TW200900463A - Curable resin composition for column spacer, column spacer, and liquid-crystal display element - Google Patents

Abstract

A curable resin composition for column spacers which has excellent develop ability and can form a column spacer which is not abraded by rubbing in a step in producing a liquid-crystal display element. Also provided are: a column spacer formed from the curable resin composition for column spacers; and a liquid-crystal display element. The curable resin composition for column spacers comprises: a urethane (meth) acryl ate compound having car boxy groups in the molecule and having a functionality of 6 or higher; and a photo initiator.

Description

200900463 IX. Description of the invention: [Technical field to which the invention pertains]. The present invention relates to a curable resin composition for a columnar spacer, :: a columnar spacer which has excellent developability and is not scraped by a rubbing treatment in a liquid crystal display element. . Further, it is also a columnar spacer in which a curable resin composition for a columnar spacer is used, and a liquid crystal display element. [Prior Art] Generally, a liquid crystal display element includes a spacer for maintaining a gap between two glass substrates, and the like includes a transparent electrode or a polarized light, and an alignment layer for aligning the liquid crystal material. Composition. Now, mainly, a particle spacer having a particle diameter of several arrays is used as a spacer. However, in the prior art method of manufacturing a liquid crystal display device, a fine particle spacer may be disposed in the pixel portion due to random scattering of the fine particle spacers on the glass substrate. If the silly sound is abnormal. There are microparticle spacers in ρ, because

The problem that the image quality is lowered is caused by the disordered I 0 in the liquid crystal alignment around the spacer, causing light leakage and lowering the contrast of the image. On the other hand, various methods of arranging the fine particle spacers in which the fine particle spacers are not disposed in the pixel portion have been studied, but any of the methods is complicated to operate and lacks practicality. In recent years, in order to improve the productivity of liquid crystal display devices, a drop-injection method (One Drop-cut τ_η〇ι〇π, which is attached to a liquid crystal sealing surface of a glass substrate, and a predetermined amount of liquid crystal is dropped, is proposed. ^The method for manufacturing a liquid crystal display element by maintaining a predetermined cell gap under a vacuum under the vacuum of the substrate of the ghost liquid crystal panel. By the method of 200900463, even if the liquid crystal display is compared with the previous method The area of Kenting is eight, the cell gap is narrow, and the sealing of liquid crystal is easy. Therefore, it is considered that the 〇F 法 method will become the mainstream of the manufacturing method of liquid crystal display elements. However, if microparticle spacers are used in the ODF method, there will be When the liquid crystal is dropped or the fine particle spacer dispersed when the opposite substrate is bonded flows with the flow of the liquid crystal, the distribution of the fine particle spacer on the substrate becomes uneven. If the distribution of the fine particle spacer becomes non-uniform Evenly, it will cause a deviation in the cell gap of the liquid crystal unit, which causes a problem of color spots on the liquid crystal display. On the liquid crystal substrate, a columnar spacer for maintaining a uniform pattern of a uniform cell gap is formed by a method of photolithography to replace the previous microparticle spacer, and is gradually put into practical use. (For example, Patent Document No. 2, Patent Document 2, etc.) If the columnar spacer is used, the problem of disposing a spacer in the pixel portion or the problem of spacer unevenness in the ODF method can be solved. When the liquid crystal display element is manufactured by the substrate of the spacer, the alignment film is usually formed on the column spacer to restrict the alignment of the liquid crystal, and the alignment film must be subjected to a rubbing treatment. However, the prior column spacer, Due to the photohardening reaction during exposure or the thermal reaction conditions during post-baking, the surface of the temple will be cut by the rubbing treatment, so that the height of the column spacers produces #I _; The early 兀 gap becomes uneven, and the display quality of the liquid crystal display element to be manufactured is lowered. (Patent Document 1) Japanese Patent Laid-Open Publication No. Hei 2 No. Hei 91-95954 (Patent Document 2) Japanese Patent Japanese Patent Publication No. 2〇〇1—1597〇7 6 200900463 [Summary of the Invention]

(1)

(2)

A1 represents a residue obtained by removing two hydroxyl groups from a polyglycol compound, a polyoxyalkylene glycol compound, or a polycaprolactone diol compound, and X represents a residue obtained by removing two isocyanate groups from a diisocyanate compound, and a2 represents Residues after removal of two hydroxyl groups and one slow base from a diol compound containing a carboxyl group, B represents a residue after removal of an epoxy group from an unsaturated compound containing an epoxy group, and R· represents a radical having a mercapto group ( The sulfhydryl compound removes the residue after the base, and m is a natural number of 1 to 50. 7 200900463 A3

C —-Ν—β*—Μ——C— ΟX- II I I. II f^|*—Β·"Μ II I ι Ο Η Η

Α3 represents a residue obtained by removing a hydroxyl group from a trifunctional or higher (meth) acrylate compound having a hydroxyl group, Β1 represents a residue obtained by removing two isocyanate groups from a diisocyanate compound, and X represents an alkanediol compound, and a poly An alkylene oxide diol compound or a polycaprolactone diol compound (having a carboxyl group in the molecule or a carboxyl group in the molecule), wherein the residue after removing two hydroxyl groups (wherein the molecule contains a carboxyl group and contains one or more The alkanediol compound, the polyoxyalkylene glycol compound, or the polycaprolactone diol compound removes the residue after the two bases, and the η is a natural number. In particular, the columnar spacer obtained by using the curable resin composition for a columnar spacer of the present invention as described above can provide excellent flexibility and compression recovery characteristics of the ruthenium. Therefore, the molecule has a carboxyl group. The 6-functional or higher (meth)acrylic acid urethane compound is preferably at least one denatured structure selected from the group consisting of denatured caprolactone, denatured ethylene oxide, and denatured propylene oxide in the molecule. Further, in the present specification, the term "denatured caprolactone" means a ring-opening or ring-opening polymerization of a portion of an (meth)acrylic acid vinegar compound derived from an alcohol and a (meth)acrylic acid group. Things. Further, the term "oxydiethylene" means that an ethylene oxide fragment is introduced between the (meth) propyl group of the (meth) acrylate compound. Further, the propylene oxide is represented by the (meth)acrylic acid S, and the propylene oxide fragment is introduced between the 200900463 and the (meth) propylene sulfhydryl group. . Further, a 6-functional or higher (meth)acrylic acid urethane carboxylic acid compound having a carboxyl group in the above-mentioned knife can also be produced by the following method. The 6-functional or higher (meth)acrylic acid urethane compound having a carboxyl group in the above molecule can be obtained by a method in which a compound having a thiol group and two or more thio groups and two or more molecules in the molecule are obtained. A method of reacting a compound of a sulfonic acid group to form a base compound containing an ethylenically unsaturated group, or a method of uniformly mixing the above compounds and reacting them. Further, the 6-functional or higher (fluorenyl) acrylamide phthalate compound having a carboxyl group in the molecule can also be obtained by reacting a diol compound having a carboxyl group with a diisocyanate compound, and further adding ethylene. A method of treating a hydroxy compound of a group, or a method of mixing the above compounds and reacting them. Among them, 'a compound obtained by reacting a compound having a carboxyl group and two or more hydroxyl groups, y with a compound having two or more isocyanate groups in the molecule, and further adding a hydroxy compound having an ethylenically unsaturated group is preferable. A compound obtained by reacting a diol compound (E1) having a carboxyl group with a diisocyanate compound (E2) and further adding a hydroxy compound containing a vinyl unsaturated group. The above-mentioned 6-functional or higher (meth)acrylic acid amino phthalic acid vinegar compound having a carboxyl group in the molecule can be specifically such that the diol compound (E1) containing a slow group and the diisocyanate compound (E2) are usually 1: The compound (E3) obtained by the molar reaction of 2 is obtained by adding an hydroxy compound (E4) containing an ethylenically unsaturated 9 200900463 group. As the carboxyl group-containing diol compound (E1), those having a molecular weight of 500 or less can be suitably used. When the molecular weight is outside the range, the solubility in the reaction solvent may be lowered to lower the reactivity with the diisocyanate compound (E2). The dicarboxylic acid compound (E 1 ) having a carboxyl group having a molecular weight of 500 or less is not particularly limited, and specific examples thereof include tartaric acid, dimethylacetic acid, bis(4-hydroxyphenyl)acetic acid, and 2, 2-bis(hydroxymethyl)propionic acid, 2,2-bis(ethyl)propionic acid, 2,2-bis(hydroxypropyl)propionic acid, 2,2-bis(hydroxymethyl)butyric acid, 4,4-bis(p-hydroxyphenyl)pentanoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, homogentic acid, and the like. Among them, 2,2-bis(hydroxymethyl)butanthene, 2,2-bis(hydroxyindenyl)propionic acid, 2,2-bis(hydroxyethyl)propionic acid, 2,2-bis(hydroxyl) can be suitably used. Propyl) propionic acid. As the diisocyanate compound (E2), a molecule of 300 or less can be suitably used. When the molecular weight is outside the range, the reactivity with the above-mentioned diol-containing diol compound (E1) may be reduced, and the diisocyanate compound (E2) having a molecular weight of 300 or less may be specifically limited. For example, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-didecyl heptane diisocyanate, octadecyl diisocyanate, 2,5-dimethylhexane can be cited. -丨,6_diisocyanate, 2,2,4-trimethylpentane-; i,5-diisocyanate, nona-nonyldiisocyanate, 2,2,4-trimethylhexyl diisocyanate, ten Methylene diisocyanate, undecyl diisocyanate, dodecamethylene diisocyanate, decamethyl diisocyanate, fifteen-decyl diisocyanate, butene diiso-10 200900463 cyanate, 1, 3-butadiene-1,4-diisocyanate decanoic acid 酝2-butyne diisocyanate,

Toluene diisocyanate S, isophor, I cyanate, 1,4- phenyldimethyl diisocyanate - 1 Benzene cyanide S 曰, 4,4,-diphenylmethane diisocyanate In the case of naphthalene diisocyanate, hexamethylene diisocyanate or diphenyldecane diisocyanate, etc., it is suitable to use hexamethylene diisocyanate. Ketone diisocyanate §, toluene diisocyanate. On the top (the compound (E3) is added to the base compound (E4) containing an ethylenically unsaturated group, it is also #### _ Do not react with polyhydric alcohol or polyol and diisocyanate compound 16 (Ε2) to extend the molecular chain. 曰 As the above polyol, preferably the molecule ^ 5 〇〇 α. If the molecule is detached from the molecule In the case of 祀 ', there is a case where the flexibility of the column spacer is lowered. The molecular weight is preferably 5 〇〇 1 to 1 〇〇〇〇, and more preferably 5 〇〇 to 4000. The horse is not particularly useful as the above polyol. Specific examples thereof include, for example, a polyether polyol, a polyg-based polyol, a polycarbonate polyol, a oxane 111, a raw bisphenol glycol, and a propylene. The polyhydric alcohol, the polybutadiene-based polyhexanol polyfluorene k-based poly-π-alcohol, etc., and further, a poly-isocyanate such as a low alcohol such as i,6-hexanediol or isophora-diisocyanate is used. A urethane dimer obtained by a molar ratio reaction of α: n (integral integer) is a trans group compound (e4) having an ethylenically unsaturated group as described above.疋', for example, 2-hydroxyethyl (meth)acrylate, (yiyi L propyl phthalate, glycerol bis(indenyl) propyl 11 200900463 acid ester, 2-hydroxy group _ 3_acryloxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Among them, 2-hydroxyethyl (meth) acrylate and (mercapto) acrylate may be suitably used. 2-hydroxypropyl ester, pentaerythritol triacrylate, dipentaerythritol pentaacrylate. In order to prepare a 6-functional (meth)acrylic acid urethane compound having a reductive group in the above molecule, the above-mentioned carboxyl group-containing diol is first used. The compound (E1) is reacted with the above diisocyanate compound (E2) to obtain a compound (E3). By using a known reaction method, for example, in a solvent such as ethyl acetate or methyl ethyl ketone, the reaction may be carried out at a temperature below the boiling point of the solvent (preferably 6 〇 to 8 〇 C). Further, as described above, The reaction molar ratio of the carboxyl group-containing diol compound (E1) to the diisocyanate compound (E2) is about 1:2, and an isocyanate can be added to both ends to add or contain a vinyl group to be described later. The addition efficiency of the hydroxy compound of the unsaturated group proceeds favorably. Then, the above polyol is added to the compound (E3) as needed, and at this time, the reaction is carried out at a temperature lower than the point of the solvent. In the reaction, it is advantageous to add a known catalyst such as dibutyltin dilaurate. The catalyst is used in an amount of about 1% by weight to about 1% by weight based on the above polyol, and is reacted for about 3 to 1 hour at 60 to 8 Torr. The reaction molar ratio of the substance (E3) to the above polyol is cold by the above-mentioned compound: call-1 (cold is 2 or more of the illusion A right, the isocyanate can be added at both ends, and according to the reaction When the molar ratio is further reacted with the diisocyanate compound (Μ), the addition of the hydroxy compound (E4) containing the 7-tetraethylene ethylenically unsaturated group described later can be efficiently performed. 12 200900463 Further, a hydroxy compound (E4) containing an ethylenically unsaturated group is added to the system to cause a reaction, and the reaction is terminated by the time point of the residual diisocyanate group being about 0.1 to 0.5% by weight. Further, a (meth)acrylic acid amino phthalic acid vinegar compound having a ruthenium functional group or more having a carboxyl group in the molecule can be obtained. The curable resin composition for a columnar spacer of the present invention contains a photoreaction initiator. The starting agent is not particularly limited, and examples thereof include previously known photoreactive initiators such as benzion, diphenylketone, diphenylethylenedione, thioxanthone, and the like. In terms of Examples include benzoin ether, benzoin ethyl ether, benzoin isobutyl ether, michlerone (Michler, sketne), [4_(phenylphenylthio)phenyl]phenyl ketone, 2,2-di曱oxy-1,2-diphenylethane-fluorenone, hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-indolyl-i-phenyl-propane-indole-ketone, [4-(2-Hydroxyethoxy)-phenyl]_2-hydroxy-2-methyl-oxime-propanone, methyl-1(4-indolyl)phenyl-2-morphin-propanone Ketone, 2-benzyl-2-diamino-1-(4-morpholinophenyl)-butane-indole-ketone, bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)_2,4,4-trimethyl-benzylphosphine oxide, 2,4,6-trimercaptobenzamide _-diphenyl-phosphine oxide, 2,4-diethyl oxime | the same, 2-chloropyrrole, etc. Further, for example, 2-(4-methylbenzyl)_2_(dimethyl Amino)-(4-morpholinophenyl)butanone, 2-(4-ethylbenzyl)_2-(dimethylamino)-1-(4-morpholinophenyl)butanone, 2-(4-isopropylbenzyl)_2-(dimethylamino)-1-(4-morpholinophenyl)butane-1-one, etc. Sales, Example 13 200900463 For example, "IRGACURE 369" and "IRGACURE 379" (Ciba

Specialty Chemicals Co., Ltd.). Further, for example, oligo[2-hydroxy-2-indolyl-l-[4-(1-methylvinyl)phenyl]propenone], "['[pendrazyl phenylsulfonyl)) Phenyl]_2-mercapto-2-(4-tolylsulfinyl)propane-fluorenone, 2,4-diethylthioxanthone, isopropyl sestonone, diphenyl- (2,4,6-trimercaptobenzylidene)phosphine oxide, 4-benzoquinone-4'-methyldiphenyl sulfide, phenyl phthalate, 4-phenyldiphenyl Base, ethyl-4-(dimethylamino)benzoate, benzyldidecyl ketal, 2-yl-2-yl-i-phenyl-indole-acetone, hydroxycyclohexylbenzene Ketone, 2-methyl-1-[4-(methylthio)-phenyl]_2-morpholinopropane-indole-ketone, mercapto-2-benzoic benzoate, 4-mercaptoyl Phenyl ketone, 2,2'-bis-(2-chlorophenyl)_ 4,5,4,5_tetraphenyl_2'1^-<1,2'> , (4,4'-bis(diethylamino)diphenyl ketone, 2,2'-bis(〇-700 phenyl)-4,4',5,5|-tetraphenyl-1, 2,-Limi, etc., 1-[9-ethyl-6-phenylhydrazin-3-oxa]-octane, small 嗣 _ 〇-acetate, 1-[9-ethyl -6-(2-methylphenylindenyl)-9·Η·-carbazole·3-based , ethane_丨-ketooxime-oxime-benzoate, 1-[9-ethyl-6-(2-methylbenzhydryl)-9.H.-carbazol-3-yl]- Ethyl_1_ketooxime.〇-acetate, ethyl_6_(1,3,5-trimethylbenzylidene)-9.H.-carbazol-3-yl]-ethane-1 -ketooxime_〇_benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9.H--oxazol-3-yl]-ethane-1 - ketooxime-0-benzoate, etc. Among them, ΐ-[9·ethyl_6_(2 曱 basic fluorenyl)-9.H·-0 carbazhen-3-yl]-ethene can be suitably used. The oxime ester compound of the ketone of the ketone is a commercially available product of the above-mentioned oxime ester compound, and examples thereof include "IRGACURE OXE02" (manufactured by Ciba Specialty Chemicals Co., Ltd.), etc. 14 200900463 The initiator may be used singly or in combination with two or more kinds of D in the curable resin composition for columnar spacers of the present invention, and the content of the photoreaction initiator is not particularly limited. 100 parts by weight of a 6-functional or higher (fluorenyl) urethane urethane compound having a carboxyl group, preferably a lower limit of 〇1 part by weight, preferably an upper limit of 50 parts by weight. When the content of the photoreactive initiator is less than the weight, the photocuring of the curable resin composition for the column spacer of the present invention may become insufficient, and it becomes difficult to obtain a pattern by development. When the content of the agent exceeds 50 parts by weight, the residue at the time of development becomes becomes =. A more preferred lower limit of the content of the above photoreaction initiator is 丨 by weight, and more preferably, the upper limit is 25 parts by weight. The composition may also be used. The reaction auxiliary agent for reducing the reaction disorder caused by oxygen in the columnar spacer of the present invention by the reaction and the light irradiation can be used in combination with the hydrogen abstraction photoreaction initiator. Hardening speed. The amine-based reaction aid is not particularly limited. For example, e rfc exemplifies a reaction aid, a phosphine-based reaction aid, and a sulfonic acid-based reaction aid. For example, dimethylaminobenzoic acid is exemplified as the above-mentioned amine-based reaction assistant, and there is no particular n-butylamine, di-n-butylamine, triethylamine, ethyltriethylammonate or p-dimethylamino. Isoamyl benzoate and the like. For example, it may be mentioned that the above-mentioned phosphine-based reaction assistant is not particularly limited to tri-n-butylphosphine. The above-mentioned acid-based reaction auxiliary agent is not particularly limited to -s-benzylisothiourea-p-toluenesulfonic acid or the like. 15 200900463 The 4 reaction auxiliaries may be used singly or in combination of two or more. In the curable resin composition for a columnar spacer of the present invention, a 6-functional or higher (meth)acrylic acid urethane compound having a carboxyl group in the molecule may be used as the alkali-soluble polymer compound ( In the second embodiment, the monomer component (the first embodiment) is used as a monomer component by using a 6-functional or higher (meth)acrylic acid urethane compound having a carboxyl group in the molecule. In the case of the curable resin composition for a columnar spacer of the first embodiment, the molecular weight of the (meth)acrylic acid amide carboxylic acid compound having a carboxyl group of 6 or more in the molecule is preferably 1 The acid value of the 6-functional or higher (meth)acrylic acid urethane compound having a carboxyl group in the above molecule is preferably from 5 to 50 mgKOH/g. When the molecular weight of the 6-functional or higher (fluorenyl) urethane urethane compound having a carboxyl group in the molecule is from 1,000 to 5,000, sufficient abrasion resistance can be ensured, and development of the residue is less likely to occur. A more preferred lower limit of the molecular weight of the (functional) (fluorenyl) acrylamide phthalate compound having a carboxyl group in the above molecule is 2 Å, and a more preferred upper limit is 4,500. Further, in the curable resin composition for a columnar spacer according to the first embodiment, as described above, in addition to the above-described (nonyl) urethane urethane compound having a carboxyl group in the molecule, it is preferred. At least one denatured polyfunctional (mercapto) acrylate compound selected from the group consisting of self-denatured caprolactone, denatured ethylene oxide, and denatured propylene oxide (hereinafter, also referred to as denatured polyfunctional (fluorenyl) group) Acrylate compound) as a monomer 16 200900463 component. As described above, the face 1 has such a denatured polyfunctional (meth) acrylate compound and is used as a monomer component. The curable resin composition for the column spacer of the form 1 is obtained, and the obtained h 4 + column is obtained. The spacers are those having excellent flexibility and compression recovery characteristics. The liquid B produced by using such a columnar spacer does not show a 7L piece', and at the same time, it can suppress the "heavy gravity" caused by the liquid crystal expansion during heating & "low temperature foaming" caused by liquid crystal shrinkage at a low temperature. In addition, the above-mentioned "gravity failure" means that the liquid crystal in the liquid crystal unit is heated and expanded during use of the liquid crystal display element, and when the cell gap is widened, the column spacer is raised from the substrate, and the column is raised. The liquid crystal which is incapable of maintaining the volume of the spacer flows downward, thereby causing a phenomenon of color spots on the upper half surface and the lower half surface of the display panel. X, the above-mentioned "low-temperature foaming" means a phenomenon in which the liquid crystal in the liquid crystal unit shrinks at a low temperature, and the internal pressure in the liquid crystal unit is rapidly lowered to cause bubbles. In the case of the polyfunctional (fluorenyl) acrylate compound obtained by denaturation of the above-mentioned denatured polyfunctional (meth) acrylate caprolactone, the polyfunctional (fluorenyl) acrylate compound is not particularly limited, and for example, Trihydromethane propane di(meth) acrylate, trishydroxy ethane bis(indenyl) acrylate, pentaerythritol bis(indenyl) acrylate vine, bis(trimethylolpropane) bis(indenyl) a compound obtained by denaturation of a bifunctional (meth) acrylate compound such as acrylate or dipentaerythritol di(meth)acrylate with caprolactone, or pentaerythritol tri(meth)acrylate or pentaerythritol tris(fluorenyl) Trifunctional or higher (fluorenyl)propene 17 such as acrylate, bis(trimethylolpropane)tri(meth)acrylate, dipentaerythritol tetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate, 200900463 A compound obtained by denaturation of a caprolactone compound or the like. Among them, a di- chelate obtained by denaturation of a trifunctional or higher hydroxy acrylate compound with caprolactone has a rapid polymerization reaction and is easy to improve the exposure sensitivity, which is particularly preferable. The denatured polyfunctional (meth) acrylate may be used singly or in combination of two or more. The degree of denaturation of the denatured caprolactone as the denatured polyfunctional (meth)acrylic acid g is not particularly limited. When the number of functional groups of the polyfunctional (meth)acrylate compound to be a matrix is n, it is relatively large. Functional (methacrylic acid vinegar compound i mole, preferably lower limit is 〇5n mole, preferably: upper limit is 5η mol. If denaturation of the above-mentioned denatured polyfunctional (subunit) propionic acid vinegar When the degree of use of the columnar spacer for the columnar spacer is used in the case of a column spacer, the flexibility of the column spacer to be produced may be changed. If the change of the denatured caprolactone of the above-mentioned denatured polyfunctional (meth)acrylic acid vine is more than 5 η mol, when the columnar spacer is produced, the reactivity of the exposed k may be lowered. The patterning of the columnar spacers produced is difficult. The lower limit of the properties of the above-mentioned denatured polyfunctional (meth)acrylic acid vinegar is ln Mo, and the upper limit of the upper limit is better. Functional (meth)acrylic acid vinegar compound The specific method of internal vinegar denaturation does not have a special P - θ w Μ "People can list: make the polyol', should, after the 50 is denatured into the caprolactone, the hydrazine (mercapto, and citric acid is vinegarized) The method of making (meth)propanol and hexyl (tetra) anti-soil), synthesizing denatured caprolactic acid (methyl)-enic acid, and then reacting it with alcohol to perform the method of '200900463' A method in which an acrylic acid, a caprolactone, and a polyhydric alcohol are subjected to an overall reaction, etc. Further, the above-mentioned denatured polyfunctional (meth) acrylate compound is a polyfunctional (meth)acrylic acid which is denatured by ethylene oxide and/or denatured with propylene oxide. In the case of an ester compound, the polyfunctional (fluorenyl) acrylate compound is not particularly limited, and examples thereof include oxidative ethylene denaturation and/or propylene oxide conversion of the above-mentioned (meth)acrylic acid vinegar compound. a compound obtained by birth, etc., wherein pentaerythritol tri(meth)acrylate, (trishydroxypropylpropane) tri(meth)acrylate, dipentaerythritol tri(meth)acrylate Preferably, dipentaerythritol tetra(meth)acrylate or a compound in which a carboxyl group is added to dipentaerythritol penta (meth) acrylate is used as the denatured ethylene oxide and/or denatured propylene oxide. The degree of denaturation of the ethylene oxide and/or the modified propylene oxide of the methyl acrylate is not particularly limited, and the number of functional groups of the polyfunctional (meth) acrylate compound of the matrix 2 is n, which is relatively large. The functional (fluorenyl) acrylate compound i mole, preferably has a lower limit of 0.5 η mol. The upper limit is preferably 15 n mol. If the above polyfunctional (meth) acrylate vinegar is denatured with ethylene oxide and/or denatured oxidation When the degree of propylene is less than 0.5 η, the flexibility of the column spacer to be produced may be insufficient. If the above-mentioned polyfunctional (meth)acrylic acid is degenerated, ethylene oxide and/or When the degree of denaturation of the modified propylene oxide exceeds "η mol, the affinity in the alkaline developing solution may become high, and the resolution due to swelling may be easily lowered. More preferably, the polyfunctional (meth)acrylic acid-modified denatured ethylene and/or denatured propylene oxide has a degree of denaturation 19 200900463 The lower limit is 3 n mol, and the upper limit is more preferably 10 n mol. The specific method of denaturing the above-mentioned polyfunctional (meth) acetoacetate g compound (4) and/or denaturing and oxidizing (4) is not particularly limited, and examples thereof include a polyol and an oxidized woman and/or a method for oxidizing propylene, & denatured vinylidene and/or denatured oxypropylene alcohol, and then subjecting the denatured ethylene oxide and/or denatured oxypropylene alcohol to (meth)acrylic acid; a method in which a methyl group of acrylic acid is reacted with ethylene oxide and/or propylene oxide to synthesize a denatured ethylene oxide and/or a denatured propylene oxide (meth)acrylic acid, and then react with an alcohol; A method of collectively reacting (meth)acrylic acid, ethylene oxide, and/or propylene oxide, and a polyol. In the curable resin composition for a columnar spacer according to the first embodiment, the amount of the denatured polyfunctional (meth) acrylate compound is not particularly limited, and a preferred lower limit is i 0 wt%, and a preferred upper limit is weight%. If the amount of the above-mentioned denatured polyfunctional (meth) acrylate compound is = 10% by weight. /. There may be cases where the flexibility of the column spacer to be manufactured and the compression recovery characteristics of the crucible are impaired. When the amount of the above-mentioned denatured polyfunctional (fluorenyl) acrylate compound exceeds 80% by weight, there is a possibility that the columnar spacer is scraped by the rubbing treatment. A more preferred lower limit of the amount of the above-mentioned denatured polyfunctional (meth) acrylate compound is 15% by weight'. The upper limit is more preferably 70% by weight. The curable resin composition for a columnar spacer of the present invention is preferably an amino phthalate (meth) acrylate compound having a hexafunctional or higher functional group having a carboxyl group in the molecule, and the photoreactive initiator. It also contains a test compound 20 200900463 polymer compound. The above-mentioned alkali-soluble polymer compound is not particularly limited as the above-mentioned alkali-soluble polymer compound, and the above-mentioned alkali-soluble polymer compound is preferably used as an anti-residue agent for developing (4) "devel". The molecular chain towel contains a H-acid anhydride or a lysine salt, and has a soluble polymer compound which can be dissolved in an aqueous solution of hydrazine hydroxide, sodium hydroxide, sodium carbonate or tetramethylammonium hydroxide. The alkali-soluble polymer compound is not particularly limited, and examples thereof include copolymers obtained by copolymerizing a monofunctional unsaturated compound having a carboxyl group and a monofunctional compound having an unsaturated double bond, and the like. The monofunctional unsaturated compound containing a carboxyl group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, and the like.

The monofunctional compound having an unsaturated double bond is not particularly limited, and examples thereof include (decyl) decyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-mercaptocyclohexyl (meth) acrylate, (A) (meth)acrylate monomer such as dicyclopentyloxyethyl acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate or benzyl (meth)acrylate. Further, the above-mentioned alkali-soluble carboxyl group-containing polymer compound may further contain an aromatic vinyl monomer, a cyanoethylene compound, an unsaturated dicarboxylic anhydride, an aromatic substituted maleimide, and an alkyl group. a component composed of maleimide or the like. 21 200900463 The aromatic vinyl monomer is not particularly enumerated, for example, "the present vinyl styrene styrene, p-methyl benzene, etc. 1 虱 虱 乙烯 乙烯 例如 例如 例如 例如 1 1 The above-mentioned random ethylene compound is not particularly limited to acrylonitrile or mercapto acrylonitrile. The unsaturated dicarboxylic acid anhydride is not particularly limited to maleic anhydride or the like. / As the above-mentioned aromatic-substituted maleene The bis-imine is particularly limited to exemplified by phenyl cis n-imine 1 - cis-butyl iodide, naphthyl-n-butylene imine, ortho-phenyl butyl succinimide The above-mentioned alkyl-substituted maleimide is not particularly limited, and examples thereof include mercapto-butyleneimine and ethyl-butyleneimine-propyl-butene. Further, the alkali-soluble carboxyl group-containing polymer compound may further contain a hydroxy group-containing monofunctional unsaturated compound to achieve solubility inhibition during development. Etc. The material is not particularly specific, for example, as a monomer having one radical in the molecule, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid _2 _, and Light propyl citrate, 4-butyl butyl acrylate, methyl butyl 4- butyl acrylate, etc. The above-mentioned polymer compound containing a carboxyl group is used as a component derived from a monofunctional unsaturated compound containing a carboxyl group. The lower limit is not particularly limited. The lower limit is 10% by weight, and the upper limit is preferably 4% by weight. 2009 22 200900463 If the ratio of the component derived from the monofunctional unsaturated compound containing a carboxyl group is less than 1% by weight, then In some cases, it becomes difficult to provide alkali solubility. When the ratio of the component derived from the monofunctional unsaturated compound containing a thiol group exceeds 40% by weight, the expansion during development may be remarkable and it may become difficult to form a pattern. A lower limit of the ratio of the component of the functional unsaturated component is preferably 15% by weight, and more preferably 30% by weight. The monofunctional unsaturated compound having a carboxyl group is copolymerized with a monofunctional compound having an unsaturated double bond. The method of the present invention is not particularly limited, and examples thereof include a radical polymerization initiator and, if necessary, a molecular weight modifier, by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or the like. A method of polymerization, wherein solution polymerization is preferred. VIII. As a solvent in the case of producing the above-mentioned test-solvent-containing octahedron compound by a solution polymerization method, for example, a pseudo-alcohol Class, celluloid '··., carbitol, esters, ethers, ketones, agents, etc.., polar organic solvents as the above aliphatic alcohols are not particularly limited to alcohol, ethanol, and For example, A is not particularly limited as the above-mentioned celluloid, and it is not particularly limited, and it is exemplified by the use of celluloid as the carbitol. Alcohol, butyl carbitol, and the like. For example, the card may be exemplified as the above-mentioned esters, and is not particularly limited, for example. Sodium, acetic acid carbitol, and propylene: alcohol monomethyl (10) acetic acid s. The ketone acetate is not particularly limited as the above-mentioned ketones, and the ketones are not particularly limited as the above-mentioned ethers, and dimethyl ether or a cyclic ether such as tetrahydrofuran is not particularly limited. Methyl ethyl ketone and methyl isobutyl g are equivalent. Examples thereof include dimethyl sapite and dimethylformamide. In particular, for example, the above-mentioned copolymer is produced by suspension polymerization or dispersion-based dispersion polymerization; liquid smoke such as non-aqueous benzene, anthracene, hexene or cyclohexene, etc., or ::He = 溶剂using a solvent, etc. ” He is non-polar organic=...There is no particular limitation on the use of a radical polymerization initiator in the case of a polymer compound having a carboxyl group, for example, an object, an azo initiator, etc. A free radical polymerization initiator is known. Further, the molecular weight modifier is not particularly limited, for example, a strip-methylstyrene dimer or a mercaptan chain transfer agent. Further, the test-soluble (meth)acrylic copolymer (A1) having a mercapto group (IV) group as the above-mentioned test polymer compound, particularly a branch group, is preferable. The alkali-soluble (meth)acrylic copolymerization force (A1) having a (meth)acryl group and a carboxyl group in a branched chain, for example, has a constituent unit having at least an acidic functional group and a constituent unit having a hydroxyl group. a main chain, and a heterocyclic acid vinegar compound containing a radical 1 & group, is bonded to at least a portion of the above-described acidic functional group via an isocyanate group of the isocyanate compound and/or at least a part of the amine group of the above hydroxyl group The acid-bonded poly 24 200900463 compound (A1 - 1 ) is preferred. In the above I & (A1 - 1 ), the amount of the radical polymerizable group-containing isocyanate compound is adjusted so that the equivalent ratio (nc〇 / 〇h) becomes 1.0 or more. The bond is introduced into the alkali-soluble southern molecular compound at a relatively high ratio to improve the sensitivity of the alkali-soluble polymer compound. Further, the content of the constituent unit having an acidic functional group can be adjusted to a suitable ratio, and the alkali solubility (developability) can be freely adjusted. In the above polymer (A1 - i), it is preferred to adjust the ratio of the isocyanate group (NCO / OH) to a content ratio of 14 mol% or more of the content of the late group. By adjusting the above equivalent ratio (NCO/OH) of the isocyanate group to ytterbium or more, the introduction ratio of the isocyanate S group can be increased, and the amount of the constituent unit having the radical group can be made mol/° or more. This can increase the portion of the isocyanate group reaction, so that a very large amount of free radicals can be introduced into the above alkali-soluble polymer compound to obtain a particularly high sensitivity. The amount of the isocyanate compound containing the radical polymerizable group is not particularly limited, and a preferred upper limit of the equivalent ratio of the isocyanato group (nc〇/〇h) is 2.0. When the above-mentioned equivalent ratio (nc〇/〇h) exceeds 2 〇, = a large amount of unreacted 3 isocyanate compound having a radical polymerizable group remains in the soluble polymer compound, and the alkali solubility is made. The physical properties of the polymer compound are lowered. Further, the constituent unit having an acidic functional group is a component which contributes to alkali developability, and the content thereof is not particularly limited, and can be appropriately adjusted according to the degree of alkali solubility required for the molecular compound described above. The monomer for introducing the structural unit having an acidic functional group into the main chain of the polymer includes a compound having a double bond group and an acidic functional group. The acidic functional group is not particularly limited, and is usually a fluorenyl group, and may be a group other than a carboxyl group as a component which contributes to alkali developability. In particular, the constituent unit having the acidic ruthenium group is preferably a constituent unit represented by the following formula (5).

R

0H (5) R-based hydrogenogen The above formula (5) and a subunit or a mercapto group contained in another formula described later. The monomer to be introduced into the early form of the composition of the above formula (5) is not particularly limited, and examples thereof include acrylic acid and mercaptoacrylic acid. The composition having the hydroxyl group is not particularly limited, and is preferably a constituent unit represented by the following formula (6).

(β) 26 200900463 The above formula (6 is the same as R of the above formula (5), and Ri represents an alkylene group having a carbon number of 2 to 4. As an ethyl group, a propyl group, a butyl group, etc. For example, it can be cited as a monomer for introducing the above-mentioned general formula (6) 煃忐 „ ^ 44 ^ y, ), and is particularly limited to, for example, acrylic acid_2_ Hydroxyethyl ester-2-'M 7 ^ ux ^ τ-based acrylic acid & E I oxime, acrylic acid _2 hydroxypropyl _, methacrylic acid hydroxy acid 4-hydroxybutyl ester, methacrylic acid _ 4 _ hydroxy Butyl ester, etc. - The above-mentioned polymer (the primary bond of A1 - D contains a constituent unit having the general formula (5), has a composition such as a 仇^^ base, a basic formula (6), etc. The polymer component may also be contained in the main chain of the above polymer, or may be contained in the group of ==. For example, the unit and/or 3 have a constituent unit having a square aromatic carbocyclic ring and/or have an ester group. The composition unit having the aromatic carbocyclic ring is not particularly limited, and is preferably a constituent unit represented by the following formula (7).

(7) Table 亍^ In the general formula (7), R of the general formula (1) is the same, & Examples of the R2 include, for example, a phenyl group and a hexyl group. The monomer to which the constituent unit of the above formula (7) is introduced is not particularly aromatic, and the vinyl styrene may be mentioned. The clothes may also be substituted with a cyclyl group such as chlorine or a dentate atom, an ethyl group or the like, an amine group such as an amine group or a dialkylamino group, and the like, and a cyano group, a carboxyl group or a sulfonic acid group. The monomer having a constituent group having an ester group is not particularly limited, and examples thereof include a compound having a main group and an ester group, and the group having the following pass bond is preferred. Λ 18)

(8)

In the above formula (1), 'R is the same as r of the above formula (5), and is not a leuco group or a aryl group (d). As such R3, for example, (iv) an alkyl group having a carbon number of 1 to 12, an aralkyl group such as a benzyl group or a phenethyl group may be mentioned. The monomer to be used as a constituent unit of the above formula (8) is particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, and (f). Butyl vinegar, (meth)acrylic acid _2_ethyl hexanoic acid, (methacrylic acid phenyl vinegar, (f-) hexahexyl acrylate, (methyl) acrylic acid bicyclic vinegar, (methyl ) Dicyclopentyloxyethyl acrylate, (meth)acrylic acid vinegar, (meth)acrylic acid section, (meth)acrylic acid, phenylethyl vinegar, etc. (meth) propylene In the main chain composed of the above-mentioned respective constituent units, the isocyanate compound containing a radical polymerizable group is bonded to the above-mentioned acidic functional molybdenum via the isocyanate 28 200900 463 base of the isocyanate compound. Partially enamined and/or bonded to the V-partic acid carboxylic acid sulphate to form a branch of the forming group. The field is an isocyanate compound containing a radical polymerizable group. The definition is, for example, preferably a formula of the following formula (radical isocyanic acid) or not (meth) propylene oxime OCN~R 4·

0 R5 -C=CH, (9) In the case of :), ..., the base is extended, and R6 represents a hydrogen atom or a methyl group. Further, the (meth) propyl anthraquinone acetoacetate of the formula (1) is preferably a (mercapto)propenyl group bonded via a carbon number of 2 to an oleic acid group (_NC〇). Specific examples thereof include 2-propane oxygen dislocation, 2-methylpropenylethyl isocyanate, and the like. :: 2-methyl propylene sulfhydryl ethyl ketone and the commercially available "kaenz MOI" manufactured by the Electric Co., Ltd., for example, the general formula of the above-mentioned polymer acidic ruthenium group formed by such a constituent unit (5) The constituent unit of the class, and the second component: The constituent unit of the temple (6), and the constituent unit of the general formula (7) containing the aromatic carbon ring; =: material: person: other constituent units The polymer raw material 5 as the main chain) is then obtained by containing a radical polyacrylate compound. The base is used as a solvent for the polymerization of the above-mentioned base polymer, preferably 29 200900463: a solvent having an active hydrogen such as a base or an amine group, and the like, a diethylene glycol dimethyl ether j... Funanyl ethyl _ diol ethers, methyl oxime: % - B ... ethylene glycol A and _ tercene acetate or other cyanosyl ester or propyl alcohol monomethyl ether acetate Ester, ethyl aromatic hydrocarbons, ketones, and the like. Oxybutene 0, 4, may also use a w1 & the polymerization initiator of the above raw material polymer is not particularly used in the conventionally known radical polymerization initiator, for example, can be listed: two: (nitrile azo polymerization) Initiator), non-nitrile couple:: (non-nitrile azo polymerization initiator), organic peroxide (polymerization initiator), hydrogen peroxide, and the like. The nitrile azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile, 2,2, azobis(2,4-dimethyl 戍 guess), and 2,2, _ couple. Nitrogen bis-(4-methoxy-2,4-dimethylvaleronitrile) and the like. The non-nitrile azo compound is not particularly limited, and examples thereof include dimethyl 2,2,-azobis(2-mercaptopropionic acid vinegar) and 2,2,-azobis (2,4). , 4_ tridecylpentane) and the like. The organic peroxide is not particularly limited, and examples thereof include third hexyl peroxyisobutyrate, tert-butyl peroxyisobutyrate, and 3,5, $_trimethylhexanyl peroxy peroxide. , octyl peroxide, laurel peroxide, stearyl peroxide, ^, 3,3-tetradecyl butylperoxy-2-ethylhexanoic acid vinegar, acridine peroxide , 2,5-dimercapto-2,5-di(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoic acid Vinegar, third hexylperoxy 2-ethylhexanoate, 4-mercaptobenzamide peroxide, benzammonium peroxide, 1,1,·bis-(t-butylperoxy Base) ring and so on. 200900463 When a peroxide is used as the radical polymerization initiator, it may be used in combination with a reducing agent to be a redox type polymerization initiator. In the production of the above raw material polymer, a molecular weight modifier may also be used to adjust the weight average molecular weight. The molecular weight modifier is not particularly limited, and examples thereof include a sulfonate-based molecular weight modifier, a thiol-based molecular weight modifier, a xanthate-based molecular weight modifier, and an E-pinene (terpin). ^ Methyl styrene dimer, etc. The functionalized alkane-based molecular weight modifier is not particularly limited, and examples thereof include dichloromethane and tetrabromocarbonized carbon. The thiol-based molecular weight modifier is not particularly limited, and examples thereof include n-hexyl mercaptan, n-octyl mercaptan, saponin, sulphur, sulphur, sulphur, and ketone. Thi〇glyc〇Uicacid) and so on. The term "treaturic acid-based molecular weight modifier" is not particularly limited, and examples thereof include - sulfurized di-subunits. , ', i 曰, diisopropyl xanthogen disulfide The above raw material polymer can be transferred to 1 && 16 is a random copolymer and a copolymer of the age of the copolymer to produce a random copolymer to the car ~ (4) Φ t, for example, the monomer of the above formula (7) U), and 8 〇 ~ II (r(: nu (4)) The compound composition, ii υ ut, under the condition of the dish, in the polymerization enthalpy of 2~ agent, make the retanning process. The above-mentioned general formula (5) to the above-mentioned polystyrene-equivalent conversion weight flat constituent unit of the raw material polymer in the ten-knife set (hereinafter referred to as "weight average 31 200900463 molecular $" or "Mw" The preferred lower limit is 5 〇〇〇, the preferred upper limit is 50,000, the preferred lower limit of the acid value is 5 mg K 〇 H / g, the preferred upper limit is mg KOH / g, and the preferred lower limit of the hydroxyl value is 5 mg K 〇 The upper limit of H/g is preferably 100 mgKOH/g. The reaction of the above-mentioned raw material, the inflammatory compound, and the acetoacetic acid compound containing a radical polymerizable group, isocyanic acid vinegar containing a radical polymerizable group The compound 'in the presence of less 1 catalyst, all of which is once added to the solution of the base polymer for a continuous reaction - for a fixed time, or A small amount is added dropwise thereto. The catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, etc., and if necessary, p-methoxysilane, hydrogen _, naphthylamine, and butyl butyl can be used. a polymerization inhibitor such as phenol or 2,3-di-t-butyl-p-cresol. The above isocyanate compound containing a radical polymerizable group, and the base of the above-mentioned base polymer Ab _ 1 S For example, a constituent unit represented by the following formula (1〇) is formed in the unit of the above formula (1). On the other hand, the above-mentioned isocyanate vinegar containing a radical polymerizable group The compound hydrazine is bonded to the meso group in the base polymer via hydrazine amide and isocyanate. For example, the formation unit of the plaque μ.+' 1 Η $ xiao upper cut (4) is subjected to an addition reaction. On the other hand, the amine phthalate smashes the bond, and the bond is formed to form a constituent unit represented by the constituent unit of the following general formula (1 〇). 32 200900463

R h2—〇^01 c=o I 0i1 oI I 0—C—*"NH·-R4—q- (1 1) 0 c—c=ch2 The polymer thus obtained has the following molecular structure: a constituent unit of the above formula (5) having an acidic functional group, a constituent unit having the above-described formula (6), and the like, and a radical polymerizable group introduced into a constituent unit having an acidic functional group a constituent unit of the formula (ig) or the like, and a constituent unit of the above formula (η) in which a radical polymerizable group is introduced into a constituent unit of the above formula (6) having a radical group is bonded in an arbitrary order. Molecular Structure.

The addition of the above-mentioned alkali-soluble polymer compound is not particularly limited to that of the above-mentioned (meth)acrylic acid urethane compound having a carboxyl group in the above molecule. The lower limit of the light weight is 20 parts by weight, and the upper limit is preferably 400 parts by weight. When the amount of the alkali-soluble polymer compound added is less than 20 parts by weight, the effect obtained by adding the above-mentioned alkali-soluble 33 200900463 polymer compound may be insufficient for μ a $ month, and the development step may be insufficient. Produce a pattern flow. When the amount of the above-mentioned test polymer compound added exceeds 400 parts by weight, development residue may occur. A more preferred lower limit of the amount of the above-mentioned test-soluble polymer compound to be added is 25 parts by weight, more preferably 300 parts by weight. The curable resin composition for a columnar spacer of the present invention preferably further contains a compound having two or more blocked isocyanate groups. The above-mentioned compound having two or more isocyanic acid S groups functions as a thermal crosslinking agent, and can be imparted to the columnar shape of the present invention by containing a compound having two or more blocked isocyanate groups. The hardener resin composition for a spacer is thermosetting. The compound having two or more blocked isocyanate groups is not particularly limited, and examples thereof include toluene: isocyanate, 4,4-diphenylmethylsulfonate/, cyanide, and toluene. Isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, and the like A polyfunctional isocyanate composed of an oligoester is obtained by blocking a blocker compound such as an active methylene group, an anthraquinone system, an intrinsic amine system or an alcohol system. The compound having two or more blocked isocyanic acid groups may be used singly or in combination of two or more. In addition, as a commercially available compound having two or more blocked isocyanate groups, for example, Duranate ΐ7Β_6〇ρχ, E-4〇2-B80T (above, manufactured by Asahi Kasei Chemicals Co., Ltd.), and the like can be mentioned. When the above-mentioned compound having two or more blocked isocyanate groups is contained in the curable resin composition for a columnar spacer of the present invention, the content of 34 200900463 is not particularly limited, and a preferred lower limit is 〇〇1% by weight. The upper limit is preferably 50% by weight. When the content of the compound having two or more blocked isocyanate groups is less than 重量1% by weight, the curable resin composition for columnar spacers of the present invention may not be sufficiently thermally cured. When the content of the compound having two or more blocked isocyanate groups exceeds 5% by weight, the degree of crosslinking of the obtained cured product may become too high to satisfy the elastic properties described later. A more preferred lower limit of s of the above-mentioned two or more blocked isocyanato sulfonate is 〇 5 parts by weight, more preferably 20 parts by weight. The curable resin composition for columnar spacers of the present invention can also be diluted by a diluent for adjusting the viscosity. The diluent is not particularly limited as long as it is selected in consideration of the compatibility with the curable resin composition for a columnar spacer of the present invention, the coating method, the film uniformity during drying, the drying efficiency, and the like. In the case where the curable resin composition for columnar spacers of the present invention is applied by a spin coater & slit coater, for example, methyl stilbene, ethyl celesta, ethyl is preferable. An organic solvent such as cyproterone, diethylene glycol, propylene glycol monoethyl ether, isopropanol or the like. These diluents may be used singly or in combination of two or more. A conventionally known additive such as a decane coupling agent for improving the adhesion to a substrate may be used as the curable resin composition for a columnar spacer of the present invention. The columnar spacer of the present invention is composed of a stone-reducing resin. 4 The compound of the (meth)acrylic acid amide phthalate 35 200900463 having the above-mentioned / and having a carboxyl group is not contained, so that it can be manufactured without A columnar spacer that is rubbed against the surface due to the rubbing treatment in the manufacturing process of the liquid crystal display element. In the present specification, the term "hardened material" means a cured product when the columnar spacer of the present invention is substantially completely cured by light irradiation (and heating). The condition of making it substantially completely hardened is to irradiate at least 50 mJ/cm2 of ultraviolet rays. Further, in the case of heating, heat treatment is applied at a temperature of 2 Torr to 25 Torr C for about 20 minutes, whereby the film can be completely cured. The preferred lower limit of the elastic modulus of the hardened resin composition for a columnar spacer of the present invention when it is hardened by light irradiation (and heating) at 25 〇c is 5%. 0·2 Gpa, the upper limit is 10 GPa. If the elastic modulus at 15% compression at 25 C is less than G2 GPa, it is too soft, and the columnar spacer formed using the curable resin composition for columnar spacers of the present invention may be difficult. Keep the cell gap. If at 25. When the elastic modulus at the time of 15% compression of the underarm is more than i〇Gpa, it is too hard, and when the substrate α is used as the substrate of the curable resin composition for columnar spacers of the present invention, the color filter layer may be pierced. And the phenomenon of elastic deformation of the filling knife necessary for the reply cannot be obtained. At 25. (The lower limit of the elastic coefficient of the lower 1 5% compression is 0.3 GPa, the upper limit is preferably 0.99 GPa, and the lower limit of the further enthalpy is 0.5 GPa, and the upper limit is further preferably 0.7 GPa. The hardened resin composition of the spacers is cured by 15% at 25 ° C by ^ gg r , , and heating, and the preferred lower limit of the recovery rate of the temple is 60%. . If the recovery rate is less than 60% at 15 °C at 30 °C, the columnar spacer recovery force between the substrates of the obtained liquid crystal display element may be too weak to obtain sufficient gravity failure. Inhibitory effect. Further, in the present specification, the 5% 5% shrinkage means that dust shrinkage is performed so that the deformation rate of the height of the columnar spacer becomes 15%. The method of producing the curable resin composition for a columnar spacer of the present invention is not particularly limited, and examples thereof include a method of mixing the above various resins or additives by a conventionally known method. In the case of a turtle, a method of producing a columnar spacer using a curable resin composition for a columnar spacer of the present invention will be described. When a columnar spacer is produced using the curable resin composition for a columnar spacer of the present invention, first, the columnar spacer of the present invention is applied onto a substrate with a curable resin composition to have a predetermined thickness. The film is formed. The coating method is not particularly limited, and examples thereof include a conventionally known coating method such as spin coating, slit & spin coating, slit coating, spray coating, dip coating, and bar coating. Then, on the formed film, active light rays such as ultraviolet rays are irradiated through the mask of the predetermined pattern formed. By this, the columnar spacer of the present invention is reacted with a photoreactive initiator in a curable resin composition in the light-irradiating portion to perform photocuring. The amount of the active light to be irradiated is not particularly limited, and is preferably 50 mj/cm 2 or more in the case of ultraviolet rays. If the amount of the active light is less than 50, the photohardening may be insufficient, and the pattern may be dissolved in the exposed portion when the alkali treatment is performed. Then, a photo-cured material after photohardening is developed to produce a columnar spacer of a predetermined pattern composed of a photocured material of a curable resin composition for a columnar spacer of the present invention. The curable resin composition for a columnar spacer of the present invention contains a 6-functional or higher (fluorenyl) urethane urethane compound having a carboxyl group in the molecule, and thus has good developability and a columnar spacer produced. It is excellent in abrasion resistance. In the case of the above-mentioned denatured polyfunctional (meth) acrylate compound, the curable resin composition for columnar spacers of the present invention has a high recovery property from compression deformation and forms a predetermined pattern. At the time of the formation, a residue is hardly formed, and a columnar spacer of a sharp pattern having excellent resolution can be formed. In the case where the curable resin composition for a columnar spacer of the present invention contains a compound having two or more blocked isocyanate groups, the patterned photocured material after the development treatment is further heated to thereby contain the test solution. The polymer compound is reacted with a compound having two or more blocked isocyanate groups. The condition of the above-mentioned heating may be appropriately determined in consideration of the size, the thickness, and the like of the above-mentioned pattern, and is preferably at least 20 (rc, 2 Å or more. The columnar shape formed of the curable resin composition for the columnar spacer of the present invention is used. The spacer is also one of the present invention. + The column spacer of the present invention has a height higher than that of the cell gap, and can be produced by a previously known method such as ODF method, whereby low-temperature foaming can be obtained. And effectively suppressing the generation of stains caused by gravity failure. 38 Liquid crystal display element of 200900463. The liquid crystal display element using the curable resin composition for columnar spacers of the present invention or the column spacer of the present invention is also According to the present invention, it is possible to provide a curable resin composition for a columnar spacer which can be developed to have excellent developability without being subjected to rubbing treatment in the manufacturing process of the liquid crystal display element. Further, a columnar spacer obtained by using the curable resin composition for the columnar spacer and a liquid crystal display element can be provided. [Embodiment] Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the examples thereof. (Polyfunctional (meth)acrylic acid urethane compound having a carboxyl group (Sample A) Manufacture) In a 1 〇 reaction vessel equipped with a stirrer, thermometer, cooling tube and air inlet tube, add trimethylhexamethylene diisocyanate 84 〇 \ g (4 moO, dimethylglycolate 148 g) (l mol), polyhexanol g-polyol (weight average molecular weight 2000) 2000 g (1 mol), denatured oxyethylene bisphenol A (molecular weight 324) 324 g (1 mol), dipentaerythritol pentaacrylate 1048 g ( 2 mol ) and 5 g of dibutyltin dilaurate were reacted at 60 ° C for 5 hours under a nitrogen atmosphere to obtain a polyfunctional methacrylate urethane compound (sample) A) The acid value of sample A is 13 mgKOH/g, the weight average molecular weight is 4400, and the number of functional groups is 10. 39 200900463 ♦ (Reactive poly(meth) acrylate urethane compound (sample B~) I) Production) Except as shown in Table 1 The acid value, the weight of the bismuth molecular weight, and the functional number of the sample B to the sample B to j were prepared in the same manner as in the sample A except that the amount of each component was shown in Table 1. (Multifunctional having no carboxyl group (A) (Preparation of acrylamide phthalate compound) " "DPHA-40H" manufactured by Sakamoto Chemical Co., Ltd. (weight 岣 岣 7000, functional number 1 〇) - (Multifunctional (曱) Production of acrylate compound) Derivatized caprolactone pentaerythritol triacrylate (a compound formed by reacting molyl pentaerythritol with 8 mol of the reaction and further abbreviating reaction with 3 mol of acrylic acid) 2 parts by weight (16·8 mm〇l), succinic anhydride i_98 parts by weight of anhydride (16 8 legs 〇1), 0.01 parts by weight as a polymerization inhibitor, and propylene glycol monomethyl as a solvent Ethyl ether; vinegar (PGMEA) 2 (3 parts by weight of the addition to the flask, - surface blowing nitrogen gas - heating. Then, the succinic anhydride was completely dissolved, and 0.02 parts by weight of triethylamine as a catalyst was added, and then reacted in an oil bath under a nitrogen atmosphere for 6 hours, and then left to cool to room temperature to obtain a carboxylic acid addition. Denatured caprolactone pentaerythritol triacrylate (A_SA_TMM). (Preparation of a polymerizable polymer compound) In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air tube, propylene glycol monomethyl ether acetate vinegar (pGMEA) 145 weight 40 200900463 was weighed and nitrogen was supplied. Mix one side and stir until warmed up. Then, 30 parts by weight of benzyl methacrylate (〇185 m〇1), bauxite 1 dilute acid 23.3 parts by weight (0.271 m〇1), and methyl methacrylate isophthalic acid vinegar 35 parts by weight (〇·161 And a monomer mixture composed of 17 parts by weight (〇〇〇8 mol) of a monomethyl acrylate vinegar (manufactured by Hitachi Chemical Co., Ltd., PA_513M) having a tricyclic smoldering skeleton, and a third butyl hydroperoxide ( Manufactured by Nippon Oil Co., Ltd., 7.6 parts by weight (45 parts by weight relative to the monomer mixture 100), which was added dropwise from the dropping funnel to the flask over 2 hours, and further at 120. Stirring was continued for 2 hours for aging. Then, the inside of the flask was replaced with air, and three (dimethyl) was added to the ripening in 15.6 parts by weight of glycidyl methacrylate (〇.11〇m〇1, 41% of carboxyl groups). 0.9 parts by weight of aminomethyl)phenol (DMP-30) and 1 part by weight of hydroquinone 145, and the reaction was continued for 6 hours at 1201, and the reaction was completed to obtain an alkali-soluble polymer compound. The obtained alkali-soluble polymer compound was subjected to the reaction. Sampling' Determination of molecular weight by gel permeation chromatography (GPC), weight average The amount of each component is 13,000'. The acid value of the solid component is 9 Å. (Examples 1 to 14 and Comparative Examples 1 to 3) (1) Preparation of a curable resin composition for a columnar spacer The ratio shown in 2 is used to prepare a curable resin composition for a ruthenium spacer. Further, each of Table 2 is abbreviated as follows. DPHA-40H: polyfunctional urethane amide (no carboxyl group, weight average) The molecular weight is 7,000 and the number of functional groups is 1〇) (manufactured by Nippon Kayaku Co., Ltd.) 41 200900463 1-907 : IRGACURE 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 17B-60PX: Block isocyanate (as manufactured by Asahi Kasei Chemicals Co., Ltd.) EDM: Diethylene Alcohol methyl ethyl ether (manufactured by Toho Chemical Co., Ltd.) (2) A columnar spacer was formed on a 150 mm x 150 mm ITO glass substrate, and the resulting columnar spacer was cured by spin coating. The film was dried by drying at 8 ° C for 2 minutes. On the obtained coating film, after irradiating ultraviolet rays of 150 mj/cm 2 through a 6-square dot image mask, 丨.丨1% of τμαη (hydrogen) The oxidized tetramethyl sulphate solution is developed for 8 sec seconds and then purified with pure water. After 3 seconds, a pattern of columnar spacers was formed, and thereafter, a columnar spacer was formed by baking for 2 minutes at 2301. The columnar spacer obtained had a bottom area of 100 μm and a height of 3 μΓ. <Evaluation> The curable resin composition for columnar spacers obtained in each of Examples 1 to 14 and Comparative Examples 1 to 3 and the columnar spacer were evaluated as follows. The results are shown in Table 2. Further, in Comparative Example 2, since the pattern could not be formed due to poor developability, evaluation of adhesiveness and abrasion resistance was not performed. (Evaluation of white turbidity of developing solution) Grab the developing solution after development, and perform visual observation of white turbidity and dynamic particle luminometer (manufactured by Internati〇nal Business Co., Ltd., NICOMP.3 80ZLS). The criteria are evaluated. 42 200900463 〇: Visually evaluated for transparency, average particle diameter is less than ι〇〇μηι △: visual evaluation «white turbidity, average particle diameter less than 5〇〇μηι X: visually evaluated as white turbidity, average particle diameter is 500 μm or more (Adhesion evaluation) Whether or not the pattern disappeared by an optical microscope was used, and evaluation was performed by the following criteria. 〇: No disappearance of the spacer pattern was observed. X: The spacer pattern disappeared. (Evaluation of developability) The presence or absence of development residuals was observed by light exposure, and evaluated by the following criteria. 〇: a state in which the spacer pattern is good and there is no development residue. X. The development residue can be confirmed, or the state in which the development remains (the evaluation of the abrasion resistance) is provided. The friction treatment machine (Kawaguchi) provided with a cotton alignment cloth (rubbing ci〇th) Manufactured by Lake Precision Co., sp_360), with a roller speed of 780 rpm (diameter 80 mm 0 ), a platform speed of 60 mm/sec, and a press-in amount of 0.7 mm, the substrate on which the column spacers are formed, with the alignment pattern The rubbing treatment was performed once in the direction along the pattern, and the substrate was subjected to surface-to-sharp observation by SEM (6 〇〇〇), and evaluated by the following criteria. 〇: No surface scraping at all. X : Confirm scraping. 43

200900463 [<ΝΪComparative Example 3 § *r> yr\ v-» fS 〇〇〇X Comparative Example 2 Ό v~> *n (NX 1 XI Comparative Example 1 1 tn 1 255 〇〇〇X Example 14 〇in 255 〇〇〇〇Example 13 g 〇wj 255 〇〇〇〇Example 12 〇g Wi 255 〇〇〇〇Example 11 § 255 〇〇〇〇Example 10 § i- 255 〇〇〇〇Implementation Example 9 § VI ! 255 〇〇〇〇 Example 8 〇〇*/*» 255 〇Ο 〇〇 Example 7 〇>T) m 255 〇0 〇〇Example 6 〇V} IT) V) < N 〇〇〇〇 Example 5 g 〇yr\ r^r 实施 Example 4 § u-> 255 o 〇〇〇 Example 3 § <n iN 〇〇〇〇 Example 2 S 1 1 255 〇〇〇〇Example 1 § 255 〇〇〇〇 Sample A Sample B Sample C Sample D Sample E Sample F Sample G Sample Η Sample I DPHA-40H验Q 1 ί 鹅 鹅 Μ ^ : 1 A-SA-TMM σ\ 17B-60PX EDM developer white turbidity adhesion developability to friction 1 f two i ®: i 韶&- | ti α Jpa Photopolymerization Initiator Block Isocyanate Solvent Evaluation 200900463 The use of the curable resin composition S for column spacers can be formed to have excellent developability without being A columnar spacer that is scraped by rubbing treatment in the manufacturing process of the liquid crystal display element. Further, a dendritic spacer and a liquid crystal display element using the curable resin composition for a columnar spacer can be provided. [Simple description of the diagram] None [Key component symbol description] None 46

Claims (1)

200900463 X. Patent application scope: 1) A curable resin composition for a columnar spacer, characterized by containing a 6-functional or higher (meth)acrylic acid urethane compound having a carboxyl group in a molecule, and light Reaction initiator. 2. The curable resin composition for columnar spacers according to the first aspect of the invention is further characterized in that it further contains an alkali-soluble polymer compound. 3. The curable resin composition for columnar spacers according to claim 1 or 2, further comprising at least one selected from the group consisting of denatured caprolactone, denatured ethylene oxide, and denatured oxidized propylene oxide. Denatured polyfunctional (meth) acrylate compounds. 4. The curable resin composition for columnar spacers of claim 2, 2 or 3, further comprising a compound having two or more blocked isocyanate groups. ^ Column spacers are characterized in that the columnar spacers of the first, second, third or fourth aspects of the application are made of a curable resin composition. 々6. A liquid crystal display element characterized in that the composition of the columnar spacer of the second, third or fourth aspect of the patent application is used for the composition of the hardening tree, or to the φ 士主查# / / The patent is called the column spacer of the fifth paragraph of the patent. XI. Schema: Benefit 47