with ultraviolet rays (wavelength 365 nm) of 300 mJ / cm ² to the column spacer forming portion. Next, the film was developed with a 0.1% aqueous sodium carbonate solution for 60 seconds and washed with pure water for 30 seconds. Then, the liquid crystal aligning protrusion and the column spacer were formed by performing a baking process at 200 ° C. for 30 minutes.

The shapes of the formed liquid crystal alignment protrusions and column spacers were observed using a scanning electron microscope (SEM). As a result, the liquid crystal alignment protrusions were generally loosely dome-shaped, and the tips of the protrusions There was no flat area and no swaying was seen.
Moreover, about the column spacer, the edge of the pattern was in a sharp state, and the pattern surface was in a smooth state.

According to the present invention, even when the bottom area is small, the liquid crystal alignment protrusion can be formed that has excellent adhesion to the substrate and is excellent in height and shape stability. A negative resist, a liquid crystal alignment protrusion, a color filter, a liquid crystal display element, and a method for manufacturing the liquid crystal display element using the negative resist for forming a liquid crystal alignment protrusion can be provided.

Claims (10)

A negative resist for forming protrusions for liquid crystal alignment containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a silane coupling agent,
The negative resist for forming a projection for liquid crystal alignment, wherein the alkali-soluble resin has a polymerizable double bond in a molecule and has an acid value of 100 mgKOH / g or more. The alkali-soluble resin is an alkali-soluble (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain, and the following formulas (1a), (1b), (1c), (1d) and ( The negative resist for forming a projection for liquid crystal alignment according to claim 1, wherein the negative resist is a copolymer comprising the structural unit represented by 1e).

In formulas (1a), (1b), (1c), (1d) and (1e), A ¹ and A ² represent hydrogen, the following formulas (2a), (2b), (2c) or (2d) , A ¹ or A ² is hydrogen, the other is any of the following formulas (2a), (2b), (2c) or (2d). R ¹ represents hydrogen and / 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 to 90, c is 5 to 50, and e is 5 ~ 60.

The negative resist for forming a projection for liquid crystal alignment according to claim 1 or 2, wherein the silane coupling agent has an acryloxy group or a methacryloxy group as a functional group. A projection for forming a liquid crystal alignment, comprising the negative resist for forming a protrusion for aligning liquid crystal according to claim 1, wherein the bottom area is 120 μm ² or less. A color filter comprising the liquid crystal alignment protrusion forming negative resist according to claim 1, or the liquid crystal alignment protrusion according to claim 4. A liquid crystal display element comprising the negative alignment resist for forming liquid crystal alignment protrusions according to claim 1, 2 or 3, the liquid crystal alignment protrusion according to claim 4, or the color filter according to claim 5. . A method for producing a liquid crystal display element using the negative resist for forming a protrusion for liquid crystal alignment according to claim 1,
A step (1) of forming a resist film by coating the substrate with the liquid crystal alignment projection forming negative resist;
Irradiating actinic rays through a mask in which a predetermined pattern is formed on the liquid crystal alignment protrusion forming portion and the column spacer forming portion of the resist film, and
A method of manufacturing a liquid crystal display element, comprising developing a resist film to form a column spacer and a liquid crystal alignment protrusion at the same time (3). A mask in which a predetermined pattern is formed on the liquid crystal alignment protrusion formation portion and the column spacer formation portion, when the active light transmittance of the column spacer pattern portion is 100%, the active light transmission of the pattern portion of the liquid crystal alignment protrusion The method according to claim 7, wherein the rate is 20 to 60%. The method for manufacturing a liquid crystal display element according to claim 7 or 8, wherein in the step (2), an ultraviolet ray of 80 to 160 mJ / cm ² is irradiated to a liquid crystal alignment protrusion forming portion of the resist film. 10. The method for producing a liquid crystal display element according to claim 7, wherein the column spacer formation portion of the resist film is irradiated with ultraviolet rays of 200 to 400 mJ / cm < ² > in the step (2).