TW200921278A - Negative-working resist for formation of protrusions for liquid crystal alignment - Google Patents

Abstract

This invention provides a negative-working resist for the formation of protrusions for liquid crystal alignment, which can realize the formation of protrusions for regulating liquid crystal alignment in a liquid crystal display device and can realize the prevention of seizing of a liquid crystal in a produced liquid crystal display device. The negative-working resist contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator and is used for the formation of protrusions for liquid crystal alignment in an MVA liquid crystal display device. The polymerizable monomer is a negative-working resist containing a novolac epoxy (meth)acrylate for the formation of protrusions for liquid crystal alignment.

Description

[Technical Field] The present invention relates to a negative resist for forming a protrusion for liquid crystal alignment, which can form a protrusion for controlling liquid crystal alignment of a liquid crystal display device, and can prevent The manufactured liquid crystal display device produces a phenomenon of liquid crystal afterimage. [Prior Art] The liquid crystal display device has a structure in which a direction in which the color filter, the black matrix, the linear transparent electrode, the alignment film, and the like are formed is perpendicular or parallel to the substrate The matching liquid crystal. In a state where no electric field is applied, the liquid crystal injected between the substrates is aligned in a direction perpendicular to the substrate or in a direction parallel to the substrate, and an electric field can be applied to change the alignment state, whereby the amount of light transmitted through the liquid crystal can be adjusted. The liquid crystal display device is practically used as a liquid-tanned television for a large-screen television because it is thinner and consumes less power than a display device using a Brown tube. However, the liquid crystal display element has a problem of narrow viewing angle as compared with a display device using a Brown tube. With the popularity of large-screen LCD TVs, there is a strong demand for improvements in viewing angles. ▲ As a method for improving the viewing angle of the liquid crystal display device, there is proposed an MVA (Multid〇 main Vertical Alignment) method in which an arcuate protrusion is formed on a transparent electrode, and the inclination of the protrusion (si, The liquid crystal is locally tilted to divide the liquid crystal into multiple directions in the _pixel. The alignment is performed as the arcuate protrusion formed on the transparent electrode. The method is as follows. Shadow method, 5 200921278 to form a protrusion having a substantially rectangular cross section, and thereafter heating the protrusion to be welded (four), thereby forming a bow shape for forming an arcuate shape on the transparent electrode, for example, Patent Document 1 discloses a positive resist containing a naphthoquinone diazide compound and a copolymer having a specific structural unit having a hydroxyl group. However, a positive anti-rheing agent is used on a transparent substrate. When the protrusion is formed, it needs to be heated and welded to form an arcuate shape, so that the obtained protrusion is obtained due to the bottom width or the heating temperature of the formed pattern. The height of the bow and the angle of contact with the substrate are different. If the height and angle of the protrusion are not good, the alignment of the liquid crystal may be uneven, and even display unevenness may occur. Further, the positive type resistance disclosed in Patent Document 1 (4) , the existence of #, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The positive-type anti-money agent exhibits a difference in solubility between the exposed portion and the unexposed portion in the in-situ developer due to the alkali-soluble carboxylic acid produced in the photolysis of the photopolymer of the second stack. Therefore, if it is negative Compared with the type of money agent, the range of development conditions of the positive type anti-money agent is narrow, and it is difficult to manage the development state such as development deterioration caused by oxygen in the air. Moreover, the manufacturing process of the liquid crystal display device is included in In addition to the step of forming a protrusion on the transparent electrode, (4) various resists are also used, but most of the steps use a negative type anti-noise agent. Therefore, a positive type resist is used only in the step of forming the protrusion. meeting The manufacturing process is complicated. In this regard, Patent Document 2 discloses that a negative-type anti-surplus agent containing a solvent-soluble resin, a photopolymerization initiator, and a photopolymerizable monomer as a main component is used for the electrode on the electrode 200921278. Patent Document 3 discloses a photosensitive dendrimer composition which is mainly composed of a ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin, and is used as a negative-resistance for forming a projection for liquid crystal division and alignment. Residual agent < simplification of the manufacture of the liquid crystal display device by using the negative type anti-agent*. However, the use of the previous negative resist to form a liquid crystal alignment protrusion liquid 曰曰 display device When the time is displayed, there is a problem in that a liquid crystal alignment dog is formed. The squeegee generates an abnormal alignment of the liquid crystal, which causes a problem of displaying a liquid crystal afterimage phenomenon in which an image remains. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-33001 (Patent Document 3) [Patent Document 3] JP-A-2006-1 1359 SUMMARY OF THE INVENTION The object of the present invention is to Provided is a negative-type anti-money agent for forming a liquid crystal alignment protrusion which can form a protrusion for controlling alignment of a liquid crystal alignment of a liquid crystal display device and can prevent a liquid crystal afterimage phenomenon from occurring in the liquid crystal display device manufactured. The present invention is a negative resist for forming a liquid crystal alignment protrusion, which contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator, and is used for forming a protrusion for liquid crystal alignment of an MVA liquid crystal display device. The above polymerizable monomer contains a novolac epoxy (meth) acrylate. The invention is described in detail below. The present inventors have found that when a negative resist containing a phenolic epoxy (meth) acrylate as a polymerizable monomer is used, a liquid crystal for forming an MVA type 200921278 liquid aa display device is multidirectional in one pixel. When the protrusions are divided and aligned, even if the display is performed for a long period of time, the abnormal alignment of the liquid crystal does not occur in the protrusion forming portion, and the liquid crystal afterimage phenomenon does not occur, and the present invention has been completed. The negative-type anti-surname agent for forming a liquid crystal alignment protrusion of the present invention (hereinafter also referred to as a negative anti-surname agent of the present invention) is used for forming a liquid crystal partial division and alignment in an Mva liquid crystal display device. An arcuate protrusion (a projection for liquid crystal alignment) formed on the substrate. Further, in addition to the above-described liquid crystal alignment protrusion, the negative resist of the present invention can be used, for example, to manufacture a column spacer which restricts the gap between the two substrates of the liquid aa display device. The negative resist contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. The polymerizable monomer is a cross-linking component which causes cross-linking of an alkali-soluble resin to be described later by light irradiation of the negative resist of the present invention. By using a phenolic epoxy (meth)propionate as the polymerizable monomer, an MVA liquid crystal display device in which a liquid crystal alignment protrusion is provided using the negative resist of the present invention can suppress liquid crystal afterimage The phenomenon occurs. The reasons are as follows. The liquid crystal afterimage phenomenon generated in the MVA liquid crystal display device is caused by the residual electric field generated between the protrusion forming portion and the counter substrate. This residual electric field is caused by a dielectric loss tangent of the protrusions and a large difference in dielectric tangential tangent with the alignment film and the liquid crystal. It is considered that the negative-type resist of the present invention containing a phenolic epoxy (meth) acrylate as a polymerizable monomer forms a liquid crystal alignment protrusion of 200921278 because of its dielectric loss tangent and alignment film and liquid crystal. The electric loss tangent is close to 'therefore, the above residual electric field can be prevented from occurring. Therefore, the MVA liquid crystal display device having the liquid crystal alignment protrusion formed by using the negative-type anti-surplus agent of the present invention does not exhibit a liquid crystal afterimage phenomenon even if it is displayed for a long period of time. The above-mentioned epoxy (fluorenyl) acrylate is not particularly limited, and examples thereof include phenol phenol epoxy (meth) acrylate, o-cresol novolac epoxy (meth) acrylate, and m-cresol phenol aldehyde. Epoxy (meth) acrylate, p-formaldehyde aldehyde epoxy (meth) acrylate, naphthol modified phenolic epoxy (meth) acrylate, halogenated phenol novolac epoxy (meth) acrylate, and the like. Further, in the present specification, (meth) acrylate means acrylate or methacrylate. The general formula indicating the above phenol-based epoxy (fluorenyl) acrylate is shown in the following formula (1).

In the formula (1), R 2 represents a hydrogen or a methyl group, and m represents a fluorene or a positive integer. The above phenolic epoxy (meth) acrylate can be obtained, for example, by an esterification reaction of a phenolic epoxy resin 200921278 with an unsaturated monobasic acid. For example, the above-mentioned sulfonated resin may be exemplified by benzene (tetra) oxy-resin, o-methyl sulfonate epoxy resin, m-brown epoxy wax, opposite age (four) bad milk wax, and naphthalene-age modified acid ring Oxygen resin, phenolized benzene (tetra) epoxy resin. The above unsaturated monobasic acid is preferably a compound having a (meth)acrylic acid group and a few groups in terms of reactivity, such as (meth)acrylic acid, itaconic acid, butyric acid, cinnamic acid. Among them, (meth)propanoid acid is preferred. The acetalization reaction may, for example, be carried out by a method such as a catalyst for epoxy oxime. The above-mentioned desired epoxy resin is reacted with the above unsaturated monobasic acid in the presence of a stabilizer such as polymerization (IV), an antioxidant, and the like at a temperature of from 3 Torr to 150 °C. Tertiary amines, imidazole compounds: hydroquinone, methyl p-benzene The above-mentioned vinegar catalysts include, for example, phosphorus compounds, organometallics, and the like. Examples of the above polymerization inhibitors include diphenol and 4-methoxyphenol. Examples of the above antioxidants include a phosphorous acid system, a phosphorous acid vinegar, and a phosphite diester. The reforming ratio of the above (meth)acrylic acid vinegar is not particularly limited, and some or all of the phenolic epoxy resin may be modified with (mercapto) acrylate. The above-mentioned conjugated epoxy (fluorenyl) acrylate vinegar preferably has a test functional group. By having an alkali-soluble functional group, the obtained negative resist of the present invention is improved. The test functional group can be introduced by reacting a hydroxyl group contained in the epoxy (meth) acrylate with a polybasic acid anhydride. The reaction method 200921278, for example, Kola + Root Field is obtained by continuing the reaction under the same conditions as the above esterification reaction. The general formula of the phenolic epoxy (meth) acrylate having no such alkali-soluble functional group is shown in the following formula (2).

In the formula (2), 'ri, r2 represents hydrogen or a sulfhydryl group, and r3 represents an atomic group derived from a polybasic k-hepatic group and having a mercapto group. Also, m and n represent 〇 or a positive integer. Examples of the polybasic acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, and pyromellitic anhydride. , trimellitic anhydride, and the like. Among them, succinic anhydride or phthalic anhydride is preferred in terms of reactivity. When the above phenolic epoxy (meth) acrylate has an alkali-soluble functional group, the upper limit of oxidation is preferably 250 mgKOH/g. When the oxidation of the phenolic epoxy (fluorenyl) acrylate having the above alkali-soluble functional group exceeds 250 mgKOH/g, the adhesion is lowered. A more preferable upper limit of the oxidation of the phenolic epoxy (methyl) diacid ester having the above alkali-soluble functional group is 200 mgKOH/g. The lower limit of the weight average molecular weight of the above phenolic epoxy (meth) acrylate is 600 in comparison with the lower limit of 200921278, and the upper limit is preferably 2,000. When the weight average molecular weight of the above phenolic epoxy (fluorenyl) acrylate is less than 600, the amount of unreacted low molecular compound in the resin increases, and the remaining low molecular compound is eluted into the liquid crystal to cause poor display of the panel. If it exceeds 2,000, residue may be generated during development, or the obtained protrusions may not be arcuate. The lower limit of the weight average molecular weight of the above phenolic epoxy (fluorenyl) acrylate is 800, and the upper limit is more preferably 1800 °. Further, in the present invention, the weight average molecular weight of the phenolic epoxy (meth) acrylate is For example, a column of Shodex LF-804 manufactured by Showa Denko Co., Ltd. is used, and is measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a developing solvent, and is obtained by polystyrene conversion. value. Commercial products of the above-mentioned novolac epoxy (fluorenyl) acrylate include, for example, EA-1020, EA-1025, EA-1026, EA-1028, EA-6320, EA-6340 (all of which are Xinzhongcun Chemical Industry) Made by the company), Ebecryl 150, Ebecryl 1150 (all manufactured by DAICEL UCB), M-208, M-210 (all manufactured by East Asia Synthesis), PNA-161H, CNA-142H, PCR-1169H, CCR- 1159H (all of which are manufactured by Nippon Kayaku Co., Ltd.), EPICLON N-695, EPICLON N-775 (all of which are manufactured by Otsuka Ink Chemical Co., Ltd.), PR-300, PR-310, PR-320, HRM-1004, HRM-1005, HRM-101, HRM-1013, HRM-2019, HRM-202 1, HRM-2027, HRM-203 1 (all of which are manufactured by Showa Polymer Co., Ltd.). The blending amount of the above phenolic epoxy (mercapto) acrylate is not particularly limited to 12 200921278 "phase: 100 parts by weight of the above-mentioned test-soluble resin, preferably lower limit of 2 虿 heavy smashing' is preferably an upper limit of 200 parts by weight. When the amount of the above-mentioned phenolic epoxy (methyl)propene (4) is less than 2 G by weight, the effect of preventing afterimage is impaired, and if it exceeds 200 parts by weight on the right, the developing dissolution rate is liable to decrease. A more preferred lower limit of the blending amount of the epoxy (meth) acrylate is 3 parts by weight, and a still more preferred upper limit is 180 parts by weight, wherein the above weight is obtained by dissolving it in a solvent or the like (4). The part refers to a value obtained by converting a solid component. The negative anti-synthesis of the present invention is aimed at improving adhesion, developability, heat resistance, acid resistance, testability, chemical resistance, and compatibility with a test resin. The agent ' may also contain a polymerizable monomer other than the above epoxy (meth) acetoacetate. The above polymerizable monomer means a compound having one or more ethylidene unsaturated bonds in the molecule. a compound having one ethylenically unsaturated bond in the knives and There is no particular limitation, and examples thereof include unsaturated carboxylic acids such as (meth)acrylic acid, butyric acid, methacrylic acid dimaleic acid, itaconic acid, and methyl maleic acid, and the alkyl group thereof. (meth)acrylonitrile, (fluorenyl) acrylamide, styrene, etc., and a compound having two ethylenically unsaturated bonds in the molecule, and is not particularly limited, and examples thereof include: neopentyl glycol (meth) acrylate, fluorenylmethyl-1,5-pentanediol di(meth) acrylate, 2-butyl-2-ethyl-hydrazine, propylene glycol _ (meth) acrylate, i, 4_ Butanediol diacrylate, hydrazine, 6-hexanediol dicarboxylate, hydroxypivalic acid neopentyl glycol ester diacrylate, diethylene glycol (meth) acrylate, triethylene glycol (曱a polyethylene glycol (meth) acrylate such as acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, pentylene glycol (meth) acrylate, or Diethylene glycol di(meth) propylene 13 200921278 acid ester, diethylene glycol di(methyl) acrylate, tetraethylene glycol di (meth) acrylate Polyethylene glycol bis(indenyl) acrylate such as hexaethylene glycol di(meth) acrylate or pentylene glycol di(meth) acrylate, etc. It has three or more ethylenic groups in the molecule. The compound of the saturated bond is not particularly limited, and examples thereof include tris(hydroxy) ethane tri(indenyl) acrylate, trishydroxypropyl propane tri(meth) acrylate, and di(trimethylolpropane) four. (fluorenyl) acrylate, pentaerythritol tri(methyl) acrylate, pentaerythritol tetra (indenyl) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol A polyfunctional (meth) acrylate compound such as hexa(meth) acrylate or the like, which is equivalent to a compound having three or more ethylenically unsaturated bonds in the molecule, and the polymerization reaction proceeds quickly, and the exposure sensitivity is easily improved. Especially good. Among them, pentaerythritol tri(meth)acrylate is preferred because it can improve developability and compatibility with an alkali-soluble resin. These polymerizable monomers may be used singly or in combination of two or more. When the polymerizable monomer U other than the above-mentioned novolac epoxy (meth) acrylate is used in combination, the above-mentioned phenolic epoxy (fluorenyl) is contained in the entire polymerizable monomer. A preferred upper limit of the ratio of the polymerizable monomer other than the acryl vinegar is 80% by weight, and if the ratio of the polyfunctional monomer having an alkali-soluble group other than the above phenolic epoxy (meth) acrylate is more than 80% by weight, Damage and the effect of preventing afterimages. A more preferable upper limit of the ratio of the polymerizable monomer having an alkali-soluble group other than the above phenolic epoxy (meth) acrylate is 75% by weight. The negative resist of the present invention contains an alkali-soluble resin. The alkali-soluble resin is not particularly limited, and can be suitably used in the molecule/there is a polycyclic double bond. Specifically, for example, a polymer compound containing an alkali-soluble carboxyl group such as a copolymer obtained by copolymerizing a monofunctional unsaturated compound having a carboxyl group 200921278 group and a monofunctional compound having an unsaturated double bond can be mentioned. The monofunctional unsaturated compound containing a carboxyl group is not particularly limited. For example, acrylic acid, methacrylic acid or the like can be mentioned. The monofunctional compound having an unsaturated double bond is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, 2-ethylhexyl acrylate (meth)acrylate, hydroxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate , (meth)acrylic acid dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, (meth)acrylic acid vinegar, etc. (meth)acrylic acid Ester monomer. The polymer compound containing an alkali-soluble carboxyl group may further contain a component derived from an aromatic vinyl monomer such as styrene, α-methylstyrene, p-methylstyrene or p-chlorostyrene, or propylene. A vinyl cyanide compound such as a nitrile or a mercapto acrylonitrile, an unsaturated diacidified liver such as maleic anhydride, 'phenyl maleimide, benzyl maleimide, naphthyl maleimide, ortho Aromatically substituted maleic imine, such as phenyl phenyl maleimide, fluorenyl maleimide, ethyl maleimide, propyl maleimide, isopropyl mala An alkylamine-substituted maleimide or the like such as an imine. The polymer compound containing an alkali-soluble carboxyl group can also contain a component derived from a monofunctional unsaturated compound having a hydroxyl group for the purpose of controlling solubility in development and the like. The above-mentioned monofunctional unsaturated compound having a hydroxyl group is not particularly limited to 15 200921278, and is, for example, a monomer having a hydroxyl group in the molecule, and examples thereof include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. 2, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. In the polymer compound containing an alkali-soluble carboxyl group, a preferred lower limit of the ratio of the component derived from the monofunctional unsaturated compound containing a carboxyl group is 5% by weight, and a preferred upper limit is 50% by weight. When the ratio of the component derived from the carboxyl group-containing monofunctional unsaturated compound is less than 5% by weight, it is difficult to impart alkali solubility, and if it exceeds 5% by weight, swelling during development is remarkable and it is difficult to form a pattern. A more preferred lower limit of the ratio of the dicing derived from the monofunctional unsaturated compound having a carboxyl group is 1% by weight, and more preferably the upper limit is % by weight. The method for copolymerizing a monofunctional unsaturated compound having an ester group with a mono-g-energy compound having an unsaturated double bond is not particularly limited, and J may be as follows: a radical polymerization initiator and If necessary, the sub-quantity adjuster 'polymerizes by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or the like. Among them, solution polymerization is preferred. The solvent used in the above-mentioned polymer compound containing a test-solvent retarding group by a solution polymerization method can be used, for example, decyl alcohol, ethanol, isopropanol, ethyl alcohol-specific aliphatic alcohol, and gold Α μ ^ ping-type celluloid 、, butyl 赛 珞 等 等 珞 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Ethers such as esters such as diethylene glycol dioxime ether, tetrahydrofuran, etc., and oxime, such as hexanone, mercaptoethyl ketone, and methyl isobutyl ketone, 9 dimethyl sulphide jr rg Earthy, dimethylformamide and other polar organic solvents 16 200921278

In addition, as a raw material for producing the above-mentioned polymer compound containing an alkali-soluble carboxyl group by a non-aqueous knife-forming polyport such as a suspension polymerization, a dispersion polymerization or an emulsion polymerization, for example, a liquid such as benzene, toluene, hexane or cyclohexane may be used. Hydrocarbons, or other non-polar organic solvents, etc. The radical polymerization initiator is not particularly limited, and for example, a conventionally known radical polymerization initiator such as a peroxide or an azo initiator can be used. Further, as the molecular weight modifier, for example, a methylstyrene dimer, a thiol-based chain transfer agent or the like can be used. In the negative resist of the present invention, the alkali-soluble resin preferably has an alkali-soluble (meth)acrylic copolymer having a (meth)acrylic group and a carboxyl group in a side chain, and has a side chain. When the (meth)acrylic acid group of the (meth)acrylic acid group and the carboxyl group is used as the alkali-soluble resin, the negative-type anti-money agent of the present invention has an antimony-sensitive antimony agent and is hardened to form a liquid crystal alignment. The protrusions have excellent resolution and adhesion to the substrate. It is considered that the reason is that since the acrylic acid on the side chain of the alkali-soluble resin is reacted based on the exposure, the alkali-soluble resin itself also enters the crosslinked structure, and as a result, the pattern peeling is suppressed. Further, since the segment of the alkali-soluble (meth)acrylic copolymer has a low polarity, it is excellent in compatibility with other components of the negative resist of the present invention. As a result, in the development process for producing the projections for liquid crystal alignment, defects such as development unevenness do not occur. The above-mentioned test-soluble (meth)acrylic copolymer is preferably a copolymer composed of the structural formula 17 200921278 represented by the following formulas (3a), (3b), (3c), (3d) and (36). .

COOH

(3b)

CH,——CR4- (3 d) COOA1

(3 e)

Equations (3a), (3b), (3c), (

And A2 represents hydrogen and in the following formulas (4a), (4b) and (3e), A when either of A1 or A2 is hydrogen, the other is (4C) or (4d), and Wei' is Any one of the formulae (4a), (4b), (4c) or (4d). R4 represents hydrogen and/or a f group, r5 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 of the formula 200921278, R6 represents a nitrile group or a phenyl group, and R7 represents an alkyl group. A hydroxyalkyl group or an aliphatic cigarette containing a radical polymerizable group. Further, 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, and c is 5 to 50. , e is 5~60. △'A2: -R7 (4a) f -C-N——R7 (4 b)

^ II I

Ο H CH2—CH-R7 (4c)

I

OH CH2 —R? (4 d)

OH U The weight average molecular weight of the above-mentioned test-soluble (meth)acrylic copolymer is not particularly limited, and a preferred lower limit is 3,000, and a preferred upper limit is 1,000,000. When the weight average molecular weight of the above-mentioned soluble (meth)acrylic copolymer is less than 3 Å, the adhesion of the liquid crystal alignment protrusion obtained by the jin is lowered, and if it exceeds 10,000 Å, the resolution is lowered. A lower limit is 5_, and a lower limit is 50,000. In the present specification, the weight average molecular weight is measured by a gel' chromatography method, and the value obtained by the conversion of polystyrene is determined. The method for producing the above-mentioned test-soluble (meth)propane-copolymer is, for example, a method in which an alicyclic epoxy group is contained, and a compound having a carboxyl group in a side chain (methyl group) The acrylic copolymer is subjected to ring-opening addition polymerization, and one part of the carboxyl group is modified, and an isocyanate compound, an epoxy compound, a lactone compound, an alcohol compound, etc., and a hydroxyl group formed by the modification and/or a residual carboxyl group are A part of the reaction. The method for producing the (meth)acrylic copolymer having a carboxyl group in the side chain is not particularly limited, and examples thereof include a method of using a radical polymerization initiator and an optional molecular weight modifier to form a bulk polymerization. ': A conventionally known method such as liquid polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or the like, wherein a monofunctional unsaturated compound containing a slow group is copolymerized with a (meth)acrylic acid vinegar monomer. The alicyclic epoxy group-containing unsaturated compound is not particularly limited, and, for example, (meth)acrylic acid 3,4-epoxycyclohexanoic acid or the like can be suitably used. The above-mentioned isocyanate compound is not particularly limited, and for example, an isocyanate-based vinegar having a carbon number of 2 to 18 and an isocyanic acid vinegar containing a polymerizable group can be used. When the above-mentioned isocyanic acid-containing polymerizable group is used, the sensitivity at the time of chemical conversion can be further improved, and various physical properties such as heat resistance and (4)-f (tetra) properties can be further improved. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Bonded to form. Specific virgin oxyethyl oleic acid vinegar, 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The basic (4) vinegar (4) 6-base isocyanic acid "nzA〇I (made by Showa Denko)) and 20 200921278 The above isocyanate compound and the above-mentioned modification of the side bond has a hydroxyl group The method of reacting the carboxyl group-containing (meth)acrylic copolymer is not particularly limited, and examples thereof include the following methods: adding or mixing the above-mentioned isocyanate compound into the presence of a small amount of a catalyst The above-mentioned modification is carried out in a (meth)propionic acid solution having a radical and/or a few groups on the side bond. The catalyst used at this time is a special acid, a dibutyltin or the like. For example, laurel may be used, and if necessary, p-methoxybenzoate, p-benzoate, amine, t-butylcatechol, and 2 3_di=agent may be used. For the purpose of suppressing and increasing the amount of money, it is also possible to use propanol, butanol, pentanol, hexanol, and heptyl alcohol. According to the above production method, when the oxime compound is reacted with the hydroxyl group and the carboxyl group in the side chain by the above modification, the olefinic acid copolymer L can be formed. ,.. The structural unit shown by the formula (2b). The oxygen compound is not particularly limited, and examples thereof include an epoxy compound having a carbon number of 2 to 18, a carbon number compound or an epoxy compound containing a polymerizable group. &oxyepoxidation two makes the epoxy compound of ::::::: as the upper_heat=study, the nature of the sex, etc.: physical properties and can further improve the resistance to the above 3 polymerizable groups The emulsification product is not particularly limited, and Example 21 200921278 is preferably a group in which a (meth)acryl fluorenyl group is bonded to an epoxy group via an alkyl group having a carbon number of 2 to fluorene. Specifically, for example, glycidol vinegar (meth)acrylate or the like can be mentioned. The method for reacting the above epoxy compound with a (meth)acrylic copolymer having a hydroxyl group and/or a carboxyl group formed on the side chain by the above modification is not particularly limited, and the following method may be mentioned: In the presence of a solvent, the above epoxy compound is added dropwise or mixed into a solution of the (fluorenyl)acrylic acid copolymer having a hydroxyl group and/or a carboxyl group in the side chain formed by the above modification. The catalyst to be used at this time is not particularly limited, and examples thereof include triethylamine, dipropylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, and the like. Methyl cetyl ammonium bromide, tetrabutylammonium bromide, trimethylbutyl bromide scale, tetrabutyl bromide scale, and the like. Further, if necessary, p-methoxyphenol, hydroquinone, naphthylamine, third decyl tea age, and 2,3·di-t-butyl-p-methyl polymerization inhibitor may be used. According to the above production method, when the epoxy compound is reacted with the (meth)acrylic copolymer having a hydroxyl group and/or a carboxyl group formed on the side chain by the above modification, the formula (2c) and (2d) can be formed. The structural unit shown. When the above 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 formed on the side chain by the above modification, the above ( The amount of the hydroxyl group contained in the fluorenyl-acrylic acid copolymer is equivalent to the amount of 〇~1〇〇mol%. Further, the isocyanate compound, the epoxy compound, the lactone compound 22, the organic compound, and the like are reacted with a (meth)acrylic copolymer having a radical and/or a group formed on the side chain by modification. In the case, τ is caused to react in an amount corresponding to 0 to 90 mol% of the carboxyl group contained in the (meth)acrylic copolymer. If it exceeds 90% by mole, the amount of remnant base remaining will be too small, which may impair alkali solubility and cause deterioration in developability. The above formulas a, b, c, d), (3b), (3e), (3d) and (3e) represent the molar ratio (%) of each component, a+b+c + d+e= When i 〇 0, the lower limit of a, b & d is 〇%, and the upper limit is 9〇%. Further, the lower limit of c is 5% 'the upper limit is 5 %. Further, the lower limit of 6 is 5%, and the upper limit is 60%. The lower limit of c is 5%, and the upper limit is (4) if the state is not full, that is, if the molar ratio of the structural unit containing the slow-base is less than 5%, it is difficult to give the test more than 50/^, and the swelling during development is remarkable. It is difficult to form a pattern. Further, the preferred lower limit of 'e is 5%, and the upper limit is preferably 6〇%. If it is not full, the cross-linking of the test-soluble resin is insufficient, resulting in a decrease in cross-linking density, and the result is destruction in the development step. If it is too large, and the liquid crystal alignment is used, the height unevenness 'if it exceeds 6〇%', the crosslink density of the crosslinked structure may be too high, resulting in difficulty in stably forming an arc shape. Further, in the negative resist of the present invention, the above-mentioned alkali-soluble tree t is preferable; and the knife has an aromatic king. When a liquid crystal factory or apparatus having a projection for liquid crystal alignment formed by using the negative resist of the present invention is used for a long time display, the dielectric loss tangent of the liquid crystal alignment protrusion is reduced by the improvement of the solubility of the aromatic ring. It is more suitable for preventing the phenomenon of liquid crystal afterimage. The test resin having an aromatic ring is not particularly limited, and it is preferred because (meth) 23 200921278 benzyl acrylate copolymer has good adhesion and developability. In the negative resist of the present invention, the lower limit of the acid value of the above-mentioned test-soluble resin is 50 mgKOH/g. When the acid value of the above-mentioned test-soluble resin is less than 50 mgKOH/g, the resolution of the negative resist of the present invention is lowered, and the arcuate liquid crystal alignment protrusion cannot be stably formed. The upper limit of the acid value of the above alkali-soluble resin is not particularly limited, and a preferred upper limit is 15 〇 mgKOH/g. When the acid value of the alkali-soluble resin exceeds 15 〇 mgKOH/g, the adhesion between the liquid crystal alignment protrusion formed by using the negative resist of the present invention and the substrate is lowered. The lower limit of the acid value of the above alkali-soluble resin is 6 〇 mg K 〇 H / g, and the upper limit is more preferably 14 〇 mg KOH / g. In addition, in the present report, the acid value of the above-mentioned test-soluble resin is represented by the following numerical values: the alkali-soluble resin lg is dissolved in an organic solvent, and phenolphthalein is used as an indicator to perform titration by hydrogenation, and the desired hydrogen Tons of potassium oxide. The content of the alkali-soluble resin in the negative resist of the present invention is usually 25% by weight or more, preferably 3% by weight or more, and usually 90% by weight or less, based on the total solid content. It is 8 〇 wt% or less. If the amount of the test-soluble resin is too small, the amount of the test-reducing resin is lowered, the development dissolution rate is lowered, and the like, if it is used, the 敏lU causes a decrease in the sensitivity of the surface, and the reproducibility of the surface shape is poor. In order to stabilize the degree of the liquid crystal alignment protrusion and the shape in contact with the substrate, the content of the alkali-soluble resin is preferably a pure ratio with the content of the polymerizable monomer. Specifically, 24 200921278 The weight ratio of the content is preferably a lower limit of 0.35, more preferably (the content of the alkali-soluble resin) / (the lower limit of the polymerizable property is 0.25', the upper limit is preferably 3 $, and the upper limit is 3. The negative anti-surplus agent of the present invention. The photopolymerization initiator is not particularly limited, and a conventionally known photopolymerization initiator can be used, for example, it can be listed as I. It can be produced by using ultraviolet rays to make ethylene inferior. The radical polymerization is free of a compound derived from a base, a compound which generates an acid by ultraviolet rays, etc. Specific examples of the above-mentioned photopolymerization & initiator include, for example, methoxyphenyl)-4,6- Double (three gas methyl) _ uniform three "Qin" 2_ (4_A克基基)_4,6_ bis(trichloromethyl)-s-triazine, 2·(4·ethoxynaphthyl)_4,6_bis(trismethyl)·s-diazine, 2-(4 -ethoxycarbonylnaphthyl)_4,6_bis(trichloroindenyl)-halothiazine and other halomethylated diazine derivatives, tooth methylated oxadiazole derivatives, 2_(o-phenyl) -4,5-diphenylimidazole dimer, 2-(o-phenyl)-4,5-bis(3'-methoxyphenyl)meridene dimer, 2-(o-fluorophenyl) _4,5_diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2_(o-methoxyphenyl)-4,5-di A timidine derivative such as phenyl glutamic acid dimer, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin, benzoin alkyl ether '2-曱基蒽g Kun, 2- Ethyl hydrazine, 2-tert-butyl fluorene, 1 - chlorohydrazine and other hydrazine derivatives, benzofluorenone derivatives, benzophenone, mazinone, 2-methyldiphenyl Dibenzophenone derivatives such as ketone, 3-mercaptobenzophenone, 4-mercaptobenzophenone, 2-benzophenone, 4-bromobenzophenone, 2-carboxybenzophenone 2,2-dimethoxy-2- -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-mercaptophenylacetone, 1-hydroxy-25 200921278 base-i-A Ethyl ethyl-(p-isopropylphenyl) ketone, r via benzyl 1 (p-docentylphenyl) ketone, 2-methyl-(4,-(f thio)phenyl)_2_? Acetophenone derivatives such as linke xiao _ 丄 三 trichloromethyl-(p-butylphenyl) ketone, thioxanthene, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2 Thiophenone derivatives such as chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p-dimethyl a benzoate derivative such as ethyl benzoate, ethyl p-ethylaminobenzoate, acridine derivative such as 9-phenyl acridine or 9-(p-methoxyphenyl) acridine , phenazine derivatives such as 9,10-dimethylbenzophenazine, dicyclopentadiene-di-titanium dihydride, di-cyclopentadienyl-titanium-bis-phenyl, di-cyclopentadiene Base_titanium-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl_titanium_bis-2,3,5,6-tetrafluorophenyl-1 -yl, di-cyclopentadienyl, titanium, bis-2,4,6-trifluorophenyl 4,yl,di-cyclopentadienyl-indole_2,6 -difluorophenyl-1-yl, di-cyclopentadienyl _ titanium-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl 鈥 双 double _2,3 ,4,5,6-pentafluorophenyl-1-yl, bis-indolylcyclopentadienyl-titanium-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl- Titanocene derivative such as titanium-2,6-difluoro-3-(indol-1-yl)-phenyl-1-yl, 2-methyl-1[4-(methylthio)phenyl]- 2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butane-1.one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate , 4-diethylaminoacetophenone, 4-didecylaminopyrrolidone, ethylhexyl-I,4-dimethylaminobenzoate, 2,5-bis(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone And other α-aminoalkyl ketone-based compounds, hydrazine, 2·octanedione, 1-[4-(phenylthio)phenyl]-2-(indolyl-benzhydrylhydrazine), ethyl ketone-l -[9-ethyl 26 200921278 winter (2-methyl benzoyl) _9H+ sitting _3_ base] + (Ethylene-based (6) and other biological products, bis (2,4,6-trimethylphenyl fluorenyl) _ phenyl phosphine oxide and other oxidized lining compounds. These photopolymerization initiators may be used singly or in combination of two or more. Among them, the phosphine oxide-based initiator is preferred because it can easily form the shape of the obtained projection for liquid crystal alignment into a bow shape. Among the above-mentioned phosphine oxide-based initiators, there are commercially available ones, for example, Irgacure 8 ί 9 (manufactured by Ciba Specialty Chemicals Co., Ltd.), __ 8! 9 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and Darocure TP〇 ( Made by Ciba Specialty Chemicals Co., Ltd., sp_246 (made by ADEKA). In the negative resist of the present invention, the content of the photopolymerization initiator is not particularly limited, and a preferred lower limit is 0" by weight based on 1 part by weight of the total of the alkali-soluble resin and the polymerizable monomer. The upper limit is preferably 4 〇 by weight. When the content of the photopolymerization initiator is less than 1 part by weight, the photocuring will be insufficient, and if the adhesion between the liquid crystal alignment protrusion and the substrate is lowered, if it exceeds 40 parts by weight, the photohardening reaction may excessively proceed. The shape of the developing residue or the obtained liquid crystal alignment protrusion is not bow-shaped, resulting in abnormal liquid crystal alignment. A more preferred lower limit of the content of the photopolymerization initiator is 0.2 parts by weight, more preferably 3 parts by weight, still more preferably 0.5 parts by weight, and still more preferably 2 parts by weight. In order to alleviate the reaction hindrance caused by oxygen, the negative resist of the present invention may further contain a reaction assistant. By using the above-mentioned reaction assistant together with the dehydrogenation type photoinitiator, the rate of hardening upon irradiation with light can be increased. The above reaction assistants may be exemplified by n-butylamine, di-n-butylamine, triethylamine, tri-ethylidene tetraamine, p-dimethylaminobenzoic acid ethyl ester, p-terracer 27 200921278-amino group stupid An amine-based reaction aid such as isoamyl phthalate, a phosphine-based reaction aid such as tri-n-butylphosphine, or a sulfonic acid-based reaction aid such as s-nodal isothiourea-p-toluenesulfonate. These reaction assistants may be used singly or in combination of two or more. The negative resist of the present invention may also contain a decane coupling agent. The above decane coupling agent has an effect of improving the adhesion between the negative resist of the present invention and the substrate. The above decane coupling agent is not particularly limited, and a previously known stone sinter coupling agent can be used. Wherein ' is preferably one having an acryloxy group or a methyl propylene oxide group as a functional group. By containing a dreaming coupling agent having an acryloxy group or a methyl propylene oxide as a functional group, the adhesion of the negative resist of the present invention to a substrate can be greatly improved. Examples of the decane coupling agent having the above propylene hydroxy group include 3-propyl methoxypropyltrimethoxysilane m (tetra)oxypropyltriethoxy decane. Further, examples of the decane coupling agent having the above-mentioned f-group acryloxy group include 3-methyl propylene methoxy propyl methyl dimethoxy decane and % methacryl methoxy propyl trimethoxy hydride. Burned, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more. In the negative resist of the present invention, the content of the above-mentioned decane coupling agent is not particularly limited. When the total of the solubility-reducing gambling and the polymerizable monomer is (10) $ parts, the preferred lower limit is 〇.丨 weight. The upper limit is preferably 4 parts by weight. When the content of the above-mentioned sulphur coupling agent is less than 1 part by weight, the adhesion to the substrate is lowered. If it exceeds 4 parts by weight, an alkaline development occurs in the photolithography 28 200921278. A more preferable upper limit of the content of the above decane coupling agent is 30 parts by weight. The lower limit is 1 weight of Dong, the agent's anti-agent, which constitutes the negative resistance of the present invention - becomes the weight: the solvent is adjusted to the lower limit of the solid concentration, the upper limit is 5 G weight%, preferably The lower limit is 10% by weight and the upper limit is 40% by weight. The organic solvent which is soluble or dispersible in the above respective components and which is excellent in the operation is not particularly limited. Specifically, one can be exemplified by methyl acesulfame, ethyl acesulfame, butyl celecoxib, diethylene glycol monomethyl hydrazine, diethylene glycol di butyl sulphate, diethylene glycol methyl sulphur, propylene glycol Hyperthyroid acetic acid vinegar (hereinafter referred to as "PGMAe"), methyl ethyl net, methyl isobutyl ketone, cyclohexyl, toluene, gas imitation, digastric hospital, ethyl acetate, methyl lactate, lactate B Vinegar, methanol, ethanol, propanol, butanol, tetrahydrofuran, etc. The above organic solvent preferably has a boiling point of from 100 to 200. More preferably, the organic solvent having a boiling point of 120 to 18 (the range of TC) is used. The method for producing the negative resist of the present invention is not particularly limited, and examples thereof include the following methods: The above-mentioned test-soluble resin, a polymerizable monomer containing a phenolic epoxy (meth) acrylate, a photopolymerization initiator, an organic solvent, and an optional additive are placed in a stirring tank, and are mixed using a stirring blade or the like. A method of manufacturing a projection for liquid crystal alignment by using a negative resist. When a negative resist of the present invention is used to produce a projection for liquid crystal alignment, 29 200921278 First, the negative resist of the present invention is coated. The coating film is formed to have a specific thickness to form a film. The coating method is not particularly limited, and examples thereof include spin coating, slit rotation, slit coating, spray coating, and dip coating. A conventionally known coating method such as a bar coating method, etc. Next, an active light such as ultraviolet rays is irradiated onto the formed film through a mask having a specific pattern, thereby making the negative of the present invention The alkali-soluble resin, the polymerizable monomer, and the photopolymerization initiator contained in the resist are photocured by the reaction in the light-irradiating portion. The active light is not particularly limited, and for example, visible light, ultraviolet light, or far ultraviolet light can be used. The electron beam and the X-ray f are preferably ultraviolet rays. The liquid crystal alignment protrusion can be formed, for example, by adjusting the amount of light irradiated to the liquid crystal alignment protrusion forming portion of the coating film. The method to be used, the method and the like: when the active light is irradiated through the mask, for example, a gray scale or a half-order light is used in order to form a bow-shaped liquid crystal alignment protrusion in an alkali development treatment to be described later. The wavelength of the active light such as ultraviolet rays to be irradiated is not particularly limited, and ultraviolet rays having a wavelength of about 200 to 600 nm are preferably used. The preferred lower limit of the irradiation amount of the active light is 1 〇mj/em 2 . The upper limit is preferably SOOmJ/cm2 ^ If the irradiation dose of the above active light is less than 1 〇mW, the photohardening will be insufficient, and the image is developed during the development step. If the irradiation amount of the active light rays exceeds 500 mJ/cm 2 , the development residue is likely to be formed. 30 200921278 Next, the photocured material after photocuring is subjected to alkaline development to form a substrate on the substrate. A liquid crystal alignment protrusion formed by a photo-cured material of a negative resist. The solvent used in the alkaline development treatment is a solvent having the ability to dissolve the coating film of the uncured portion. There is no particular limitation, and examples thereof include inorganic compounds such as sodium carbonate, sodium hydrogencarbonate, carbon _, hydrogencarbon hydride, sodium phthalate, potassium citrate, sodium hydroxide, and hydrazine, or diethanol slaves. An aqueous solution of diethylamine, triethanolamine, oxidized tetraalkylammonium oxide, and cerium oxide tetramethyl-specific organic basic compound. The above-mentioned organic developer may also contain an interfacially active water-soluble, an organic solvent, a wet agent, a low molecular compound having a transbasic group or a few acid groups, as needed. In particular, the interface activity is called "cloth", and there are many improvement effects on developability and solution. Therefore, it is preferable to add a surfactant in comparison with w. The surfactant used in the above-mentioned animated developer is, for example, an anionic surfactant of the ancient sodium sulfonate, and a non-dissociating M of the polyalkylene group. w I. cationic frog frog <&, active agent, cationic surfactant having a tetraalkylammonium group, and the like. The method of qualitative development treatment, 廿 成 成 抑, preferably 15~45t =, special system, pass (four) in 10~ fog development, brush development, two temperatures, using immersion development, spray ^ super Method such as oral wave development. It is finally reconstituted in a drying oven. (: The following, dry welding, dry knife filling. The drying temperature is preferably 250. The drying time is preferably 6〇 minutes^ and the drying time is extended by more than 6〇. The right temperature is over 250X:, on the color concentrating sheet. When the liquid crystal alignment protrusion is formed, the coloring pigment or dye to the opening portion is damaged by 31 200921278, and the display quality itself is lowered. The liquid crystal alignment formed by using the negative resist of the present invention is used. The protrusion is also one of the inventions. The color filter having the protrusion for liquid crystal alignment of the present invention is also one of the inventions. The color filter of the present invention has the above-described negative resist of the present invention. In the liquid crystal display device, the liquid crystal display device formed by using the color filter has a wide viewing angle. The liquid crystal display device formed by using the negative resist of the present invention or the color filter of the present invention is also Further, by using the negative resist of the present invention, columnar spacers for limiting the cell gap of the liquid crystal display device can be formed. The negative resist of the present invention is used. In the method of forming the columnar spacer, for example, a portion which becomes a columnar spacer on the substrate formed on the substrate by the above method, for example, is irradiated more than the exposure energy required for producing the protrusion for liquid crystal alignment. After a large amount of light, the above alkaline development is carried out. According to the above method, the negative electrode (4) of the present invention can be sufficiently polymerized and cured by the light irradiated to the film, thereby forming higher than the liquid crystal alignment. According to the present invention, a columnar spacer for forming a liquid crystal alignment protrusion can be provided, which can be opened to control the liquid crystal alignment of the liquid crystal display device. Moreover, the liquid crystal afterimage phenomenon can be prevented from occurring in the manufactured liquid crystal display device. [Embodiment] 32 200921278 The following examples are given to further illustrate the aspects of the invention, but the invention is not limited to the embodiments. (Example 1) (1) Production of color filter A Cr thin film pattern was formed on a transparent substrate by photolithography. On the above, a red, blue, and green photosensitive resin composition is patterned by photolithography to form red, blue, and green pixels. Further, an ITO film was formed on the entire surface by extinction of money to form a transparent conductive film layer, thereby producing a color light-emitting sheet. (2) Synthesis of alkali-soluble resin 150 parts by weight of PGMAe was placed in a flask equipped with a mixing device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while stirring, and the temperature was raised to 1 Torr. Hey. Then, a monomer mixture composed of 3 2 · 6 parts by weight of methacrylic acid and 31.1 parts by weight (0.31 mol) of methyl methacrylate was added from a dropping funnel over 2 hours. And 3.6 parts by weight of a third butyl hydroperoxide (manufactured by NOF, PERBUTYL®) was added dropwise to the flask at 110. (: aging was continued for 3 hours while stirring. " Next, 36.4 parts by weight (0.20 mol) of 3,4_epoxycyclohexyl methacrylate, 0.36 part by weight of triphenylphosphine, and 15 parts by weight of hydrazine were added. The hydrazine-based benzene is equal to im: the next reaction is 1 M. The reaction is carried out under an air/nitrogen atmosphere, whereby an acid value of IGGmgKOH/g and a double bond equivalent (per 1 mole of unsaturated group) can be obtained. The g-weight of the resin is 5 Å of a test resin solution having an average molecular weight of 15 Å (solid content: 33 200921278 %). (3) Preparation of a negative-type resist agent for forming a liquid crystal alignment protrusion 200 parts by weight The phenolic phenolic epoxy acrylate as a polymerizable monomer (solid content: 80%, PGMAc: 20%, EA-6320, manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts by weight of Irgacure 819 as a photoreaction initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., fluorenylphosphine oxide), and 1 part by weight of 3-propenyloxypropane as a decane coupling agent having an acryloxy group. Base trimethoxy stone shochu (ΚΒΜ-5 ΙΟ3'^^ Vietnam Chemical Co., Ltd. And a PGMAc as a solvent, and a negative resist for forming a liquid crystal alignment protrusion is prepared. (4) Production of a color filter substrate on which a liquid crystal alignment protrusion is formed, the obtained liquid crystal The alignment protrusion formation negative-working resist was spin-coated on the color filter manufactured in (1), and then dried at 8 ° C for 2 minutes to obtain a coating film. The circular pattern light was passed through 8 // m After the obtained coating film was irradiated with ultraviolet rays of 100 mJ/cm 2 , it was developed with 〇 1 % sodium carbonate aqueous solution for a second, and then washed with pure water for 30 seconds. Thereafter, it was dried at 200 ° C for 3 minutes. The color filter substrate having the protrusion for the alignment control was obtained. (Example 2) 150 parts by weight of PGMAc was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube. Nitrogen replacement, while stirring, the temperature was raised to 11 〇 ° C. Next, 'from the dropping funnel, 22.6 parts by weight (〇38 mol) of thioglycolic acid, 31.1 parts by weight (0.18 mol) of sulfhydryl group was added for 2 hours.丙浠34 200921278 Monomer mixture of benzyl acetate The compound and 3.6 parts by weight of a third butyl hydroperoxide (manufactured by Nippon Oil & Fats Co., Ltd., PERBUTYL®) were added dropwise to the flask, and aging was continued for 3 hours under 11 Torr. Next, 36.4 parts by weight were added. (0.20 mol) of 3,4-epoxycyclohexyl methacrylate, 0.36 part by weight of triphenylphosphine, and 0.15 part by weight of methyl hydroquinone'. This is equal to 100. (: 1 reaction) Hour. The reaction was carried out under an air/nitrogen atmosphere. Thus, an alkali-soluble resin solution P-2 (solid content: 40%) having an acid value of 10 mg/kg and a weight average molecular weight of 15,000 was obtained. A color light-emitting sheet substrate having protrusions for liquid crystal alignment was obtained in the same manner as in Example 1 except that the obtained alkali-soluble resin solution P-2 was used. (Example 3) A color calender substrate 0 having a projection for liquid crystal alignment (Examples 4 to 18) was obtained in the same manner as in Example 1 except that Irgacure 65 1 was used as the photoinitiator. The color filter substrate having the protrusions for liquid crystal alignment was obtained in the same manner as in Example 1 so that the blending ratio was as shown in the table. (Comparative Example 1) A liquid crystal alignment protrusion was formed in the same manner as in Example 1 except that pentaerythritol triacrylate (pe_3a, manufactured by Kyoei Co., Ltd.) was used instead of phenol novolac epoxy acrylate (ΕΑ·6320). Negative Resist, 35 200921278 A negative-type resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 2) In the same manner as in Example 1, except that pentaerythritol tetraacrylate (SR295, manufactured by SARTOMER Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320), a negative electrode for liquid crystal alignment was prepared. In the type of the resist, a negative-type anti-surname agent for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having protrusions for liquid crystal alignment. (Comparative Example 3) A liquid crystal alignment protrusion was prepared in the same manner as in Example 1 except that dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320). A negative-type resist is formed, and a negative-type resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 4) In the same manner as Example 1, except that 1,4-butanediol diglycidyl ether diacrylate (ARONIX M450, manufactured by Toagosei Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320). In the same manner, a negative resist for forming a projection for liquid crystal alignment is prepared, and a negative resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 5) In place of benzoic acid epoxy acrylate, tris(propylene oxyethyl) isocyanurate (TEICA, manufactured by Industrial Pharmaceutical Co., Ltd.) was used instead.

In the same manner as in Example 1, except that the liquid crystal 200921278 (ΕΑ_6320) was used, the negative resist for forming a liquid crystal alignment protrusion was prepared, using the examples 1 to 18 and the comparative example T. A color filter substrate having a projection for liquid crystal alignment is obtained by forming a negative anti-surname agent for the liquid crystal alignment protrusions. (Evaluation) The following evaluations were performed on Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Tables 1 to 3. (Residual image evaluation) , , 8 VI Days The MVA_LCD was fabricated by using a raised color filter substrate. Thereafter, a voltage was continuously applied to the MVA_LCD at room temperature for 24 hours to perform image display. The images after 24 hours of continuous display were visually observed. The display pattern was evaluated immediately as "Zy", and the case was evaluated as "?", and the case where it disappeared within 1 minute was evaluated as "〇", and the case where it did not disappear within 1 minute was evaluated as "X: (Development residue evaluation) X ° The liquid crystal alignment slag was evaluated by optical microscopy and SEM. The developer's dry residue will be smothered at the periphery of the pattern and will not be seen as "◎, will be in the _ An H pan, the situation of Go / check ^" will see very few in the periphery of the pattern The development & + condition is evaluated as "〇", and it will be evaluated in the picture of Honggang, but the situation of i " residual is evaluated as "eight, ^ " △ of the shell residue" will see more development residue (protrusion shape and light removal evaluation) ', ,, X". By optical microscopy and SEM, the shape of the liquid crystal alignment is observed. 37 200921278 38 (Moldworm 14) Flute protrusion shape Development residue evaluation afterimage evaluation Other solvent Photopolymerization initiator i Polymerizable monomer alkali-soluble resin decane coupling agent PGMAc sc 3 1 Os C rS 垂«> SO 5 w Q a in* L· ^ p>>>Lu'^<· 1,4-butanediol diglycidyl ether diacrylate | (ARONIXM450: manufactured by Toagosei Co., Ltd.) /—N α s ι» &gt ; * .•洚^ a 扦 ί ί 漭婢 漭婢 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ V 〇 〇 511 511 511 511 511 511 511 511 511 511 511 511 511 511 ^ ^ ^ ^ ^ ^ ^ ^ ^ IW ou 14® ·.二|;E * ^ s ·. Η ^ ^ ^ 5 W ^ Q ^ WO ru _ .,S nl nj —peak s ..Η ^ § >>抻Ο f ·ν> | W *211 G Barrier » of _Every §; ..H ^ ^ >yn S ϋ w /-~SU) 14 S舛1φ ·Mold Card Dicky Insect Today 4i c^ ^ _ Curtain S, Book 8冷屝 y 1 1 〇〇〇I—· 〇〇1 5 1 1 1 1 1 1 1 1 g 1 200 Example 1 ου 〇◎ 〇>—· 〇1 1 1 1 1 1 1 1 1 g 200 1 Example 2; trapezoidal 〇〇〇 1 1 1 1 1 1 1 1 1 g 1 200 Example 3 1 μ 1 ◎ 〇 5 〇 〇 〇 1 1 1 1 1 1 1 1 1 1 1 Example 4 (4) 1 ◎ 〇〇〇 1 o 1 1 1 « 1 1 1 1 I o Example 5 1 bow ◎ 〇〇 1 1 > 1 垂 1 1 t 1-^ g 1 1 200 Example 6 I bow | ◎ 〇〇ο t 1 1 1 1 g 1 1 g 1 1 200 Example 7 «Λ ◎ ◎ ο t 1 1 1 1 1 1 δ 1 M 〇 1 Example 8 , bow ◎ 〇〇 ο 1 st 1 1 1 1 1 g 1 t to o Example 9 ◎ 〇 5 ο 1 5 1 1 ( m* 1 1 ig 1 200 | Example ίο | 200921278 39

(Mg_14) Mai r荦 protrusion shape; Development residue evaluation afterimage evaluation Other agent photopolymerization initiator Polymerizable single experience solvent resin decane coupling agent PGMAc 〇C 1 GS 1—* β Ρ 1 00 s 5 W 5 ^ ^: REVIEW 5? >> ^ 靡Vw/ 1,4-butanediol diglycidyl ether diacrylate (ARONIXM450: manufactured by Toagosei Co., Ltd.) 〇S 1' > ^ ••洚CT ^ 3踝\w/ ,~\ ζΛ S Ό ^ * ί a 〇a工> 1U W ^ :»审>> ^ *5!i Wen Hong S k ^ ^ @ » ^ ^ S Ν««* m helmet>藓» ° | Ι4ί · it ^>5 J + ξ s H® # 5; ..H ^ έ _迕Ο »婢健审^ S atr G脔> ^ ϊέ| ^>55 _ ́ § ..Η ^ S , § ^ ^ Screening s: , _✓ ΠΓΓ ς; 蔺 s*u- > ^ » έ | W r, !z ni ^11 H® S . .H ^ rt ^ ^ is v-^ ΠΚΓ W > os /s UJ 1# o do w® ·.Muscle card drive: moldy today 5 miscellaneous 4ι π- pt one to 3 ·. Η万5 _琛〇t *> » 〇· οσ w 3 辟·"TJ NJ y bow ◎ ◎ 〇1—* 〇1 1 1 1 1 1 1 1 g > 〇1 Example 11 i trapezoid ◎ 〇〇〇〇1 1 1垂t 1 1 1 g 1 1 2 00 1 Embodiment 12 "Bow shape| ◎ 〇〇〇 1 1 1 1 1 1 1 g 1 1 1 200 Example 13 丨 bow shape| ◎ ◎ 〇 1 t 1 1 垂 1 1 g 1 1 200 1 Example 14 trapezoid ◎ 〇〇〇1 1 1 1 < 1 1 g 1 1 1 200 Example 15 丨 bow shape | 〇〇〇〇 1 1 1 1 1 1 g 1 t 1 1 ο Example 16 i I bow | > ◎ 5 〇垂1 1 垂1 1 g 垂t t 1 200 1 |Example 17 Trapezoidal > 〇〇〇1 垂1 1 1 1 g 1 < 1 1 200 |Example 18 I [Mu 2] 200921278 :κί PGMAc

Irgacur? 651

Irgacure - 819 1,4-1-Bu Pho.^Yayao wears black l·31荼踝温(ARONIXM450:^商命许冷^濉缂) Bu ^^@骤^也审踝-(DPHA: 3 ^-^^3雔)) (SR295: SARTOMER.^·^^^) (PE-3A: 氺澉, 雔硌) 录 簿 涔 涔 涔 涔 涔 涔 涔 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (驾士士-啷卜鲥冷^鸿蝌) (衅4-^苏今屮*: 4000) 蔺漭辫众烊鸡卜f^翠磷if^a^stsl (EA-7140: 鸯卡^-噼卜刺冷^嫜辟) (Time t card even today 屮t two 800) 漭 漭 埤涔 埤涔 Λ舛 Λ舛 磷 磷 Phosphorus chain potassium ^ 琛 琛 ΕΑ ΕΑ 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340辟) _^1+苏今屮*:1200) 舛零翠磷麻衅31粢踝si (EA-6320: Driving card 噼-噼卜鵃冷3嬅娲) (tt Kasu today 屮t: 1000) ρ·2 P-1 〇5 50 5 °°0 200

S Δ 10 100 5 80 200 > s 100 s § 200 - swim weight 3 > 10 100 5 § 200

S Δ 5 50 10 § 200 - 齐^5 200921278 [Industrial Applicability] According to the present invention, a negative resist for forming a liquid crystal alignment protrusion can be provided, which can form a liquid crystal for a liquid crystal display device The protrusions are controlled to be controlled, and the phenomenon of liquid crystal afterimage of the liquid crystal display device produced can be prevented. [Simple description of the diagram] None [Key component symbol description] None 41

Claims (1)

200921278 X. Patent application: 1 · A negative resist for forming a liquid crystal alignment protrusion, comprising an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator for forming an MVA liquid crystal display device The liquid crystal alignment protrusion is characterized in that the polymerizable monomer contains a novolac epoxy (fluorenyl) acrylate. 2. The negative resist for forming a projection for liquid crystal alignment according to the first aspect of the invention, wherein the phenolic epoxy (fluorenyl) acrylate has a weight average molecular weight of 600 to 2,000. 3. The negative-type anti-money agent for forming a liquid crystal alignment protrusion according to claim 1 or 2, wherein the epoxy (meth) acrylate has a solubility functional group. 4. The negative resist for forming a projection for liquid crystal alignment according to the first, second or third aspect of the patent application, wherein the alkali-soluble resin has a (fluorenyl)acrylic group, a slow-base group and a sulfhydryl group. 5. The negative resist for forming a liquid crystal alignment protrusion according to the first, second, third or fourth aspect of the invention, wherein the photopolymerizable initiator contains a phosphine oxide ruthenium initiator. XI. Schema: Benefit 42