JPWO2019216107A1 - Photosensitive resin composition, photo spacer and liquid crystal display device - Google Patents

Abstract

INDUSTRIAL APPLICABILITY The present invention is a photosensitive resin composition in which, when used as a spacer, a photospacer having a high recovery rate in which plastic deformation is suppressed, yet scraping of a liquid crystal alignment film provided on an opposing substrate is extremely suppressed. A photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound, with an object of providing a method for producing a photospacer and a liquid crystal display device using the same. A photosensitive resin composition having a required urethane equivalent of 1000 to 50,000 g / mol and an ethylenically unsaturated group equivalent of 100 to 155 g / mol, and a photospacer using this. The main purpose is to form a liquid crystal display device using this.

Description

The present invention relates to a photosensitive resin composition, a photo spacer using the same, and a liquid crystal display device.

Liquid crystal display devices are used in various applications such as notebook computers, personal digital assistants, smartphones, digital cameras, and desktop monitors, taking advantage of their characteristics such as light weight, thinness, and low power consumption.

The liquid crystal display device includes a liquid crystal layer between a color filter substrate and a TFT (Thin Film Transistor) array substrate, which controls light transmission on a pixel-by-pixel basis by orientation by an electric field, thereby enabling image display. Therefore, maintaining a uniform spacing (cell gap) between these substrates is one of the important factors that affect the image quality.

As a means for keeping the cell gap uniform, it has been conventionally practiced to form a spacer having a height corresponding to the cell gap in a non-display area on the substrate. The spacer is formed by, for example, photolithography in which a radiation-sensitive resin is uniformly applied onto a substrate, pattern-exposed, and then alkaline-developed (a spacer formed using the radiation-sensitive resin is also referred to as a photospacer). ..

However, when the liquid crystal display panel is manufactured, the color filter and the TFT array substrate are crimped, and the resin spacer is easily plastically deformed by the pressure during crimping, while the pressure during crimping is within the surface of the liquid crystal panel. Since it is not uniform, the height of the spacer varies, and as a result, there is a problem that display unevenness is likely to occur in the pixels.

As a technique for suppressing plastic deformation of the spacer, a photosensitive resin composition for a spacer containing an alkali-soluble resin, a photopolymerization initiator, and a polymerizable monomer as main components, and the acrylic equivalent of the entire photosensitive resin composition is A photosensitive resin composition for spacers having a value of 200 or less (see, for example, Patent Document 1) has been proposed.

Further, in recent years, in order to improve the yield, a technique using a liquid crystal alignment agent for photo-alignment that does not require rubbing (see, for example, Patent Document 2) has been proposed.

Further, a technique of blending isocyanate with a resin composition to form a urethane bond during thermosetting of the resin composition is also known (see, for example, Patent Document 3), but the reaction is sufficient due to restrictions in the selection of thermosetting conditions. Therefore, the optimum characteristics could not be obtained.

Japanese Unexamined Patent Publication No. 2005-292269 JP-A-2017-2030980 Japanese Unexamined Patent Publication No. 2006-276159

In the invention described in Patent Document 1, it is shown that the ethylenically unsaturated group equivalent in the resin composition is reduced as a means for reducing the elastic deformation rate. When the ethylenically unsaturated group equivalent in the resin composition is reduced, the spacer becomes hard. On the other hand, a liquid crystal alignment film is provided on the substrate in order to control the orientation direction of the liquid crystal. However, the liquid crystal alignment film has a problem that the mechanical strength is weak and it is easily scratched, and this tendency is particularly seen in the liquid crystal alignment agent for photoalignment, which has been used in place of the cloth rubbing alignment agent in recent years. It is remarkable.

That is, in the technique of Patent Document 1 for reducing the ethylenically unsaturated group equivalent, there is a trade-off relationship in which the hardened spacer scrapes the alignment film provided on the opposite substrate.

Therefore, the present invention is a photosensitive resin composition in which, when used as a spacer, it is a photospacer having a high recovery rate in which plastic deformation is suppressed, but scraping of a liquid crystal alignment film provided on an opposing substrate is extremely suppressed. It is an object of the present invention to provide an object and a method for manufacturing a photo spacer and a liquid crystal display device using the object.

In order to solve the above problems, the present invention mainly has the following configurations.

That is, it is a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound, and the urethane equivalent required for the solid content of the resin composition is 1000 to 50,000 g / mol, and
A photosensitive resin composition having an ethylenically unsaturated group equivalent of 100 to 155 g / mol.

Another aspect of the present invention is a photo spacer formed by using the photosensitive resin composition, and a liquid crystal display device provided with the photo spacer.

According to the present invention, when used as a photo spacer, it is possible to obtain a photo spacer having a high restoration rate in which plastic deformation is suppressed, and the phenomenon of scraping the liquid crystal alignment film provided on the opposing substrate is extremely suppressed. Will be done.

An example of a load-deformation amount hysteresis curve representing the elastic characteristics of a photospacer.

The photosensitive resin composition of the present invention contains at least an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound. By containing a photopolymerization initiator and a polymerizable compound, the exposed part can be photocured by photopolymerization and insolubilized in an alkaline developer, and by containing an alkali-soluble resin, alkaline development can be performed. Since the unexposed portion can be removed through the developing step with a liquid, so-called optical lithography technology can be applied, and a desired pattern can be formed by exposure and development.

In the photosensitive resin composition of the present invention, the urethane equivalent required for the solid content of the resin composition is 1000 to 50,000 g / mol, and the ethylenically unsaturated group equivalent is 100 to 155 g / mol. ..

The solid content referred to here refers to a component excluding the solvent contained in the photosensitive resin composition. The solid content in the case of a resin composition that cannot be separated into each component can be determined by heating at 130 ° C. for 1 hour to disperse the solvent and measuring the mass of the residue.

As understood from the fact that the photosensitive resin composition of the present invention has a predetermined ethylenically unsaturated group equivalent in its solid content, it contains a compound containing an ethylenically unsaturated group.

Here, the ethylenically unsaturated group equivalent means the number of grams of the compound required to provide 1 mol of the ethylenically unsaturated group, and the smaller the value, the more the ethylenically unsaturated group contained per unit mass. Indicates that the amount of groups is large. The ethylenically unsaturated group equivalent is infinite in a compound having no ethylenically unsaturated group. Further, where a plurality of compounds can be contained in the solid content of the photosensitive resin composition of the present invention, for example, the solid content is a three-component system, and the ethylenically unsaturated group equivalent of component A, which is one component thereof, can be determined. Ea, the mass fraction in the solid content is Wa, similarly, the ethylenically unsaturated group equivalent of the B component is Eb, the mass fraction in the solid content is Wb, and the ethylenically unsaturated group equivalent of the C component is When Ec and the mass fraction in the solid content are Wc, the ethylenically unsaturated group equivalent (Etotal) as the solid content can be obtained by using the following formula. Here, since the system of this example is a three-component system, Wa + Wb + Wc = 1. Even in cases other than the three-component system, the ethylenically unsaturated group equivalent of the solid content can be obtained in the same manner when a plurality of components are contained.

(1 / Etotal) = (1 / Ea × Wa + 1 / Eb × Wb + 1 / Ec × Wc).

However, when it is difficult to determine the ethylenically unsaturated group equivalent of each of the components constituting the solid content, the mass of the solid content is determined, and the total amount of the ethylenically unsaturated groups contained in the solid content is also determined. Can be obtained by a spectroscopic method or a chemical method, and the ethylenically unsaturated group equivalent of the solid content can be obtained.

The ethylenically unsaturated group equivalent required for the solid content of the photosensitive resin composition of the present invention is 100 to 155 g / mol. If it exceeds 155 g / mol, the plastic deformation when the spacer is used will be reduced. On the other hand, when it is less than 100 g / mol, the volume shrinkage when used as a spacer is significantly smaller than the volume shrinkage of the liquid crystal, and as a result, the liquid crystal foams easily when the liquid crystal panel is stored at a low temperature, resulting in inferior display quality. In addition, the spacer may be missing during development.

As a method for lowering the ethylene unsaturated group equivalent required for the solid content of the resin composition, a polymerizable compound having a low ethylene unsaturated group equivalent can be used, or an ethylenically unsaturated group can be introduced into an alkali-soluble resin. , A method of using an adhesion improver or a surfactant as an additive into which an ethylenically unsaturated group is introduced can be mentioned. Needless to say, in adjusting to the range specified in the present invention, the ethylenically unsaturated group equivalent of each component and its mass fraction may be adjusted.

As understood from the fact that the photosensitive resin composition of the present invention has a predetermined urethane equivalent in its solid content, it contains a compound containing a urethane bond.

Here, the urethane equivalent means the number of grams of the compound required to give 1 mol of urethane bond, and the smaller the value, the larger the amount of urethane bond contained per unit mass. Urethane equivalents are infinite in compounds that do not have urethane bonds. Further, where a plurality of compounds can be contained in the solid content of the photosensitive resin composition of the present invention, the method of determining the urethane equivalent in such a case is determined by the same concept as the above-mentioned ethylenically unsaturated group equivalent. It should be noted that the method of obtaining the urethane equivalent of each of the components constituting the solid content in the case where it is difficult to obtain the urethane equivalent is also understood in the same manner as described above. Incidentally, since the urethane bond has a ^{peak near 1550 cm -1} in infrared spectroscopic analysis, it is possible to determine the amount of urethane bond by the calibration curve method.

The urethane equivalent required for the solid content of the photosensitive resin composition of the present invention is 1000 to 50,000 g / mol. When the urethane equivalent exceeds 50,000 g / mol, the damage to the liquid crystal alignment film provided on the facing substrate is not sufficiently suppressed, and when it is less than 1000, the developability is lowered when the spacer is used, and the spacer is used. It is difficult to adjust the shape and height of the liquid crystal.

In the photosensitive resin composition of the present invention, it is preferable to use a compound having a molecular weight of 3000 or less as the compound containing the urethane bond described above, because the development margin tends to be widened.

Further, in the photosensitive resin composition of the present invention, it is desirable that the value obtained by dividing the urethane equivalent by the ethylenically unsaturated group equivalent is 5 to 200. It is easy to be both hard to hurt.

The urethane equivalent required for the solid content of the resin composition can be adjusted by the urethane equivalent of the compound having the urethane bond to be used and the mass fraction in the solid content, but the urethane bond is the main chain of the alkali-soluble resin. Alternatively, it can be introduced into the side chain, or can be introduced into the polymerizable compound by reacting the isocyanate compound with the acrylic monomer at the time of preparing the polymerizable compound. As another method, as will be described later, a silane coupling agent containing a urethane bond can also be used.

The polymerizable compound in the present invention is a compound that causes a polymerization reaction by the action of a photopolymerization initiator used together, and a typical photopolymerizable functional group includes an ethylenically unsaturated group. Further, the polymerizable compound in the present invention has a molecular weight of 3000 or less. Examples of the polymerizable compound used in the present invention include monofunctional or polyfunctional monomers and oligomers. The polymerizable compound used in the present invention is preferably a polyfunctional monomer because the crosslink density is still increased in one molecule and the elastic restoration rate is improved. In particular, it is preferable to use one having 6 or more ethylenically unsaturated groups in one molecule because the elastic recovery rate when processed into a spacer tends to increase. More preferably, one molecule having 6 or more and 25 or less ethylenically unsaturated groups is used. Examples of the polyfunctional polymerizable monomer include tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and trimethyl propantri (meth). Acrylate, pentaerythritol tri (meth) acrylate, triacrylic formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tri. Pentaerythritol octa (meth) acrylate, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxy) Propoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, tripentaerythritol octaacrylate , A reaction product of dipentaerythritol pentaacrylate and succinic anhydride and the like. As the polymerizable compound, one type may be used, or two or more types may be used.

Further, it is preferable that the polymerizable compound has a molecular weight in the range of 700 to 3000 and contains a urethane bond. Specific examples of such compounds include a pentaerythritol tetraacrylate adduct of hexamethylene diisocyanate (765 (numbers indicate molecular weight; the same applies hereinafter in this paragraph)) and a dipentaerythritol pentaacrylate adduct of hexamethylene diisocyanate. (1217), Hexamethylene diisocyanate tripentaerythritol octaacrylate adduct (1670), Hexamethylene diisocyanate uretdione pentaerythritol tetraacrylate adduct (905), Hexamethylene diisocyanate uretdione dipentaerythritol pentaacrylate adduct (1670) 1357), tripentaerythritol octaacrylate adduct of hexamethylene diisocyanate uretdione (1810), acrylic acid adduct of hexamethylene diisocyanate isocyanurate (721), pentaerythritol tetraacrylate adduct of hexamethylene diisocyanate isocyanurate (1399) ), Dipentaerythritol pentaacrylate adduct of hexamethylene diisocyanate isocyanurate (2078), tripentaerythritol octaacrylate adduct of hexamethylene diisocyanate isocyanurate (2757), dipentaerythritol triacrylate of hexamethylene diisocyanate isocyanurate -Alkylene oxide modified product adduct (2927), pentaerythritol tetraacrylate adduct of phenylenediocyanate (757), dipentaerythritol pentaacrylate adduct of phenylenediocyanate (1209), tripentaerythritol octaacrylate adduct of phenylenediocyanate (1662) ), Pentaerythritol tetraacrylate adduct of tolylene diisocyanate (771), dipentaerythritol pentaacrylate adduct of tolylene diisocyanate (1223), tripentaerythritol octaacrylate adduct of tolylene diisocyanate (1676), penta of isophorone diisocyanate. Elythritol tetraacrylate adduct (819), dipentaerythritol pentaacrylate adduct of isophorone diisocyanate (1271), tripentaerythritol octaacrylate adduct of isophorone diisocyanate (1724), Dicyclohexylmethane diisocyanate pentaerythritol tetraacrylate adduct (859), dicyclohexylmethane diisocyanate dipentaerythritol pentaacrylate adduct (1311), dicyclohexylmethane diisocyanate tripentaerythritol octaacrylate adduct (1764), diphenylmethane diisocyanate pentaerythritol tetra Aacrylate adduct (847), dipentaerythritol pentaacrylate adduct of diphenylmethane diisocyanate (1299), tripentaerythritol octaacrylate adduct of diphenylmethane diisocyanate (1752), pentaerythritol tetraacrylate adduct of norbornene diisocyanate (801), norbornene diisocyanate Dipentaerythritol pentaacrylate adduct (1253), tripentaerythritol octaacrylate adduct of norbornene diisocyanate (1706), and the like. When such a polymerizable compound is used, urethane development residue is less likely to be generated. It is more preferable that the polymerizable compound has a molecular weight in the range of 1000 to 3000 and contains a urethane bond because the alignment film is not easily damaged. Here, when it is attempted to introduce a urethane bond into the polymerizable compound by reacting an isocyanate group and a carboxyl group, it is preferable to reduce the remaining isocyanate group because the elastic recovery rate can be maximized. Further, from the viewpoint of stability of the resin composition, the isocyanate equivalent of the polymerizable compound is preferably 50,000 g / mol or more. The upper limit is not particularly limited, and it is most desirable that the isocyanate equivalent is infinite, that is, no isocyanate group is detected, but it is practically about 500,000 g / mol or less. The isocyanate group equivalent is determined by the method described in the section of Examples. If the measurement is difficult, it can be calculated by the calibration curve method based on the peak of ^{2260 cm -1 by performing infrared spectroscopic measurement.}

The polymerizable compound used in the present invention is preferably a compound represented by the following general formula (1) or the following general formula (2).

Here, in the general formula (1) and the general formula (2), R ^{1 to} R ³ and R ^{7 to} R ⁸ are independently alkylene groups having 1 to 20 skeleton carbon atoms which may have substituents. , An alkylene oxide group having 1 to 20 skeleton carbon atoms which may have a substituent, or an arylene group having 7 to 30 skeleton carbon atoms which may have a substituent. Here, the substituents are an alkoxy group having 3 or less carbon atoms, a carbonyl group having 4 or less carbon atoms, an ester group having 4 or less carbon atoms, an amide group having 4 or less carbon atoms, a vinyl group, an acrylic group, a methacrylic group, and an amino group. , A hydroxyl group, a carboxy group, a nitro group, a halogen group, an isocyanate group and a nitrile group. R ^{4 to} R ⁶ and R ^{9 to} R ¹⁰ each independently represent a group represented by the general formula (3).

Here, n is an integer of 1 to 7, and R ^{11 to} R ¹³ each represent a monovalent group represented by the general formula (4). It is desirable that n is 2 to 7 because it is easy to increase the elastic recovery rate.

Here, R ¹⁴ represents a hydrogen atom or a methyl group.

When a compound represented by the general formula (1) or the general formula (2) is used as the polymerizable compound, these contain a ring structure that is difficult to bend in the chemical structure. Unsaturated groups are not unevenly distributed and are evenly distributed, and it is easy to exhibit performance. In particular, since the polymerizable compound represented by the general formula (1) contains three urethane bonds in one molecule, the alkali-soluble resin used in the present invention, which is easy to maximize the softness performance, has a carboxyl as a structural unit. A compound having an acidic group such as a group or a hydroxyl group and being dissolved in an alkaline developer, and having a molecular weight of more than 3000. Further, it is preferable that the side chain contains an ethylenically unsaturated group in order to increase the elastic recovery rate as a photospacer. Urethane bonds may be included to prevent damage to the alignment film.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, a methacrylic group and the like. As a method of introducing an ethylenically unsaturated group into an alkali-soluble resin, an ethylenically unsaturated compound having an epoxy group, an acrylic acid chloride, a methacrylate chloride, or the like is added to a resin serving as a group having a carboxyl group or a hydroxyl group to carry out an addition reaction. There is a method to introduce it. Examples of the method for introducing the urethane bond include a method for adding a urethane group using isocyanate. When a compound having an ethylenically unsaturated group is added using isocyanate, urethane and an ethylenically unsaturated group can be introduced at the same time.

Examples of the alkali-soluble resin having an ethylenically unsaturated group in the side chain include "Cyclomer" (registered trademark) P (ACA) Z250 (dipropylene glycol monomethyl ether 45% by mass solution) manufactured by Daicel Ornex Co., Ltd. Acid value 110 mgKOH / g, weight average molecular weight 20,000), manufactured by ADEKA Co., Ltd., "Adeca Alkalus" WR301 (dipropylene glycol monomethyl ether 45% by mass solution, acid value 100 mgKOH / g, weight average molecular weight 5,900) , KRX-3802 (dipropylene glycol monomethyl ether 45% by mass solution, acid value 80 mgKOH / g, weight average molecular weight 5,500) alkali-soluble cardo resin and the like.

Examples of the alkali-soluble resin having a urethane bond include "Acryt (registered trademark)" 8UA-017 (50% by mass solution of ethyl acetate, 11 mgKOH / g, weight average molecular weight 40,000) manufactured by Taisei Fine Chemicals Co., Ltd.

In the present invention, the alkali-soluble resin has A) a structural unit represented by the following general formula (5), B) a structural unit represented by the following general formula (6), and C) the following general formula (7). It preferably has the structural unit represented. By having the structural unit represented by the general formula (5), the solubility of the resin in the alkaline developer can be improved, and unevenness in the exposure step can be suppressed. Further, by having the structural unit represented by the general formula (6), the sensitivity in exposure and development and the elastic restoration rate of the photo spacer can be improved by the ethylenically unsaturated group introduced into the side chain. Further, by having the structural unit represented by the general formula (7), it is possible to suppress the variation in the height of the photo spacer due to the lens scan exposure.

Here, R ¹⁵ represents a hydrogen atom or a methyl group.

Here, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. X is −CH ₂ CH (OH) CH ₂ O (C = O) −, −CH ₂ CH ₂ NH (C = O) O (CH ₂ ) _m O (C = O) − or − (CH ₂ ) _n O (C = O) NHCH ₂ CH ₂ O (C = O)-is shown. Note that m and n independently represent integers of 1 to 4, respectively. Among them, X is preferably −CH ₂ CH (OH) CH ₂ O (C = O) −.

Here, Y has an aryl group having 6 to 11 skeletal carbon atoms which may have a substituent, and an aralkyl group or a substituent having 7 to 10 skeletal carbon atoms which may have a substituent. A good skeleton shows a cycloalkyl group having 3 to 10 carbon atoms. Here, the substituents that can be used are the same as the substituents described in ^{R 1 to} R ³ and R ^{7 to} R ⁸ of the general formula (1) and the general formula (2). Further, among all the structural units of the alkali-soluble resin, the general formula (5), the general formula (6) and the general formula (7), which are regarded as repeating units, preferably occupy 70 mol% or more and 100 mol% or less.

The alkali-soluble resin having the structural units represented by the general formula (5), the general formula (6) and the general formula (7) is a compound having an unsaturated double bond unit having a corresponding side chain structure. It can be obtained by using and polymerizing. Further, other components may be copolymerized.

Examples of the copolymerizing component giving the structural unit represented by the general formula (6) include (meth) acrylic acid; glycidyl (meth) acrylate, 2-isocyanatoethyl methacrylate and 2-hydroxyethyl (meth) acrylate. Can be mentioned. Two or more of these may be used. Among these, it is preferable to add glycidyl (meth) acrylate to (meth) acrylic acid.

Examples of the copolymerization component giving the structural unit represented by the general formula (7) include N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Two or more of these may be used. Of these, N-cyclohexylmaleimide is preferable.

Other copolymerization components include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, benzyl (meth) Unsaturated carboxylic acid alkyl ester such as meta) acrylate and isobornyl (meth) acrylate; unsaturated carboxylic acid aminoalkyl ester such as aminoethyl acrylate, polyvalent carboxylic acid such as mono (2- (meth) acrylicyloxyethyl) Acrylic acid monoester; aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic nitrile, Vinyl cyanide compounds such as α-chlor (meth) acrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl Ethylene unsaturated compounds having a tricyclodecane skeleton or dicyclopentadiene skeleton such as (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate; monocarboxylic acids such as crotonic acid and vinylacetic acid or acid anhydrides thereof; Examples thereof include dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, or acid anhydrides thereof.

In the alkali-soluble resin used in the present invention, the ethylenically unsaturated group equivalent is preferably 400 g / mol or less because the elastic recovery rate is likely to be improved. The ethylenically unsaturated group equivalent of the alkali-soluble resin is more preferably 360 g / mol or less. For example, B) having an ethylenically unsaturated group, the higher the content ratio of the structural unit represented by the general formula (6), the smaller the ethylenically unsaturated group equivalent can be. The ethylenically unsaturated group equivalent of the alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound having an ethylenically unsaturated group. The ethylenically unsaturated group equivalent can be calculated by measuring the iodine value by the method described in Section 6.0 of the test method of JIS K 0070: 1992.

The weight average molecular weight (“Mw”) of the alkali-soluble resin used in the present invention is preferably 3,000 to 100,000. By setting Mw to 3,000 or more, the viscosity of the prebake film can be increased, and even when exposed by the lens scan method, the height variation can be further suppressed. Mw is more preferably 20,000 or more. On the other hand, by setting Mw to 100,000 or less, unevenness on the surface of the pattern can be suppressed and the surface shape of the pattern can be improved. Mw is more preferably 80,000 or less. Here, Mw of the alkali-soluble resin in the present invention is a conversion value based on standard polystyrene, and can be measured by using gel permeation chromatography.

The alkali-soluble resin used in the present invention preferably has an acid value of 60 to 100 mgKOH / g. By setting the acid value to 60 mgKOH / g or more, the height variation can be further reduced. The acid value is more preferably 65 mgKOH / g or more. On the other hand, by setting the acid value to 100 mgKOH / g or less, the unevenness of the pattern surface can be suppressed and the surface shape of the pattern can be improved. The acid value is more preferably 95 mgKOH / g or less. The acid value of the alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound having a carboxyl group. Here, the acid value of the alkali-soluble resin in the present invention can be determined by the neutralization titration method of Section 3.1 of the test method of JIS K 0070: 1992. When measuring using an alkali-soluble resin solution having a solid content concentration of about 30% by mass, 5 g of the alkali-soluble resin solution is placed in an aluminum cup (φ45 mm) and heated at 130 ° C. for 1 hour to remove the solvent. This makes it possible to obtain an amount of alkali-soluble resin required for measurement.

The content of the alkali-soluble resin contained in the photosensitive resin composition of the present invention is preferably 10 to 45% by mass in the solid content. By setting the content of the alkali-soluble resin to 10% by mass or more, the variation in the height of the spacer can be further suppressed. On the other hand, by setting the content of the alkali-soluble resin to 45% by mass or less, the elastic recovery rate can be further improved.

The photopolymerization initiator used in the present invention refers to a compound that decomposes and / or reacts with radiation (including visible light, ultraviolet rays, and electron beams) to generate radicals. Examples of the photopolymerization initiator include oxime ester compounds, alkylphenone compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, acylphosphine oxide compounds, and titanosen compounds. Examples include compounds. Two or more of these may be contained.

Examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole) -3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-Carbazole-3-yl]-, 1- (O-Acetyloxime), "Adeca Arculus" (registered trademark) N-1919, NCI-831, NCI-930 (all manufactured by ADEKA Co., Ltd.) ), "IRGACURE" (registered trademark) OXE01, OXE02, OXE03, OXE04 (all of which are manufactured by BASF Japan Co., Ltd.) and the like. Examples of the alkylphenone-based compound include 2,2-diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and 2- (dimethylamino) -2-[(4). -Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-hydroxyisobutylphenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Examples thereof include phenyl-propane-1-one and "IRGACURE" (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.). Examples of the benzophenone compound include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like. Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diiso. Examples thereof include pyrthioxanthone, 1-chloro-4-propylthioxanthone, 1-hydroxycyclohexylphenyl ketone and the like. Examples of the imidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. Examples of the benzothiazole-based compound include 2-mercaptobenzothiazole. Examples of the benzoxazole-based compound include 2-mercaptobenzoxazole. Examples of the acylphosphine oxide-based compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. Examples of the titanocene compound include bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium. Be done. Among these, oxime ester compounds and alkylphenone compounds are preferable from the viewpoint of further improving the sensitivity. Among the oxime ester compounds, "Adeka Arcurus" (registered trademark) N-1919 is more preferable, and among the alkylphenone compounds, "IRGACURE" (registered trademark) 907 is more preferable.

In the present invention, the content of the photopolymerization initiator contained in the photosensitive resin composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass in the solid content. When it is 30% by mass or less, the ethylenically unsaturated group equivalent and the urethane equivalent can be easily increased. If it is 1% by mass or more, the sensitivity can be easily increased.

The photosensitive resin composition of the present invention includes a filler, a sensitizing aid, an ultraviolet absorber, an adhesion improver, a surfactant, a polymerization inhibitor, a polymer compound other than the above-mentioned alkali-soluble resin, an organic acid, and an organic amino compound. , Additives such as hardeners and solvents may be included.

By containing the filler, the photosensitive resin composition of the present invention can further increase the viscosity of the prebaked film after drying and further suppress the height variation. Examples of the filler include inorganic oxide particles such as silica, alumina, titania and barium sulfate; metal particles; resin particles such as acrylic, styrene, silicone and fluorine-containing polymer. Two or more of these may be contained. Among these, it is preferable to use silica particles from the viewpoint of particle size and dispersibility. The average particle size of the filler in terms of specific surface area is preferably 4 to 120 nm. When the average particle size of the filler is 4 nm or more, the variation in height when used as a spacer can be further suppressed. On the other hand, when the particle size is 120 nm or less, the unevenness of the surface of the spacer pattern obtained through the photolithography step can be suppressed, and the surface shape of the pattern can be improved.

When the filler is not contained, the ethylenically unsaturated group equivalent and the urethane equivalent in the resin can be easily increased, which is preferable.

The photosensitive resin composition of the present invention can improve the sensitivity by containing a sensitizing aid. Examples of the sensitizing aid include aromatic or aliphatic tertiary amines.

By containing the ultraviolet absorber, the photosensitive resin composition of the present invention can easily form a highly transparent, fine and short-tapered photospacer. As the ultraviolet absorber, an organic compound-based ultraviolet absorber such as a benzotriazole-based compound, a benzophenone-based compound, or a triazine-based compound is preferable from the viewpoint of transparency and non-coloring property. Two or more of these may be contained. Among these, benzotriazole-based compounds are preferable.

Examples of the benzotriazole-based compound include 2- (2H-benzotriazole-2-yl) -p-cresol and 2- (2H-benzotriazole-2-yl) -4-6-bis (1-methyl-1). -Phenylethyl) phenol, 2- [5 chloro (2H) -benzotriazole-2-yl] -4-methyl-6- (tert-butylphenol), 2,4 di-tert-butyl-6- (5-chloro) Bentriazole-2-yl) phenol, 2- (2H-benzotriazole-2-yl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-tert-pentylphenol, 2- (2H-) Bentriazole-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol, 2 [2-hydroxy -3- (3,4,5,6 tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole and the like can be mentioned.

Examples of the benzophenone compound include octabenzophenone and 2-hydroxy-4-n-octoxybenzophenone.

Examples of the triazine-based compound include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol.

The content of the ultraviolet absorber that can be contained in the photosensitive resin composition of the present invention is preferably 0.3 to 10% by mass in the solid content. By setting the content of the ultraviolet absorber to 0.3% by mass or more, the tapered portion can be further shortened. The content of the ultraviolet absorber is more preferably 2% by mass or more. On the other hand, by setting the content of the ultraviolet absorber to 10% by mass or less, high sensitivity can be maintained. The content of the ultraviolet absorber is more preferably 8% by mass or less. The solid content refers to a component excluding the solvent contained in the photosensitive resin composition.

Examples of the adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2). -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 − Silane coupling agents such as mercaptopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-isocyandiapropyltriethoxysilane and the like can be mentioned. These may be contained in 2 or more types. Further, it is preferable to use a compound having a urethane bond or an ability to form a urethane bond, and examples of such a compound include pentaerythritol tetraacrylate of 3-ureidopropyltrialkoxysilane and 3-isocyanatepropyltriethoxysilane. Additives can be mentioned.

The content of the adhesion improver that can be contained in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass in the solid content. By setting the content of the adhesion improver to 0.1% by mass or more, the development adhesion can be improved. The content of the adhesion improver is more preferably 0.5% by mass or more. On the other hand, by setting the content of the adhesion improver to 20% by mass or less, aggregation of the alkali-soluble resin and the polymerizable compound can be suppressed. The content of the adhesion improver is more preferably 10% by mass or less.

Examples of the above-mentioned surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; and lauryldimethylamine oxide. , Amphoteric surfactants such as laurylcarboxymethyl hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate; perfluorobutyl sulfonate, perfluoroalkyl Fluorine-based surfactants such as group-containing carboxylates, perfluoroalkyl group-containing trimethylammonium salts, perfluoroalkyl group-containing phosphoric acid esters, or perfluoroalkylethylene oxide adducts; polyether-modified polymethylalkylsiloxanes, polyether-modified Silicone-based surfactants such as polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, and polyester-modified hydroxyl group-containing polydimethylsiloxane. Be done. Two or more of these may be contained. Among these, polyether-modified polydimethylsiloxane "BYK" (registered trademark) 333 (manufactured by Big Chemie) is preferable.

The content of the surfactant that can be contained in the photosensitive resin composition of the present invention is preferably 0.001 to 10% by mass in the solid content. By setting the content of the surfactant to 0.001% by mass or more, the coatability of the photosensitive resin composition can be improved. The content of the surfactant is more preferably 0.01% by mass or more. On the other hand, by setting the content of the surfactant to 10% by mass or less, the unevenness of the pattern surface can be suppressed and the surface shape of the pattern can be improved. The content of the surfactant is more preferably 1% by mass or less.

Examples of the polymerization inhibitor described above include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, and 2,5-bis (1,1-dimethylbutyl). Hydroquinone hydroquinone-based polymerization inhibitors such as catechol, catechol-based polymerization inhibitors such as tert-butyl catechol and the like. Two or more kinds of polymerization inhibitors may be contained.

The content of the polymerization inhibitor that can be contained in the photosensitive resin composition of the present invention is preferably 0.01 to 0.5% by mass in the solid content. By setting the content of the polymerization inhibitor to 0.01% by mass or more, the stability of the photosensitive resin composition over time can be improved. On the other hand, by setting the content of the polymerization inhibitor to 0.5% by mass or less, it is possible to suppress the occurrence of erosion and stains on the film surface due to a decrease in sensitivity when immersed in a polar solvent.

Examples of the polymer compound other than the alkali-soluble resin include acrylic resin, alkyd resin, melamine resin, polyvinyl alcohol, polyester, polyether, polyamide, and polyamide-imide, which are hardly soluble in the alkali developing solution by themselves. Examples include polyimide and polyimide precursors. Two or more kinds of such polymer compounds may be used.

Examples of the above-mentioned solvent include ether solvents, ester solvents, alcohol solvents, ketone solvents, xylene, ethylbenzene, solvent naphtha and the like. Two or more kinds of solvents may be used.

Examples of the ether solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether and the like. Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and diethylene glycol methyl ethyl ether are preferable.

Examples of the ester solvent include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-butyl acetate and 3-methoxy-3-methyl. -Butyl acetate, diethyl oxalate, ethyl acetoacetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propio Nate, propylene glycol monoethyl ether acetate, pentyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopentyl acetate and the like can be mentioned. Among these, 3-methoxy-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate and the like are preferable.

Examples of the alcohol solvent include butanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol.

Examples of the ketone solvent include cyclopentanone and cyclohexanone.

The photosensitive resin composition of the present invention is formed into a truncated cone having an upper bottom surface diameter of 6 μm, a lower bottom surface diameter of 9 μm, and a height of 3 μm, and has an elastic recovery rate of 60% when a load of 50 mN is applied. The above is preferable. The detailed molding conditions are as described in the section of Examples. When the elastic recovery rate is 60% or more, the variation in the height of the spacer at the time of cell crimping is further suppressed, and the display unevenness due to the plastic deformation of the photo spacer can be further reduced. The elastic recovery rate is more preferably 70% or more. The closer the elastic recovery rate is to 100%, the more the influence of the deformation of the photo spacer on the cell gap and the resulting uneven display can be suppressed. The above shape is a typical shape of a photo spacer, and the above load is an example of a load that the photo spacer receives during manufacturing or use. By such a method, the difficulty of plastic deformation of the photosensitive resin composition used for forming the photo spacer can be relatively evaluated.

FIG. 1 shows a schematic view of an example of a hysteresis curve representing the elastic characteristics of the photo spacer. When a load is applied to the photo spacer and the load is removed, a hysteresis curve of the load applied to the photo spacer and the amount of deformation of the photo spacer is obtained as shown in FIG. By obtaining the total deformation amount Ha [μm], the plastic deformation amount Hb [μm], and the elastic deformation amount of the photo spacer from the hysteresis curve, the elastic recovery rate of the photo spacer (((Ha−Hb) / Ha) × 100) ( %) Can be calculated. Here, the hysteresis curve is obtained after applying pressure at a speed of 2.5 mN / sec until a load of 50 mN is reached using a hardness tester Fisher (Fisherscope H100; Helmut Fisher GmbH & Co) and a flat indenter of φ50 μm. , Obtained by opening at a speed of 2.5 mN / sec.

In order to keep the elastic recovery rate when the photospacer is formed in the above range, it is preferable to use a photosensitive resin composition in which the ethylenically unsaturated group equivalent is in the above-mentioned preferable range.

The photosensitive resin composition of the present invention contains an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound in an arbitrary ratio of other additives such as a surfactant, a polymerization inhibitor, a solvent and an ultraviolet absorber, if necessary. It can be obtained by mixing with.

The photosensitive resin composition of the present invention can be preferably used for forming a photo spacer.

The shape of the photo spacer is preferably a truncated cone shape, and the diameter of the upper base is preferably 15 μm or less in order to improve the definition of the color filter. The ratio of the diameter of the upper base to the diameter of the lower bottom (upper base / lower lower) is preferably 0.3 to 2.0.

Next, the method for manufacturing the photospacer of the present invention will be described by taking the case of forming it on a substrate as an example. It is preferable that the above-mentioned photosensitive resin composition of the present invention is applied onto a substrate and dried to obtain a prebake film, and the prebake film is subjected to lens scan exposure and development to form a photospacer. Further, it is preferable to heat-treat the developed coating film pattern to cure it. The photo spacer of the present invention may be provided not only when it is provided in direct contact with the substrate, but also when it is provided on various elements (for example, a black matrix, a flattening film, an electrode, a liquid crystal alignment film) configured on the substrate. it can.

Examples of the substrate include transparent substrates such as glass and polymer films.

Examples of the method for applying the photosensitive resin composition include a dip method, a roll coater method, a spinner method, a die coating method, and a wire bar coating method.

Examples of the drying method include vacuum drying and heat drying (pre-baking) using an oven or a hot plate. In the case of vacuum drying, the heating temperature is preferably 100 ° C. or lower from the viewpoint of suppressing recondensation of the drying solvent on the inner wall of the vacuum chamber. The vacuum drying pressure is preferably equal to or lower than the vapor pressure of the solvent contained in the photosensitive resin composition, and is preferably 1 to 1000 Pa. The vacuum drying time is preferably 10 to 600 seconds. In the case of prebaking, the heating temperature is generally 60 to 200 ° C., and the heating time is generally 1 to 60 minutes.

In the present invention, the viscosity of the prebaked film obtained by the following preparation method at 23 ° C. ^{is preferably 1 × 10 3} to 1 × 10 ⁸ Pa · s. By exposing the pre-baked film having a viscosity of 1 × 10 ³ Pa · s or more at 23 ° C., the fluidity of the pre-baked film is appropriately suppressed, and in the pre-baking film transport step, the exposure step, and the heat drying (post-baking) step. The occurrence of unevenness can be further suppressed. Viscosity at 23 ° C. and more preferably not less than 1 × ¹⁰ 5 Pa · s. On the other hand, by exposing the prebaked film viscosity is less 1 × 10 8 ^Pa · s at 23 ° C., thereby improving the developing property. Here, the viscosity of the pre-baked film at 23 ° C. is measured ^{by collecting 90 mm 3} or more of the pre-baked film, using a rheometer (MCR-302; manufactured by Anton Pearl Co., Ltd.) and a plate having a diameter of 15 mm, and measuring thickness: 0.5 mm. The viscosity at 23 ° C. when measured while raising the temperature from 20 ° C. to 110 ° C. at a heating rate of 0.083 ° C./sec under the conditions of frequency: 1 Hz and strain: 0.5%. In the process of manufacturing the photo spacer on the color filter substrate, the temperature of the prebaked film is heated to about 100 ° C. in the drying process, but it is generally about room temperature (about 23 ° C.) by cooling before exposure. Is. Therefore, in the present invention, attention is paid to the viscosity at 23 ° C. as the prebake film temperature at the time of general exposure.

It is preferable that the exposed portion is cured by exposing the obtained prebaked film through a mask, and the unexposed portion is removed by developing with an alkaline developer to form a pattern.

Examples of the exposure method include proximity exposure, lens scan exposure, mirror projection exposure, stepper exposure, and the like. In the present invention, lens scan exposure excellent in high-definition pattern processing on a large substrate is preferably used. Since the photosensitive resin composition of the present invention can suppress variations in height, two rows of lenses, a 1st lens and a 2nd lens, are lined up as an apparatus configuration, and there is an exposure time difference at the joint of these lenses, so that the prebake film is formed. It can be suitably used even in a lens scan exposure in which height variation is likely to occur due to the flow. Examples of the lens scan exposure apparatus include FX-65S (manufactured by Nikon Corporation).

As the developing step, development with an alkaline developer is preferable. Examples of the alkaline developer include an organic alkaline developer and an inorganic alkaline developer. As the inorganic alkali developer, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferable. As the organic alkali developer, an amine-based aqueous solution such as tetramethylammonium hydroxide aqueous solution or methanolamine is preferable. The content of the alkaline substance in the alkaline developer is preferably 0.02% by mass or more from the viewpoint of development solubility of the unexposed portion. On the other hand, from the viewpoint of further improving the pattern processability of the exposed portion, 2.0% by mass or less is preferable. The developer preferably contains a surfactant in order to improve the uniformity of development. Since the developing speed changes depending on the temperature of the developing solution, it is preferable to appropriately select the developing solution temperature in the range of 18 to 40 ° C.

Examples of the developing method include dip development, shower development, paddle development and the like. It is preferable to appropriately select the temperature, flow rate and shower injection pressure of the developer, the washing temperature after development, the flow rate and the shower injection pressure conditions. In order to remove the residue on the substrate, it is preferable to inject the developer or washing water at a high pressure, and the ejection pressure is preferably 0.01 MPa to 20 MPa.

Examples of the heat treatment device for the coating film pattern after development include a hot air oven and a hot plate. The heating temperature is preferably 180 to 300 ° C., and the heating time is preferably 5 to 90 minutes.

Next, the color filter substrate having the photospacer and the liquid crystal display device of the present invention will be described as an example.

In one aspect, the color filter substrate has the photospacers and pixels of the present invention on the substrate. If necessary, it may have a black matrix, a flattening film, a transparent electrode, an alignment film, and the like. The photo spacer of the present invention can also be formed on the side of the TFT array substrate.

Examples of the substrate include those exemplified as a substrate on which a photospacer is formed.

Examples of the pixel include a red pixel, a green pixel, a blue pixel, and the like. The pixels may contain colorants, resins, polymerizable compounds, photopolymerization initiators, other additives and the like, or may be formed from a cured product of a composition containing one or more of them. Examples of the colorant include organic pigments, inorganic pigments, and dyes. Examples of the resin, the polymerizable compound, the photopolymerization initiator, and other additives include those exemplified as the components of the transparent photosensitive resin composition of the present invention.

Examples of the pixel shape include rectangles, stripes, squares, polygons, and wavy shapes. From the viewpoint of increasing the opening area and improving the transmittance, the pixel width is preferably 1 μm or more. On the other hand, from the viewpoint of displaying a more detailed image, the pixel width is preferably 100 μm or less. The film thickness of the pixels is preferably about 1 to 5 μm.

It is preferable to have a black matrix (hereinafter, “BM”) between adjacent pixels. The BM has an effect of improving the contrast of the displayed image by blocking the light between the pixels. The BM may be a color-overlapping BM formed by overlapping a part of pixels adjacent to each other, but in order to suppress a step between the pixels to further improve the displayed image and obtain a high light-shielding property, the resin and the BM may be used. It is preferable to contain a light-shielding material. As the resin, a polyimide resin or an acrylic resin is preferable. Examples of the light-shielding agent include titanium black, titanium nitride, titanium carbide, carbon black and the like. Further, an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant and the like may be contained.

The film thickness of the BM is preferably 0.5 μm or more, more preferably 0.8 μm or more, from the viewpoint of improving the light-shielding property and the resistance value. On the other hand, the film thickness of BM is preferably 2.5 μm or less, more preferably 2.0 μm or less, from the viewpoint of improving flatness.

When the color filter substrate having pixels or BM has a step, it is preferable to have a flattening film. The flattening film may be formed on the entire surface of the pixel or BM, or may be selectively formed on a portion to be flattened. When the flattening film is formed on the entire surface of the pixel or BM, the flattening film is preferably made of a cured product of a thermosetting resin composition, and when the flattening film is selectively formed, the flattening film is formed. Is preferably composed of a cured product of the photosensitive resin composition.

The flattening film preferably contains a resin, and may further contain an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant and the like.

The film thickness of the flattening film is preferably 0.5 μm or more, and more preferably 1.0 μm or more, from the viewpoint of flatness and suppressing elution of impurities from the pixels. On the other hand, the film thickness of the flattening film is preferably 3.0 μm or less, more preferably 2.0 μm or less, from the viewpoint of improving transparency.

The color filter substrate of the present invention can be obtained by forming the photospacer and pixels of the present invention, a black matrix, a flattening film, or the like, if necessary, on the substrate. Examples of the method for forming the pixel, the black matrix, and the flattening film include a photolithography method, a printing method, and an electrodeposition method.

The liquid crystal display device of the present invention is formed by using the resin composition of the present invention arranged between the color filter substrate and the drive element side substrate, the color filter substrate and the drive element side substrate arranged so as to face each other. The photospacer is provided with a liquid crystal compound filled between the two substrates. The color filter-board and the drive element-side board usually have a liquid crystal alignment film for controlling the orientation direction of the liquid crystal. For example, when using a color filter substrate having a black matrix, it is preferable to have a photo spacer in a non-display area, that is, above the black matrix. The drive element-side substrate may have a photo spacer, and in this case as well, it is preferable to have a photo spacer above the non-display region on the drive element-side substrate. Since the photo spacer is provided for the purpose of maintaining a uniform distance between two opposing substrates, it can be manufactured without distinction between a hard substrate such as glass and a soft substrate such as a film. .. It can also be used in applications such as liquid crystal display devices and electrowetting devices. As the liquid crystal alignment film, a resin film such as polyimide is preferable.

The photosensitive resin composition used to form the photospacer is uniformly applied onto the substrate. The coating thickness is preferably 0.5 μm to 500 μm, preferably 1 μm or more from the viewpoint of increasing the elastic recovery rate, and preferably 5 μm or less from the viewpoint of coating uniformity. Subsequently, it is exposed, developed, and dried in a predetermined pattern, and if necessary, it is cured to form a photo spacer. When the shape of the photo spacer is observed from above the substrate, a striped shape, a polygonal shape, or a circular shape is preferable. A polygon or a circle having an octagon or more is preferable because the size variation is small, and a quadrangle is preferable because misalignment is unlikely to occur. It is preferable to create a striped photo spacer orthogonal to both substrates because the contact area is less likely to vary. The cross-sectional shape is preferably rectangular, trapezoidal with a wide lower side, trapezoidal with a wide upper side, or hemispherical. A rectangle is preferable in order to maximize the effective volume, and a hemisphere is preferable in order to prevent the alignment film from being damaged. It is also preferable to provide a plurality of heights by using multi-stage exposure and halftone exposure. It is also preferable to simultaneously provide a main spacer that mainly supports the gap and a sub spacer that is slightly lower than the main spacer because the number of steps can be reduced. It is further preferable to provide the flattening film at the same time.

Next, an example of a method for manufacturing a liquid crystal display device using the above-mentioned color filter substrate will be described. It is preferable to have a step of manufacturing a photo spacer on the color filter substrate and / or the drive element side substrate by the above-mentioned manufacturing method. Specifically, the above-mentioned color filter substrate and the drive element side substrate are opposed to each other, bonded to each other via a photo spacer, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed. Finally, it is preferable to mount an IC driver or the like. When the liquid crystal display device has a liquid crystal alignment film, it is preferable that the polyimide liquid is applied and heat-treated, and then the surface is treated by rubbing treatment or ultraviolet treatment. From the viewpoint of suppressing the generation of fine dust and static electricity and aligning the liquid crystal molecules uniformly and with high definition, it is preferable to perform surface treatment by ultraviolet treatment.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples thereof, but the present invention is not construed as being limited to these examples.

Each physical property and property was measured or evaluated by the following method.

(Ethylene unsaturated group equivalent)
The ethylenically unsaturated group equivalent of each component was calculated by measuring the iodine value by the method described in Section 6.0 of the test method of JIS K 0070: 1992. The ethylenically unsaturated group equivalent of the solid content of the resin composition was determined from the mass ratio of each component constituting the solid content and the ethylenically unsaturated group equivalent of the component.

(Isocyanate group equivalent)
The isocyanate group equivalent was determined by the method described in the test method of JIS K 1556: 2006.

(Urethane equivalent)
Regarding the polymerizable compounds U-1 to 10 and the acrylic soluble resin AC-2 obtained from Production Examples 1 to 10 and 12 using the isocyanate and the hydroxyl group as raw materials, the peak of isocyanate was 2260 cm ^-1 as measured by infrared spectroscopy. It was confirmed that the strength was 0.000001 or less. Since all the isocyanate groups were converted into urethane bonds, the urethane equivalent was calculated from the charged composition. In addition, the measurement of the molecular weight was determined as a standard polystyrene-equivalent value by a gel permeation chromatograph, unless it is known.

Production Example 11 Regarding the obtained alkali-soluble resin AC-1, the molecular weight was determined as a standard polystyrene-equivalent value using gel permeation chromatography, and the molecular weight was calculated from the amount of urethane bonds contained in the raw materials.

(Acid value)
The acid value was measured by the neutralization titration method of Section 3.1 of the test method of JIS K 0070: 1992.

Production Example 1 (Polymeric Compound U-1)
168.2 parts by mass of hexamethylene diisocyanate isocyanulate and 0.1 parts by mass of dibutyltin dilaurate were charged in a reaction vessel equipped with a cooling tube, a stirrer and a thermometer, and the temperature was raised to 50 ° C., and then dipentaerythritol pentaacrylate. After dropping 524.52 parts by mass over 1 hour, the reaction was carried out by stirring at 90 ° C. for 5 hours. When the amount of residual isocyanate in this reaction solution was measured, the amount of isocyanate was below the detection limit, and a polymerizable compound (U-1) subjected to the urethanization reaction was obtained. The molecular weight of U-1 is 2078.2, the isocyanate equivalent is infinite (that is, the isocyanate group could not be detected. The meaning of infinity is the same below), the urethane equivalent is 692.6 g / mol, and ethylene. The sex unsaturated group equivalent was 138.5. The number of ethylenically unsaturated groups in one molecule was 15.

Table 1 shows the characteristic values of the polymerizable compounds of Production Examples 1 to 10 and Production Examples 12 shown below.

Production Example 2 (Polymeric Compound U-2)
A polymerizable compound (U-2) was obtained in the same manner as in Production Example 1 except that pentaerythritol triacrylate was 298.29 parts by mass instead of 524.52 parts by mass of dipentaerythritol pentaacrylate in Production Example 1.

Production Example 3 (Polymeric Compound U-3)
A polymerizable compound (U-3) was obtained in the same manner as in Production Example 1 except that tripentaerythritol heptaacrylate 750.75 parts by mass was used instead of 524.52 parts by mass of dipentaerythritol pentaacrylate in Production Example 1. ..

Production Example 4 (Polymeric Compound U-4)
Hexamethylene diisocyanate isocyanulate of Production Example 1 was replaced with 168.2 parts by mass with 154.17 parts by mass of hexamethylene diisocyanate uretdione, and dipentaerythritol pentaacrylate was replaced with 724.52 parts by mass with acrylic acid by 72.06 parts by mass. A polymerizable compound (U-4) was obtained in the same manner as in Production Example 1 except for the above.

Production Example 5 (Polymeric Compound U-5)
A polymerizable compound (U-5) was obtained in the same manner as in Production Example 4 except that pentaerythritol tetraacrylate 298.29 parts by mass was used instead of 72.06 parts by mass of acrylic acid in Production Example 4.

Production Example 6 (Polymeric Compound U-6)
A polymerizable compound (U-6) was obtained in the same manner as in Production Example 4 except that dipentaerythritol pentaacrylate 524.52 parts by mass was used instead of 72.06 parts by mass of acrylic acid in Production Example 4.

Production Example 7 (Polymeric Compound U-7)
A polymerizable compound (U-7) was obtained in the same manner as in Production Example 6 except that the amount of tripentaerythritol heptaacrylate was 750.75 parts by mass instead of 72.06 parts by mass of acrylic acid in Production Example 4.

Production Example 8 (Polymeric Compound U-8)
A polymerizable compound (U-8) was obtained in the same manner as in Production Example 4 except that the hexamethylene diisocyanate uretdione compound of Production Example 4 was replaced with 84.1 parts by mass of hexamethylene diisocyanate.

Production Example 9 (Polymeric Compound U-9)
168.2 parts by mass of hexamethylene diisocyanate isocyanul compound and 0.1 part by mass of dibutyltin dilaurate were charged in a reaction vessel equipped with a cooling tube, a stirrer and a thermometer, and the temperature was 25 ° C., and then dipentaerythritol pentaacrylate 524. After dropping 52 parts by mass over 1 hour, the reaction was carried out by stirring at 25 ° C. for 1 day to obtain a polymerizable compound group U-9.

When this U-9 was measured by GPC, it was a mixture of three types, U-9-1, U-9-2, and U-9-3, and the measured values were sorted and measured. The urethane reaction was not completed due to the presence of isocyanate residues. U-9-1 (composition ratio 25%, molecular weight 2078.2, isocyanate equivalent infinite, urethane equivalent 692.7 g / mol, ethylenically unsaturated group equivalent 138.55 1 molecule of ethylenically unsaturated groups 15), U -9-2 (composition ratio 30%, molecular weight 1553.63, isocyanate equivalent 1553.6 g / mol, urethane equivalent 776.8 g / mol, ethylenically unsaturated group equivalent 155.36 1 molecule of ethylenically unsaturated groups 10 ), U-9-3 (composition ratio 45%, molecular weight 1029.11, isocyanate equivalent 514.6 g / mol, urethane equivalent 1029.1 g / mol, ethylenically unsaturated group equivalent 205.82 1 molecule of ethylenically unsaturated The weight average molecular weight, isocyanate equivalent, ethylenically unsaturated group equivalent and urethane equivalent of U-9 as a whole, which had the number of groups 5), were as shown in Table 1.

The structural formulas of the polymerizable compounds U-1 to U-9-3 are shown below.

Production Example 10 (Polymeric Compound U-10)
Instead of 524.52 parts by mass of dipentaerythritol pentaacrylate in Production Example 1, 807 parts by mass of dipentaerythritol triacrylate alkylene oxide variant (“KAYARAD” (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) A polymerizable compound (U-10) was obtained in the same manner as in Production Example 1 except for the above.

Production Example 11 (Alkali-soluble resin AC-1)
72 g of methacrylate (MA), 40 g of N-cyclohexylmaleimide (CHMI), 30 g of methyl methacrylate (MMA), 3 g of 2,2'-azobis (2-methylbutyronitrile), 0.5 g of lauryl mercaptan. And 220 g of propylene glycol monomethyl ether (PGME) was charged in a polymerization vessel and stirred at 90 ° C. for 2 hours in a nitrogen atmosphere, then the liquid temperature was raised to 100 ° C., and the mixture was further heated and stirred for 5 hours to react. Next, the inside of the polymerization vessel was replaced with air, and 97 g of glycidyl methacrylate (GMA), 1.2 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the obtained reaction solution at 110 ° C. After stirring for 6 hours, PGME was added to obtain a solution of alkali-soluble resin 1 (AC-1) having a solid content concentration of 25.0% by mass. The obtained AC-1 had a Mw of 40,000, an ethylenically unsaturated group equivalent of 350 g / mol, and an acid value of 85 mgKOH / g. In the alkali-soluble resin AC-1, MA constitutes a structural unit represented by the general formula (3), GMA gives a structural unit represented by the general formula (4), and CHMI is the general formula (5). Gives the structural unit represented by.

Production Example 12 (Alkali-soluble resin AC-2)
686 g of propylene glycol monomethyl ether acetate (PGMAc), 332 g of glycidyl methacrylate (GMA), and 6.6 g of azobisisobutyronitrile (AIBN) are added to a 5-port reaction vessel having a content of 2 liters, and nitrogen is blown into the reaction vessel. While heating at 80 ° C. for 6 hours, a polymer solution of GMA was obtained.

Next, 168 g of acrylic acid (AA), 0.05 g of methquinone (MQ) and 0.5 g of triphenylphosphine (TPP) were added to the obtained polymer solution of GMA, and the mixture was heated at 100 ° C. for 24 hours while blowing air. Then, an acrylic acid adduct solution of GMA resin was obtained.

Further, 186 g of tetrahydrophthalic anhydride was added to the acrylic acid adduct solution of the obtained resin, and the mixture was heated at 7 ° C. for 10 hours.

Further, 117.22 g of methacryloyloxyethyl isocyanate (“Karens MOI” manufactured by Showa Denko) and 117.22 g of propylene glycol monomethyl ether acetate (PGMAc) were added, and the mixture was heated at 60 ° C. for 12 hours while blowing air, and PGME was added. An alkali-soluble resin (AC-2) solution having a solid content concentration of 25.0% by mass was obtained. The obtained AC-2 has a Mw of 16,000 and an ethylenically unsaturated group equivalent of 260 g / mol. The urethane equivalent was 1061.94 g / mol. The number of ethylenically unsaturated groups per molecule was 61.5, and the urethane equivalent was 1061.9 g / mol.

Production Example 13 (Preparation of alignment film for photoalignment)
To a 500 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 2.2636 g of the compound represented by the formula (8) and 104.0 g of N-methyl-2-pyrrolidone were added. The solution was ice-cooled to a liquid temperature of 5 ° C., 3.7364 g of the compound represented by the formula (9) was added, and the mixture was stirred at room temperature for 12 hours. 10.0 g of γ-butyrolactone and 80.0 g of butyl cellosolve are added thereto, and the solution is heated and stirred at 60 ° C., and the solute has a weight average molecular weight of 16,000 and a resin concentration of 3% by mass. The composition for use was obtained.

Production Example 14 (Alkali-soluble resin AC-3)
95.3 g of methacrylic acid (MA), 3.0 g of 2,2'-azobis (2-methylbutyronitrile), 0.5 g of lauryl mercaptan and 239 g of 3-methoxy-1-butanol solution in a polymerization vessel. After stirring at 90 ° C. for 2 hours in a nitrogen atmosphere, the liquid temperature was raised to 100 ° C., and the mixture was further heated and stirred for 5 hours to react. Next, the inside of the polymerization vessel was replaced with air, and 143.7 g of glycidyl methacrylate (GMA), 1.2 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and 110 After stirring at ° C. for 6 hours, 3-methoxy-1-butanol was added to obtain a solution of alkali-soluble resin 3 (AC-3) having a solid content concentration of 40.0% by mass. The obtained AC-3 had a Mw of 10,000 and an ethylenically unsaturated group equivalent of 250 g / mol).

(Viscosity of pre-baked film)
Pre-baking under the same conditions and conditions as described in each example, except that a non-alkali glass substrate (OA-10; manufactured by Nippon Electric Glass Co., Ltd .; 50 mm × 70 mm, thickness 0.7 mm) was used as the coating target. A membrane was prepared. ^{Collect 90 mm 3} or more of the obtained prebaked film using a spatula, and use a rheometer (MCR-302; manufactured by Anton Pearl Co., Ltd.) and a φ15 mm plate to measure thickness: 0.5 mm, frequency: 1 Hz, distortion. : The viscosity at 23 ° C. was measured while raising the temperature from 20 ° C. to 110 ° C. at a heating rate of 0.083 ° C./sec under the condition of 0.5%.

(Evaluation of elastic recovery rate and elastic recovery rate of photo spacers)
A truncated cone-shaped photospacer formed in each Example and Comparative Example was loaded with a hardness tester Fisher (Fisherscape H100; Helmut Fisher GmbH & Co) and a flat indenter of φ50 μm at a speed of 2.5 mN / sec. A hysteresis curve was created when pressure was applied until the temperature reached 50 mN and the mixture was held for 5 seconds, then opened at a speed of 2.5 mN / sec and held for 5 seconds after reaching 0 mN. From the obtained hysteresis curve, the total deformation amount Ha [μm] and the plastic deformation amount Hb [μm] were obtained, and the elastic recovery rate of the photospacer (((Ha−Hb) / Ha) × 100) (%) was calculated. .. The number average value measured at 5 points was calculated and evaluated according to the following criteria as the elastic recovery rate evaluation. B judgment or higher was regarded as passing.
E: Elastic recovery rate is less than 50% D: Elastic recovery rate is 50% or more and less than 55% C: Elastic recovery rate is 55% or more and less than 60% B: Elastic recovery rate is 60% or more and less than 65% A: Elastic recovery rate Is 65% or more and less than 70% AAA: Elastic recovery rate is 70% or more and less than 75% AAA: Elastic recovery rate is 75% or more.

(Sliding resistance of photo spacer)
The liquid crystal panel was fixed to a pedestal that reciprocates at 2 cm per second, and was subjected to a sliding tester with a stainless ball having a radius of curvature of 5 mm under a load of 240 g to prepare a panel tested from 500 times to 15,000 times in increments of 500 times. .. This panel was disassembled and the opposing alignment films were observed, and the operation with the sliding tester was continued until scratches were confirmed, and the maximum number of times no scratches were observed was defined as the sliding resistance. In addition, the slidability was evaluated according to the following criteria. B judgment or higher was regarded as passing.
E: Sliding resistance is 500 or less D: Sliding resistance is more than 500 and less than 2000 C: Sliding resistance is more than 2000 and less than 3000 B: Sliding resistance is more than 3000 and 6000 Less than A: The number of sliding resistance exceeds 6000 and less than 10000 AA: The number of sliding resistance exceeds 10000 and less than 15000 AAA: The number of sliding resistance is 15000 or more.

(Viscosity stability evaluation)
The viscosity of the resin composition was measured with an E-type viscometer, and the following determination was made based on the ratio of the viscosities after storage at 40 ° C. for 1 week to the first day of adjustment. B judgment or higher was regarded as passing.
E: Viscosity change is ± 90% or more D: Viscosity change is less than ± 90% and ± 10% or more C: Viscosity change is less than ± 10% and ± 3% or more B: Viscosity change is less than ± 3% and ± 2% A: Viscosity change is less than ± 2% and ± 1% or more AA: Viscosity change is less than ± 1% and ± 0.1% or more AAA: Viscosity change is less than ± 0.1%.

(Variation in height of photo spacer)
Among the conical trapezoidal photospacers formed in each Example and Comparative Example, in a range of 20 mm square in the substrate surface, at a portion corresponding to a joint portion between a plurality of lenses provided in the lens scan exposure apparatus. Twenty photo spacers are selected at regular intervals in a direction perpendicular to the direction in which the plurality of lenses are arranged in two rows, and height variation (maximum height-minimum) is performed using a step measuring device. Height) was measured, and the height variation of the photo spacer was evaluated according to the following criteria.
E: Height variation is 0.060 μm or more D: Height variation is 0.050 μm or more and less than 0.060 μm C: Height variation is 0.040 μm or more and less than 0.050 μm B: Height variation is 0. 020 μm or more and less than 0.040 μm A: Height variation is 0.010 μm or more and less than 0.020 μm AA: Height variation is 0.005 μm or more and less than 0.010 μm AAA: Height variation is less than 0.005 μm.

(Evaluation of development margin)
In each Example and Comparative Example, the photospacer of the color filter substrate whose development time was increased or decreased from 20 seconds to 100 seconds in 5 second increments was evaluated in a time range in which there was no development chipping or residue.
E: Development time without chipping-development time without residue 10 seconds or less D: Development time without chipping-development time without residue 15 seconds C: Development time without chipping-development time without residue 20 seconds B : Development time without chipping-Development time without residue 25 seconds A: Development time without chipping-Development time without residue 30 seconds AA: Development time without chipping-Development time without residue 35 seconds AAA: Development time without chipping Development time without residue-Development time without residue is 40 seconds or more.

(Preparation of Comparative Photosensitive Resin Composition 1 (HK-1))
As an alkali-soluble resin solution, AC-3 (ethylene unsaturated group equivalent 250 g / mol, urethane equivalent infinite (that is, urethane bond could not be detected. The meaning of infinity is the same below)): 50.07 parts by mass. , As a polymerizable compound, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD” (registered trademark) DPHA; Nippon Kayaku; hereinafter, “DPHA”) (ethylene unsaturated group equivalent 101.6, Molecular weight 559, urethane equivalent infinite): 8.58 parts by mass, photopolymerization initiator "Adeca Arculus" (registered trademark) N-1919; hereinafter, "N1919": 0.18 parts by mass (ethylene unsaturated group equivalent) Infinity (that is, the ethylenically unsaturated group could not be detected. The meaning of infinity is the same below), urethane equivalent infinity), "IRGACURE" (trademark registration) 907 (manufactured by BASF Japan Co., Ltd.); "IC907": 0.27 parts by mass (ethylene unsaturated group equivalent infinite, urethane equivalent infinite), 2,4-diethylthioxanthone ("KAYACURE" (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd. ; "DETX"): 0.45 parts by mass (ethylene unsaturated group equivalent infinite, urethane equivalent infinite), surfactant "BYK" (registered trademark) -333 (manufactured by Big Chemie Japan Co., Ltd.) : Hereinafter, "BYK-333") 0.11 part by mass (ethylene unsaturated group equivalent infinite, urethane equivalent infinite), polymerization inhibitor 2,5-bis (1,1,3,3-tetramethylbutyl) Hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter, "DOHQ"): 0.07 parts by mass (ethylene unsaturated group equivalent infinite, urethane equivalent infinite) and propylene glycol monomethyl ether (PMA 40 parts by mass at room temperature) To obtain a comparative photosensitive resin composition (HK-1).

This comparative photosensitive resin composition (HK-1) contains 66.77% by mass of an alkali-soluble resin AC-3 having an ethylenically unsaturated group equivalent of 250 g / mol in a solid component, and has an ethylenically unsaturated group equivalent. The ethylenically unsaturated group equivalent of this resin composition containing 28.61% by mass of the polymerizable compound DPHA having a value of 101.6 g / mol in the solid component was 182.3 g / mol.

(Comparative Photosensitive Resin Compositions HK-2 to HK-3, Implementation Photosensitive Resin Compositions JK-1 to JK-17)
The comparative photosensitive resin composition was prepared by the same procedure as that of HK-1, except that the mass compounding ratio was as shown in Tables 2 to 4.

(Comparative Example 1)
(Preparation of resin composition for black matrix)
Carbon black (MA100 manufactured by Mitsubishi Chemical Co., Ltd.) 150 g, polymer dispersant ("BYK" (registered trademark) 6919, 60% by mass solution manufactured by Big Chemie) 75 g, "Cyclomer" (registered trademark) P (ACA) Z250 ( A 45% by mass solution of dipropylene glycol monomethyl ether, an acid value of 110 mgKOH / g, a molecular weight of 20,000), 100 g, and 675 g of propylene glycol monomethyl ether acetate (PMA) were mixed to prepare a slurry. A beaker containing the slurry was connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm were used as a medium to carry out a dispersion treatment at a peripheral speed of 14 m / s for 8 hours. Was produced.

BMD-1 56.54, "Cyclomer" P (ACA) Z250 3.14 g, DPHA monomer as a polymerizable compound ("Kayarad" (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.) 2.64 g, photopolymerization started Agent ("ADEKA CORPORATION" (registered trademark) NCI-831 (hereinafter NCI-831)) 0.330 g, surfactant ("BYK" (registered trademark) -333 (hereinafter BYK-333) manufactured by Big Chemie Co., Ltd. )) 0.04 g and 0.01 g PMA 37.30 g of a polymerization inhibitor (tershalibutylcatechol (TBC) manufactured by DIC Co., Ltd.) were added to prepare a black matrix resin composition 1 (BM-1) for a black matrix. did.

(Preparation of red resin composition)
C. I. Pigment Red 177 (“Kromoftal” Red (registered trademark) A2B manufactured by Ciba Speciality Chemical Co., Ltd.) 150 g, “BYK” 6919 75 g, “Cyclomer” P (ACA) Z250 100 g, and PMA 675 g were mixed to prepare a slurry. .. A beaker containing the slurry is connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm are used as a medium to carry out a dispersion treatment at a peripheral speed of 14 m / s for 8 hours to prepare a dispersion liquid for red (RD-1). Made.

RD-1 56.54, "Cyclomer" P (ACA) Z250 3.14g, DPHA Monomer 2.64g, Photopolymerization Initiator (NCI-831) 0.330g, Surfactant (BYK-333) 0.04g , 0.01 g of polymerization inhibitor (TBC) PMA 37.30 g was added to prepare a red resin composition (R-1).

(Preparation of blue resin composition)
C. I. Pigment Blue 15: 6 (EP193 manufactured by DIC Corporation) 150 g, "BYK" 6919 75 g, "Cyclomer" P (ACA) Z250 100 g, and PMA 675 g were mixed to prepare a slurry. A beaker containing the slurry is connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm are used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours to obtain a blue dispersion (BD-1). Made.

BD-1 29.02, "Cyclomer" P (ACA) Z250 12.70 g, DPHA monomer 4.68 g, photopolymerization initiator (NCI-930) 0.585 g, surfactant (BYK-333) 0.04 g , 0.01 g of a polymerization inhibitor (TBC) and 52.96 g of PMA were added to prepare a blue resin composition (B-1).

(Preparation of colorant dispersion)
C. I. Pigment Green 59 (FASTGEN Green C100) 105g, C.I. I. Pigment Yellow 45 (“Hostaperm” Yellow HN4G manufactured by Clariant), 75 g of a polymer dispersant (“BYK” 6919), 100 g of a binder resin (“ADEKA ARCLUDS” WR301), and 675 g of PMA were mixed to prepare a slurry. A beaker containing the slurry was connected to a dyno mill with a tube, and zirconia beads having a diameter of 0.5 mm were used as a medium for dispersion treatment at a peripheral speed of 14 m / s for 8 hours. Pigment Green 59 dispersion (D-1) Was produced.

Colorant dispersion D-1 47.361 g, WR301 1.111 g DPHA monomer (Nippon Kayaku "Kayarad" (registered trademark) DPHA acid value 0.1 mgKOH / g) 1.863 g, photopolymerization initiator (Co., Ltd.) ) ADEKA "ADEKA ARCLUS" (registered trademark) NCI-831) 0.192g, chain transfer agent (Showa Denko Corporation "Karenzu" (registered trademark) MT-PE1 0.021g), adhesion improver (Shinetsu) KBM-503 manufactured by Kagaku Kogyo Co., Ltd. 0.160 g, surfactant (“BYK” (registered trademark) -333 manufactured by Big Chemie) 0.040 g, polymerization inhibitor (tershaributyl catechol (TBC) manufactured by DIC) 0. A green resin composition was prepared by adding 009 g, PMA 7.243 g, and dipropylene glycol monomethyl ether acetate (DPMA) 42.001 g.

(Manufacturing of color filter substrate)
The black matrix resin BM-1 was applied onto the non-alkali glass so that the film thickness after curing was 1.5 μm, and vacuum dried. ^{Exposed with i-line 40 mJ / cm 2} through a striped photomask with a pixel pitch of 50 μm and a black matrix width of 5 μm, developed with a 0.3 mass% tetramethylammonium aqueous solution for 50 seconds, and heated at 230 ° C. for 30 minutes. Curing was performed to form a black matrix.

A red resin composition R-1 was applied thereto so that the film thickness was 2.5 μm, and the mixture was vacuum dried. ^{It was exposed at 40 mJ / cm 2} i-line through a 50 μm wide striped photomask, developed with a 0.3 mass% tetramethylammonium aqueous solution for 50 seconds, heat-cured at 230 ° C. for 30 minutes, and had a pixel pitch of 50 μm. Red pixels were formed.

Further, the blue resin composition B-1 was applied thereto so that the film thickness was 2.5 μm, and the mixture was vacuum dried. ^{It was exposed at 40 mJ / cm 2} i-line through a 50 μm wide striped photomask, developed with a 0.3 mass% tetramethylammonium aqueous solution for 50 seconds, heat-cured at 230 ° C. for 30 minutes, and had a pixel pitch of 50 μm. A blue pixel was formed.

Further, a green resin composition was applied thereto so that the film thickness became 2.5 μm after curing, and the mixture was dried by heating at 90 ° C. for 10 minutes. ^{It was exposed at 100 mJ / cm 2} i-line through a 50 μm wide striped photomask, developed with a 0.3 mass% tetramethylammonium aqueous solution for 60 seconds, heat-cured at 230 ° C. for 30 minutes, and had a pixel pitch of 50 μm. After forming the green pixels of the above, an overcoat layer was prepared.

Further, the comparative photosensitive resin composition 1 was applied thereto. After drying under reduced pressure for 200 seconds under the conditions of temperature: 25 ° C. and pressure: 45 Pa, the mixture was heat-dried (prebaked) at 105 ° C. for 10 minutes and then cooled to room temperature to form a prebaked film. Next, as a lens scan exposure device, FX-65S (manufactured by Nikon Corporation) includes wavelengths of i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm through a circular photomask having a diameter of 7 μm. Using ultraviolet rays as irradiation light, exposure was performed at an exposure amount of ^{60 mJ / cm 2 (i-line conversion).}

Next, an aqueous solution at 23 ° C. containing 0.3% by mass of TMAH and 0.3% by mass of A-60 was used as a developing solution, shower-developed for 60 seconds, washed with water, and drained. Finally, a plurality of color filter substrates having photospacers having an upper base of 6 μm, a lower base of 9 μm, and a height of 3 μm were prepared by heating and drying (post-baking) in an oven at 230 ° C. for 30 minutes. Evaluations such as elastic recovery rate evaluation were performed with a few sheets, and the rest proceeded to the manufacturing process of the display device.

(Manufacturing of display device)
A TFT element, a transparent electrode, and the like were formed on non-alkali glass to prepare a TFT array substrate. The composition for an alignment film for photoalignment of Production Example 12 is applied to the color filter substrate and the array substrate obtained by the above method under the condition that the film thickness becomes 100 nm after curing, and the polarizing plate is applied from the vertical direction to the substrate. The linearly polarized light of ultraviolet rays was irradiated through the light, and the light was deflected ^{at 1.3 J / cm 2 at a wavelength of 365 nm.} The firing treatment was performed at 230 ° C. for 20 minutes.

A sealant kneaded with a micro rod was printed on the array substrate, and the array substrate and the color filter substrate were bonded together. After injecting IPS liquid crystal from the injection port provided in the seal portion, polarizing films were attached to both sides of the liquid crystal cell so that the polarization axes were vertical to obtain a liquid crystal panel. A backlight light source was attached to this liquid crystal panel, a TAB module, a printed circuit board, and the like were mounted, and a liquid crystal display device was manufactured.

The ethylenically unsaturated group equivalent of this comparative photosensitive resin composition (HK-1) was 176.7, the elastic recovery rate was 48.1, and the elastic recovery rate evaluation was E. Urethane does not include only the following IR measurement limit, although urethane equivalent is virtually infinite, was calculated to measure the lower limit value as 1.0 × 10 ⁹ adopted. The sliding resistance was 4000 times and the evaluation was B.

(Comparative Examples 2-3, Examples 1-17)
A prebake film, a photo spacer, and a liquid crystal display device were produced in the same manner as in Comparative Example 1 except that the composition of the photosensitive resin composition was changed as shown in Tables 2 to 4. The results of evaluating the mass% of the resin composition, ethylene unsaturated bond equivalent, urethane equivalent, urethane equivalent / ethylene unsaturated bond equivalent, elastic recovery rate, elastic recovery rate evaluation, sliding resistance frequency, and slidability evaluation It is shown in Tables 5 to 7.

(Comparison of Comparative Examples 1 to 3)
In Comparative Examples 2 and 3 in which the compounding ratio was changed and the ethylenically unsaturated bond equivalent was reduced as compared with Comparative Example 1, there was a correlation between the ethylenically unsaturated group equivalent and the elastic recovery rate, and the elastic recovery rate was passed B. It can be said that 155 g / mol or less is required in order to exceed the judgment. In addition, as the elastic recovery rate improves, the number of sliding resistances decreases, which is a trade-off relationship, and it can be said that increasing or decreasing the ethylenically unsaturated bond equivalent is incompatible.

(Comparison between Example 1 and Comparative Example 3)
In Example 1 in which the urethane equivalent was adjusted to 14523 g / mol by substituting a part of DPHA with the polymerizable compound U-1 containing a urethane bond with respect to Comparative Example 3, the restoration rate evaluation was resistant while maintaining AA. The number of sliding times increased from 500 times to 3500 times, and the slidability evaluation improved from E to B. It can be said that the inclusion of urethane made it possible to achieve both restoration rate evaluation and slidability evaluation. It can be said that also in Examples 2 to 16, by using the polymerizable compound containing the urethane bond or the alkali-soluble resin, the slidability evaluation becomes B judgment or higher while the elastic recovery rate evaluation maintains AA.

(Comparison of Examples 2 to 5)
Looking at Example 2 and Examples 3 to 5 in which the value of urethane equivalent is smaller than that, the correlation between the urethane equivalent and the number of sliding resistances is confirmed. If the urethane equivalent is 50,000 g / mol or less, it can be said that the evaluation of the elastic recovery rate can be compatible.

If the value obtained by dividing the urethane equivalent by the ethylenically unsaturated group equivalent is 10 to 200, it can be said that both are easy to achieve.

(Comparison of Examples 7-14 and 17)
When Examples 7-14 with different polymerizable compounds are compared. In Example 10 in which the number of ethylenically unsaturated groups in one molecule was 2, in Examples 7 to 9 and 11 to 14 in which the number of ethylenically unsaturated groups in one molecule was 6 or more, the number of sliding resistances was high. There were many. In the same comparison, when the molecular weight of the polymerizable compound containing urethane is 700 to 3000, the number of sliding resistances is high, and when it is 1000 to 3000, the number of sliding resistances is even higher.

(Comparison of Examples 7 to 9)
In Examples 7 to 9, when a polymerizable compound common in that it has the structure of the general formula (1) is used, the more ethylenically unsaturated groups in one molecule, the larger the number of sliding resistances.

(Comparison of Examples 10 to 13)
In Examples 10 to 13, when the polymerizable compound common in that it has the structure of the general formula (2) is used, the more ethylenically unsaturated groups in one molecule, the larger the number of sliding resistances.

(Comparison of Examples 7, 12 and 14)
Example 12 using U-6 obtained by reacting dipentaerythritol pentaacrylate with the structure of the general formula (2) uses Example 14 using U-8 obtained by reacting hexamethylene isocyanate with dipentaerythritol pentaacrylate. The number of sliding resistances was higher than that of. Similarly, Example 7 using U-1 in which dipentaerythritol pentaacrylate was reacted with the structure of the general formula (1) had a higher number of sliding resistances than Example 10.

(Comparison of Example 9 and Example 16)
Example 16 containing an alkylene oxide modified product in the polymerizable compound can significantly improve the sliding resistance from 11,000 times to 18,000 times while having the same elastic recovery rate as that of Example 9. It was.

(Example 18)
The viscosity of the resin composition JK-1 was measured with an E-type viscometer, and the ratio of the viscosities after storage at 40 ° C. for 1 week to the first day of adjustment was measured and evaluated according to the above-mentioned criteria. The viscosity stability was AAA, which was particularly excellent.

Among the truncated cone-shaped pattern photospacers formed in the resin composition JK-1, the direction in which a plurality of lenses are lined up in two rows in the substrate surface within a range of 20 mm square in the substrate surface corresponding to the joint portion between the lenses. Twenty photo spacers are selected at regular intervals in the direction perpendicular to the lens, and the height variation (maximum height-minimum height) is measured using a step measuring device to evaluate the height variation of the photo spacers. did. The height variation was C.

In the color filter substrate prepared using the resin composition JK-1, only the development time of the photo spacer was changed from 20 to 100 seconds in 5 second increments, and the development margin was increased by the length of time without residue and omission. evaluated. The development margin was AAA.

(Examples 18 to 34)
Examples 18 to 34 were carried out in exactly the same manner except that the resin compositions JK-1 of the examples were replaced with JK-2 to JK-17, respectively.

The isocyanate equivalent, dry viscosity, height variation evaluation, and viscosity stability are shown in Tables 8-9.

In Example 19 using the alkali-soluble resin containing the structure of the general formula (5) with respect to Example 18, the dry viscosity can be increased, and the height variation evaluation can be increased from C to B accordingly. It was.

(Comparison of Example 19 and Example 23)
In Example 23 in which the amount of the alkali-soluble resin containing the structure of the general formula (5) was increased with respect to Example 19, the height variation evaluation could be raised from B to AAA.

(Comparison of Examples 18-31 and 32)
When the isocyanate equivalent is 50,000 g / mol or more, it can be said that the viscosity stability is good and the development margin is good.

(Comparison of Examples 18-31 and 34)
It can be said that the development margin is good when urethane is derived from a polymerizable compound having a molecular weight of 3000 or less.

(Analysis of resin composition)
JK-16 having a solid content concentration of 30.0% by mass, which was blended as shown in Table 4, was placed in an aluminum cup (φ45 mm) in an amount of 5 g and heated at 130 ° C. for 1 hour to remove the solvent. The solid content concentration was 30.0% by mass. The molecular weight of the sample diluted with tetrahydrofuran and adjusted to 0.2% by mass was measured by GPC, and each component was separated. The composition ratio was determined from the area ratio. The structure of each component was identified by 1H-NMR, and the ethylene unsaturated group equivalent and the urethane equivalent were calculated. When the ethylene unsaturated group equivalent and urethane equivalent of the resin composition were calculated based on the ethylene unsaturated group equivalent and urethane equivalent of the raw materials used, it was confirmed that they showed very high consistency.

The photosensitive resin composition of the present invention is suitably used as a material for forming a photo spacer of a liquid crystal display device.

Ha: Total deformation of photo spacer [μm]
Hb: Amount of plastic deformation of photo spacer [μm]

Claims (16)

A photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator and a polymerizable compound, wherein the urethane equivalent required for the solid content of the resin composition is 1000 to 50,000 g / mol, and
A photosensitive resin composition having an ethylenically unsaturated group equivalent of 100 to 155 g / mol. The photosensitive resin composition according to claim 1, wherein at least one component of the polymerizable compound has 6 or more ethylenically unsaturated groups in one molecule. The photosensitive resin composition according to claim 1 or 2, wherein at least one component of the polymerizable compound has 6 or more and 25 or less ethylenically unsaturated groups in one molecule. The photosensitive according to any one of claims 1 to 3, wherein the polymerizable compound has a molecular weight in the range of 700 to 3000, and the polymerizable compound has a urethane bond. Resin composition. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polymerizable compound contains a polymerizable compound represented by the following general formula (1) or the following general formula (2).

Here, in the general formulas (1) and (2), R ^{1 to} R ³ and R ^{7 to} R ⁸ are each independently substituted with an alkylene group having 1 to 20 skeleton carbon atoms which may have a substituent. It represents an alkylene oxide group having 1 to 20 skeleton carbon atoms which may have a group, and an arylene group having 7 to 30 skeleton carbon atoms which may have a substituent. R ^{4 to} R ⁶ and R ^{9 to} R ¹⁰ each independently represent a monovalent group represented by the general formula (3).

Here, n is an integer of 1 to 7, and R ^{11 to} R ¹³ each represent a monovalent group represented by the following general formula (4).

Here, R ¹⁴ represents a hydrogen atom or a methyl group. As the alkali-soluble resin,
A) The structural unit represented by the following general formula (5) and
B) The structural unit represented by the following general formula (6) and
C) The photosensitive resin composition according to any one of claims 1 to 5, which contains a resin having a structural unit represented by the following general formula (7).

(R ¹⁵ indicates a hydrogen atom or a methyl group.)

(R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. X represents −CH ₂ CH (OH) CH ₂ O (C = O) −.)

(Y has an aryl group having a skeleton carbon number of 6 to 11 which may have a substituent, and an aralkyl group or a substituent having a skeleton carbon number of 7 to 10 which may have a substituent. A good skeleton shows a cycloalkyl group having 3 to 10 carbon atoms.) The photosensitive resin composition according to any one of claims 1 to 6, wherein the isocyanate equivalent required for the solid content of the polymerizable compound is 50,000 g / mol or more. The photosensitive resin composition according to any one of claims 1 to 6, wherein the isocyanate equivalent required for the solid content of the polymerizable compound is 50,000 g / mol or more and 5,000,000 g / mol or less. The photosensitive resin composition is heat-treated, applied to a thickness of 3 μm, treated under reduced pressure at 25 ° C. and 45 Pa for 200 seconds, and then heat-dried at 105 ° C. for 10 minutes to obtain a film having a viscosity of 1 × 10 ³ to 23 ° C. The photosensitive resin composition according to any one of claims 1 to 8, which is 1 × 10 ^{8 Pa · s.} The claim is characterized in that it is formed into a truncated cone shape having a diameter of the upper bottom surface of 6 μm, a diameter of the lower bottom surface of 9 μm, and a height of 3 μm, and has an elastic recovery rate of 60% or more when a load of 50 mN is applied. The photosensitive resin composition according to any one of 1 to 9. A photospacer obtained by using the photosensitive resin composition according to any one of claims 1 to 10. The photospacer according to claim 11, which is arranged between the color filter substrate and the drive element side substrate, the color filter substrate and the drive element side substrate, and the color filter substrate and the drive element side substrate, which are arranged so as to face each other. A liquid crystal display device having a liquid crystal compound encapsulated between them. The liquid crystal display device according to claim 12, further comprising a photoalignment film. A step of applying the photosensitive resin composition according to any one of claims 1 to 10 onto a color filter substrate or a substrate on the driving element side, a step of heating and drying the applied film to obtain a prebaked film, and a step of obtaining a prebaked film. A method for manufacturing a substrate with a photospacer, which comprises a step of exposing and developing the prebake film to form a photospacer. A step of forming a precursor film of a photoalignment film on a substrate with a photospacer obtained by the method for manufacturing a substrate with a photospacer according to claim 14, a step of irradiating the precursor film with polarized ultraviolet rays to form a photoalignment film. A method for manufacturing a substrate with a photoalignment film, which comprises a step of A method for manufacturing a liquid crystal display device in which a color filter substrate and a drive element side substrate are arranged to face each other and a liquid crystal compound is sealed between them. The color filter substrate and the drive element side substrate are claimed on at least one substrate. A method for manufacturing a liquid crystal display device, which comprises using a substrate with a photoalignment film obtained by the method according to 15.

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