JP2009109879A - Negative-working resist for formation for protrusion for liquid crystal alignment, protrusion for the liquid crystal alignment, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative-working resist for the formation of protrusions for liquid crystal alignment, the resist allowing formation of protrusions for regulating liquid crystal alignment, in a liquid crystal display device and preventing seizure of a liquid crystal in a produced liquid crystal display device, and to provide protrusions for liquid crystal alignment, comprising the negative-working resist for formation of protrusions for liquid crystal alignment, and to provide a color filter and a liquid crystal display device. <P>SOLUTION: The negative-working resist for forming protrusions for liquid crystal alignment contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator, wherein the alkali-soluble resin has a structure having two or more bonded phenylene skeletons. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention provides a negative resist for forming a protrusion for liquid crystal alignment, which can form a protrusion for controlling the liquid crystal alignment of the liquid crystal display device, and can prevent a liquid crystal burn-in phenomenon from occurring in the manufactured liquid crystal display device. The present invention relates to a liquid crystal alignment protrusion, a color filter, and a liquid crystal display device using a negative resist for forming an alignment protrusion.

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.

In recent years, as a method for improving the viewing angle of a liquid crystal display device, 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 so-called MVA (Multidomain Vertical Alignment) system is known in which divisional alignment is performed. 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. 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. . It is considered that the use of these negative resists can simplify the production of the liquid crystal display device.
However, in a liquid crystal display device in which projections for liquid crystal alignment are formed using a conventional negative resist, when liquid crystal alignment projections are formed for a long time, abnormal alignment of liquid crystals occurs at the portion where the projections for liquid crystal alignment are formed, and the display image of such portions is displayed. There was a problem that image sticking (liquid crystal image sticking phenomenon) occurred.
JP-A-7-92689 JP 2003-330011 A JP 2006-11359 A

In view of the above situation, the present invention can form a protrusion for controlling the liquid crystal alignment of a liquid crystal display device, and can prevent a liquid crystal burn-in phenomenon from occurring in the manufactured liquid crystal display device. It is an object of the present invention to provide a liquid crystal alignment protrusion, a color filter, and a liquid crystal display device using the mold resist, the liquid crystal alignment protrusion forming negative resist.

The present invention is a negative resist for forming a protrusion for liquid crystal alignment, which contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator, and the alkali-soluble resin has a structure in which two or more phenylene skeletons are bonded. A negative resist for forming a protrusion for aligning liquid crystal.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have developed a negative resist containing an alkali-soluble resin having a specific structure with protrusions for dividing and aligning the liquid crystal of an MVA liquid crystal display device in multiple directions within one pixel. It is found that the manufactured MVA type liquid crystal display device does not cause abnormal alignment of liquid crystal in the projection forming portion and does not cause liquid crystal burn-in phenomenon even if the display is performed for a long time. The present invention has been completed.

The negative resist for forming projections for liquid crystal alignment of the present invention contains an alkali-soluble resin having a structure in which two or more phenylene skeletons are bonded.
By containing such an alkali-soluble resin, protrusions for controlling the liquid crystal alignment of the liquid crystal display device can be formed, and the liquid crystal image sticking phenomenon can be prevented from occurring in the manufactured liquid crystal display device.
Specific examples of the structure in which two or more phenylene skeletons are bonded include biphenylene, triphenylene, quarter phenylene, and the like.

In particular, the alkali-soluble resin preferably has at least one phenylene skeleton selected from the group consisting of the following general formulas (1), (2), (3) and (4) in the side chain.

R ^{1 to} R ⁹ represent H, CH ₃ , OH, COOH, NH ₂ , CN, NO ₂ , Cl, Br, I, and Y represents CH ₂ , O, CO, COO, COONH. M is a natural number of 2 to 4, and n is 1 or 2.
The general formulas (1) to (4) represent that a phenylene skeleton can be linked to the ortho, meta, and para positions with respect to the side chain.

The alkali-soluble resin is not particularly limited, but those having a polymerizable double bond in the molecule are preferably used. Specifically, for example, a monomer having a structure in which two or more phenylene skeletons are bonded and an unsaturated divalent resin are used. Examples include alkali-soluble carboxyl group-containing polymer compounds such as copolymers obtained by copolymerization with carboxyl group-containing monofunctional unsaturated compounds having a heavy bond.
Hereinafter, the alkali-soluble carboxyl group-containing polymer compound will be described in detail.

Monomers having a structure in which two or more phenylene skeletons are bonded include, for example, an epoxy ring-opening addition reaction or an esterification reaction between a compound having a structure in which two or more phenylene skeletons are bonded and a compound having an unsaturated double bond. can get.

Of the compounds having a structure in which two or more phenylene skeletons are bonded, the compound having a structure in which two phenylene skeletons are bonded is not particularly limited, and examples thereof include phenylphenol derivatives, phenylbenzoic acid derivatives, phenylaniline derivatives, biphenylyl isocyanate. Examples thereof include a narate derivative, a phenylstyrene oxide derivative, a biphenylmethanol derivative, and a biphenylacetic acid derivative.

A monomer having a structure in which three or more phenylene skeletons such as triphenylene and quarterphenylene are linearly bonded is a precursor of a compound having a halogenated phenyl group or a halogenated biphenyl group by using a cross-coupling reaction such as a Grignard reaction. Is prepared and then added to a compound having an unsaturated double bond.

The compound having a halogenated phenyl group or a halogenated biphenyl group is not particularly limited, and examples thereof include a chlorobenzene derivative, a phenylbromobenzene derivative, a phenyliodobenzene derivative, a phenylbromobenzene derivative, and a phenyliodobenzene derivative.

The compound having an unsaturated double bond is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, glycidyl acrylate, and glycidyl methacrylate.

Among them, those having a biphenylene skeleton are preferable, and specific examples include phenylphenol glycidyl ether (meth) acrylate, hydroxyethylated phenylphenol (meth) acrylate, and the like.

The carboxyl group-containing monofunctional unsaturated compound having an unsaturated double bond is not particularly limited, and examples thereof include acrylic acid and methacrylic acid.

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.

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 having an unsaturated double bond 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 producing an alkali-soluble carboxyl group-containing polymer compound by copolymerizing a monomer having a structure in which two or more phenylene skeletons are bonded and a carboxyl group-containing monofunctional unsaturated compound having an unsaturated double bond is particularly limited. For example, a method of polymerizing by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization using a radical polymerization initiator and, if necessary, a molecular weight regulator may be mentioned. 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.

The alkali-soluble carboxyl group-containing polymer compound preferably has a (meth) acryl group and a carboxyl group in the side chain.
When an alkali-soluble carboxyl group-containing polymer compound having a (meth) acryl group and a carboxyl group in the side chain is selected as the alkali-soluble resin, the negative resist for forming liquid crystal alignment protrusions of the present invention is cured. High sensitivity, resolution, and adhesion by the substrate can be obtained in the liquid crystal alignment protrusions. The reason for this is thought to be that development misalignment and peeling of the pattern are suppressed as a result of the alkali-soluble resin itself being taken into the cross-linked structure due to the reaction of the side chain acrylic groups during exposure.
In addition, since the alkali-soluble carboxyl group-containing polymer compound having a (meth) acryl group and a carboxyl group in the side chain has a low segment polarity, the phase in the negative resist for forming liquid crystal alignment protrusions of the present invention is not limited. Excellent solubility. Thereby, problems such as development unevenness do not occur in the development processing at the time of manufacturing the liquid crystal alignment protrusions and column spacers.

The method for introducing a (meth) acryl group and a carboxyl group into the side chain of the alkali-soluble carboxyl group-containing polymer compound is not particularly limited, and is alicyclic with respect to the carboxyl group of the alkali-soluble carboxyl group-containing polymer compound. Ring-opening addition polymerization of an epoxy group-containing unsaturated compound to modify a part of the carboxyl group, and further, an isocyanate compound, an epoxy compound, and a lactone compound are formed on the hydroxyl group generated by the modification and / or a part of the remaining carboxyl group. And a method of reacting an alcohol compound and the like.

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 alkali-soluble carboxyl group-containing polymer compound 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 catalyst. The method of dripping or mixing in the solution of the alkali-soluble carboxyl group containing polymer compound which has a hydroxyl group and / or a carboxyl group in the side chain produced by the said modification | denaturation is mentioned.
The catalyst used in this case is not particularly limited, and examples thereof include lauric acid and dibutyltin.
Further, 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 an isocyanate compound is reacted with an alkali-soluble carboxyl group-containing polymer compound having a hydroxyl group and a carboxyl group in the side chain produced by the modification according to the above production method, the structural unit represented by the following general formula (5) is It is formed.

R ¹⁰ represents an alkyl group, a hydroxyalkyl group or a radical polymerizable group-containing aliphatic hydrocarbon. The same applies hereinafter.

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 of reacting the epoxy compound with the alkali-soluble carboxyl group-containing polymer compound 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 alkali-soluble carboxyl group containing polymer compound which has a hydroxyl group and / or a carboxyl group in the side chain produced by the said modification | denaturation is mentioned.
The catalyst used in this case is not particularly limited. For example, triethylamine, tripromylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylcetylammonium bromide, tetrabutylammonium bromide, trimethylbutylphosphonium bromide, tetra 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 an alkali-soluble carboxyl group-containing polymer compound having a hydroxyl group and / or a carboxyl group in the side chain produced by the modification according to the above production method, the following general formula (6) and the following general formula: The structural unit shown in (7) is formed.

When the above-mentioned isocyanate compound, epoxy compound, lactone compound, alcohol compound, or the like is reacted with the alkali-soluble carboxyl group-containing polymer compound having a hydroxyl group and / or a carboxyl group in the side chain generated by the modification, the alkali-soluble carboxyl is used. The amount corresponding to 0 to 100 mol% of the hydroxyl groups contained in the group-containing polymer compound can be reacted.

In addition, when the above-mentioned isocyanate compound, epoxy compound, lactone compound, alcohol compound or the like is reacted with the alkali-soluble carboxyl group-containing polymer compound having a hydroxyl group and / or a carboxyl group in the side chain generated by modification, the alkali-soluble carboxyl group is reacted. Among the carboxyl groups contained in the group-containing polymer compound, 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.

Although it does not specifically limit as a weight average molecular weight of the said alkali-soluble resin, 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 and column spacers 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.

The ratio of the structure in which two or more phenylene skeletons are bonded in the alkali-soluble resin is not particularly limited, but a preferable lower limit is 10% by weight and a preferable upper limit is 95% by weight. When it is less than 10% by weight, burn-in may occur when it is used as a liquid crystal alignment protrusion, and when it exceeds 95% by weight, the ratio of components due to the carboxyl group-containing monofunctional unsaturated compound decreases, The developability to an alkaline aqueous solution is lowered and an arch shape cannot be obtained. A more preferred lower limit is 15% by weight, and a more preferred upper limit is 90% by weight.

The alkali-soluble resin preferably has a lower acid value of 100 mgKOH / g. If it is less than 100 mgKOH / g, the resolution of the negative resist for forming a liquid crystal alignment protrusion of the present invention is lowered, and the arch-shaped liquid crystal alignment protrusion may not 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 formed by using the negative alignment resist for forming liquid crystal alignment protrusions 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.

Further, the content of the alkali-soluble resin in the negative resist for forming protrusions for liquid crystal alignment of the present invention is usually 40% by weight or more, preferably 50% by weight or more, and usually 90% by weight, based on the total solid content. Hereinafter, it is preferably 80% by weight 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 for liquid crystal alignment protrusion formation of the present invention contains a polymerizable monomer.
The polymerizable monomer is a crosslinking component that crosslinks an alkali-soluble resin, which will be described later, by light irradiation to the negative resist for forming a projection for liquid crystal alignment of the present invention.

The polymerizable monomer means a compound having at least one ethylenically unsaturated bond in the molecule, but the difference in the solubility of the developer in the exposed portion and the non-exposed portion due to the polymerizable property, the crosslinkability and the accompanying property. From the viewpoint that it can be expanded, a compound having two or more ethylenically unsaturated bonds in the molecule is preferable, and the unsaturated bond is more preferably an acrylate compound derived from a (meth) acryloyloxy group. preferable.

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.

Of these, a polymerizable monomer containing an aromatic ring is preferred. By containing an aromatic ring, the dielectric loss tangent of the liquid crystal alignment protrusion after photocuring is reduced, which is effective in preventing the generation of a residual electric field on the protrusion surface.

Examples of commercially available polymerizable monomers containing the aromatic ring include EA-1020, EA-1025, EA-1026, EA-1028, EA-6320, and EA-6340 (all of which are Shin-Nakamura Chemical Co., Ltd.). Kogyo Co., Ltd.), Ebecryl 150, Ebecryl 1150 (Daicel UCB), M-208, M-210 (Toa Gosei Co., Ltd.), and the like.

Although the content of the polymerizable monomer in the negative resist for forming a projection for liquid crystal alignment of the present invention is not particularly limited, the preferable lower limit is 10% by weight and the preferable upper limit is 50% by weight with respect to the total solid content. is there. 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.

The negative resist for forming a protrusion for liquid crystal alignment 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- o-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-methyl Bennes such as benzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone Zophenone derivatives, 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 xanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, acridine derivatives such as 9-phenylacridine and 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 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-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-dimethylaminoethylben Zoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7- Α-aminoalkylphenone compounds such as diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- ( O-benzoyloxime), ethanone, oxime derivatives such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) It is done. These photoinitiators may be used independently and 2 or more types may be used together.

In the negative resist for forming liquid crystal alignment projections of the present invention, the content of the photopolymerization initiator is not particularly limited, but the preferred lower limit is 100 parts by weight in total of the alkali-soluble resin and the polymerizable monomer. 0.1 parts by weight, and a preferred upper limit is 20 parts by weight. If it is less than 0.1 parts by weight, the photocuring may be insufficient, and the adhesion of the liquid crystal alignment protrusions to the substrate may be reduced. If it exceeds 20 parts by weight, the photocuring reaction proceeds so much that the development residue remains. It may occur or the shape of the liquid crystal alignment protrusion produced through the steps described later becomes close to that of the column spacer, which may cause a liquid crystal alignment abnormality. A more preferred lower limit is 0.2 parts by weight, a more preferred upper limit is 15 parts by weight, a still more preferred lower limit is 0.5 parts by weight, and a still more preferred upper limit is 10 parts by weight.

The negative resist for forming projections for liquid crystal alignment according to the present invention may contain a reaction aid in order to reduce reaction hindrance 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 assistant include amines such as n-butylamine, di-n-butylamine, triethylamine, triethylenetetramine, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate; triphenylphosphine, tri-n -Phosnic compounds such as butylphosphine; sulfonic acid such as s-benzylisothuronium-p-toluenesulfinate can be used. These reaction aids may be used alone or in combination of two or more.

The negative resist for liquid crystal alignment projection formation of the present invention may contain a silane coupling agent.
The silane coupling agent plays a role in improving the adhesion between the negative resist for forming liquid crystal alignment projections of the present invention and the substrate, and is not particularly limited as such a silane coupling agent. 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 to the substrate of the negative resist for forming a projection for liquid crystal alignment of the present invention 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 for forming liquid crystal alignment projections of the present invention, the content of the silane coupling agent is not particularly limited, but is preferable when the total of the alkali-soluble resin and the polymerizable monomer is 100 parts by weight. The lower limit is 0.1 parts by weight, 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 for forming a projection for liquid crystal alignment of the present invention, usually, each component constituting the negative resist for forming a liquid crystal alignment projection of the present invention described above uses an organic solvent, and the lower limit of the solid content concentration is 5 wt. %, The upper limit is 50% by weight, preferably the lower limit is 10% by weight, and the upper limit is 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 diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMAc”), methyl ethyl ketone, methyl isobutyl ketone, Examples include cyclohexanone, toluene, 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 producing a liquid crystal alignment protrusion using the liquid crystal alignment protrusion forming negative resist of the present invention will be described.
In order to produce a liquid crystal alignment protrusion using the liquid crystal alignment protrusion forming negative resist of the present invention, first, the liquid crystal alignment protrusion forming negative resist of the present invention is formed on a substrate so as to have a predetermined thickness. To form a film.
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 for forming a projection for liquid crystal alignment according to the present invention are reacted and photocured.
The actinic light is not particularly limited and, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but ultraviolet light is preferable.

The liquid crystal alignment protrusion can be formed, for example, by adjusting the amount of light applied to the liquid crystal alignment protrusion forming portion of the coating film. As a method for adjusting the irradiation amount, a conventionally used method may be used. For example, when irradiating actinic rays through the mask, an arch-shaped projection for liquid crystal alignment is performed by an alkali development process described later. For example, a method using a gray scale, a halftone mask, or the like can be used.

The wavelength of actinic rays such as ultraviolet rays to be irradiated is not particularly limited, but it is preferable to use ultraviolet rays having a wavelength of about 200 to 600 nm, and the preferable lower limit is 10 J / cm ² and the preferred upper limit is 500 mJ / cm ² . If it is less than 10 mJ / cm ² , the photocuring may be insufficient, and a pattern may flow in the development process, resulting in poor adhesion. When it exceeds 500 mJ / cm ² , a development residue is likely to occur.

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 for forming a liquid crystal alignment projection 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.

Note that columnar column spacers for regulating the cell gap of the liquid crystal display device can also be formed by using the negative resist for forming protrusions for liquid crystal alignment according to the present invention.
As a method for forming a column spacer using the negative resist for forming a liquid crystal alignment projection according to the present invention, for example, a projection for forming a liquid crystal alignment is formed on a portion of the coating formed on the substrate by the above-described method. There is a method in which the alkali development described above is performed after the light is irradiated in excess of the exposure energy required to prepare the film. According to such a method, the negative resist for forming a projection for liquid crystal alignment of the present invention is sufficiently polymerized and cured by the light applied to the film, so that a columnar column spacer higher than the projection for liquid crystal alignment can be formed. it can.

Such a liquid crystal alignment protrusion using the negative resist for forming a liquid crystal alignment protrusion of the present invention is also one aspect of the present invention.
Furthermore, a negative resist for forming a liquid crystal alignment protrusion of the present invention or a color filter having the liquid crystal alignment protrusion of the present invention is also one aspect of the present invention.

When the color filter of the present invention has a liquid crystal alignment protrusion made of the above-described negative resist for forming a liquid crystal alignment protrusion of the present invention, the liquid crystal display device using the color filter has a wide viewing angle.
The liquid crystal display device using the negative resist for liquid crystal alignment projection formation of the present invention or the color filter of the present invention is also one aspect of the present invention.

According to the present invention, a negative resist for forming a protrusion for liquid crystal alignment, which can form protrusions for controlling the liquid crystal alignment of the liquid crystal display device and prevent the liquid crystal image sticking phenomenon from occurring in the manufactured liquid crystal display device, A liquid crystal alignment protrusion, a color filter, and a liquid crystal display device 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) Production of color filter A Cr thin film was formed on a transparent substrate by a photoetching method. A red, blue, and green photosensitive resin composition was patterned thereon by photolithography to form red, blue, and green pixels. Further, an ITO film was formed on the entire surface by sputtering to form a transparent conductive film layer, and a color filter was manufactured.

(2) 150 parts by weight of PGMAc (propylene glycol monomethyl ether acetate) was placed in a flask equipped with an alkali-soluble resin A synthesis stirrer, dropping funnel, condenser, thermometer, and gas introduction tube, and stirred while purging with nitrogen at 110 ° C. The temperature was raised to.
Next, a monomer mixture comprising 32.6 parts by weight (0.38 mol) of methacrylic acid and 31.1 parts by weight (0.10 mol) of o-phenylphenol glycidyl ether acrylate (NK ester 401P, manufactured by Shin-Nakamura Chemical Co., Ltd.) Then, 3.6 parts by weight of t-butyl hydroperoxide (manufactured by NOF Corporation, Perbutyl O) was dropped into the flask over 2 hours from the dropping funnel, 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 reacted at 100 ° C. for 10 hours. I let you. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin solution (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.

(3) Preparation of negative resist for forming liquid crystal alignment protrusions 200 parts by weight of the alkali-soluble resin solution obtained in (2), pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha) 80 as a weight monomer Parts by weight, 5 parts by weight of Irgacure 819 (manufactured by Ciba Specialty Chemicals) as a photoinitiator, 5 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals), 3-acryloxypropyltrimethoxy as a silane coupling agent having an acryloxy group A negative resist for forming protrusions for liquid crystal alignment was prepared by mixing 10 parts by weight of silane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by weight of PGMAc as a solvent.

(4) Manufacture of color filter substrate on which liquid crystal alignment protrusions are formed A negative resist for forming liquid crystal alignment protrusions obtained in (3) is spin-coated on the color filter manufactured in (1), and then 80 ° C. The coating film was obtained by drying for 2 minutes. 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, a baking process at 200 ° C. for 30 minutes was performed to obtain a color filter substrate having alignment control protrusions.

(5) Fabrication of MVA-LCD An MVA-LCD was fabricated using the color filter substrate having the liquid crystal alignment protrusions obtained. After that, when an image was displayed by applying a voltage to the MVA-LCD for a long time, the image sticking phenomenon did not occur, and good display performance was exhibited.

(Example 2)
(1) Synthetic stirrer of alkali-soluble resin B, dropping funnel, condenser, thermometer, 150 parts by weight of PGMAc were placed in a flask equipped with a gas introduction tube, stirred while purging with nitrogen, and heated to 110 ° C.
Next, from 32.6 parts by weight (0.18 mol) of methacrylic acid 32.6 parts by weight (0.38 mol) and hydroxyethylated phenylphenol acrylate (NK ester A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) To the monomer mixture, 3.6 parts by weight of t-butyl hydroperoxide (Nippon Yushi Co., Ltd., Perbutyl O) is dropped into the flask over 2 hours from the dropping funnel, and further stirred at 110 ° C. for 3 hours for aging. It was.
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 reacted at 100 ° C. for 10 hours. I let you. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin solution (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) Manufacture of a color filter substrate on which liquid crystal alignment protrusions are formed A negative resist for forming liquid crystal alignment protrusions is prepared in the same manner as in Example 1 except that the alkali-soluble resin A is changed to the alkali-soluble resin B. Using this, a color filter substrate having a liquid crystal alignment protrusion was obtained.

(3) Fabrication of MVA-LCD An MVA-LCD was fabricated using the color filter substrate having the liquid crystal alignment protrusions obtained. After that, when an image was displayed by applying a voltage to the MVA-LCD for a long time, the image sticking phenomenon did not occur, and good display performance was exhibited.

(Comparative Example 1)
(1) Synthetic stirrer of alkali-soluble resin C, dropping funnel, condenser, thermometer, 150 parts by weight of PGMAc were placed in a flask equipped with a gas introduction tube, 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 reacted at 100 ° C. for 10 hours. I let you. The reaction was carried out in an air / nitrogen atmosphere. As a result, an alkali-soluble resin solution (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) Manufacture of a color filter substrate on which liquid crystal alignment protrusions are formed A negative resist for forming liquid crystal alignment protrusions is prepared in the same manner as in Example, except that the alkali-soluble resin is changed from No. 1 to No. 3. Using this, a color filter substrate having a liquid crystal alignment protrusion was obtained.

(3) Fabrication of MVA-LCD An MVA-LCD was fabricated using the color filter substrate having the liquid crystal alignment protrusions obtained. Thereafter, when an image was displayed by applying a voltage to the MVA-LCD for a long time, a burn-in phenomenon occurred and the display performance was not good.

(Comparative Example 2)
(1) Manufacture of color filter substrate on which protrusions for liquid crystal alignment were formed For forming protrusions for liquid crystal alignment in the same manner as in Example except that alkali-soluble resin A was changed to vanaresin PSY-700 (manufactured by Shin-Nakamura Chemical) A negative resist was prepared, and a color filter substrate having liquid crystal alignment protrusions was obtained using the negative resist.

(2) Production of MVA-LCD An MVA-LCD was produced using the obtained color filter substrate having the liquid crystal alignment protrusions. Thereafter, when an image was displayed by applying a voltage to the MVA-LCD for a long time, a burn-in phenomenon occurred and the display performance was not good.

According to the present invention, a negative resist for forming a protrusion for liquid crystal alignment, which can form protrusions for controlling the liquid crystal alignment of the liquid crystal display device and prevent the liquid crystal image sticking phenomenon from occurring in the manufactured liquid crystal display device, A liquid crystal alignment protrusion, a color filter, and a liquid crystal display device using the negative resist for forming a liquid crystal alignment protrusion can be provided.

Claims (6)

A negative resist for forming protrusions for liquid crystal alignment containing an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator,
The negative resist for forming a projection for liquid crystal alignment, wherein the alkali-soluble resin has a structure in which two or more phenylene skeletons are bonded. The alkali-soluble resin has at least one phenylene skeleton selected from the group consisting of the following general formulas (1), (2), (3) and (4) in the side chain. Negative resist for forming protrusions for liquid crystal alignment.

R ^{1 to} R ⁹ represent H, CH ₃ , OH, COOH, NH ₂ , CN, NO ₂ , Cl, Br, I, and Y represents CH ₂ , O, CO, COO, COONH. M is a natural number of 2 to 4, and n is 1 or 2. 3. The negative resist for forming a protrusion for liquid crystal alignment according to claim 1, wherein the alkali-soluble resin has a biphenylene skeleton. 4. A liquid crystal alignment protrusion comprising the negative alignment resist for forming a liquid crystal alignment protrusion according to claim 1, 2 or 3. A color filter comprising the liquid crystal alignment protrusion forming negative resist according to claim 1, 2 or 3, or the liquid crystal alignment protrusion according to claim 4. A liquid crystal display device comprising the negative resist for forming a protrusion for aligning liquid crystal according to claim 1, or the color filter according to claim 5.