JP2006276159A - Radiation-sensitive composition for spacer formation, method for manufacturing substrate for liquid crystal display using the same, and substrate for the liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To simultaneously prevent unevenness in gravity, low-temperature foaming and faulty display, due to local load by providing columnar spacers which are compressed fully, even under weak load and exhibit an excellent elastic recovery rate. <P>SOLUTION: A radiation sensitive composition for forming spacers of a liquid crystal display is provided which comprises (I) an alkali-soluble resin, (II) a polyfunctional monomer, (III) a photopolymerization initiator, (IV) a blocked isocyanate and (IV) a solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a spacer in a liquid crystal display device, a method for producing a substrate for a liquid crystal display device using the radiation-sensitive composition, and a substrate for a liquid crystal display device.

  A liquid crystal display device is manufactured by bonding two substrates facing each other and enclosing a liquid crystal compound in the gap. In the liquid crystal display device, display is performed by changing the amount of light transmitted through the liquid crystal layer by controlling the alignment of the liquid crystal by voltage. Since the amount of light transmitted through the liquid crystal layer changes depending on the distance between two substrates (cell gap), maintaining the cell gap constant and uniform prevents display unevenness such as color unevenness and is good. It is a very important technique for making a clear display.

  As a method for maintaining the cell gap constant and uniform, there is a method in which a large number of spherical particles of a certain size made of glass, alumina or the like are distributed as spacers in the liquid crystal layer. However, in the method using spherical particles, since spherical particles are also present in the display region, there are problems such as disturbing the liquid crystal alignment around the spherical particles, and there is a problem that display performance such as contrast ratio is deteriorated. there were.

  As a method for solving the problems when these spherical particles are used as a spacer, a columnar spacer having a height corresponding to the cell gap is formed at a position where the black matrix layer is formed on the substrate, that is, in a non-display area. (Refer to Patent Document 1). The columnar spacer is formed, for example, by photolithography in which a radiation-sensitive resin is uniformly applied on a substrate, pattern exposure is performed, and then alkali development is performed. Here, the columnar spacer may be formed on either of the two substrates as long as it is a non-display area.

  In recent years, a liquid crystal dropping method called “One Drop Filling” has become mainstream as a method for filling liquid crystal into a liquid crystal device, instead of the conventional vacuum press-fitting method. However, in a liquid crystal display device manufactured by a liquid crystal dropping method, the occurrence of uneven gravity described below is a problem.

  In the liquid crystal dropping method, a vacuum press method in which a compressive load is smaller than that of a conventional mechanical press method is used as a sealing method. When the columnar spacer is sealed in a state where it is not sufficiently compressed by the vacuum press method, the columnar spacer cannot follow the thermal expansion of the liquid crystal layer when used at a high temperature, and the columnar spacer is separated from the counter substrate. The liquid crystal is unevenly distributed in the lower part of the liquid crystal display device due to its own weight, thereby causing display unevenness called gravity unevenness.

  In addition, the columnar spacer not only follows the thermal expansion when used at high temperatures, but also has the flexibility to follow the thermal contraction of the liquid crystal that occurs when used for a long time in a low temperature environment. Causes a display defect called low-temperature foaming due to the smaller than the volume inside the cell.

Furthermore, it is important that the columnar spacer not only be flexible, but also not be plastically deformed by a large load. When plastic deformation is caused by a large load, display unevenness due to a local load occurs.
JP-A-11-174464 (Claim 1)

  The present invention has been made in view of the above problems, and in a liquid crystal display device, is intended to prevent the occurrence of display unevenness due to the above-described gravity unevenness, low-temperature bubbles, and local load, and has flexibility, The main object of the present invention is to provide a radiation-sensitive composition for forming a spacer which does not cause plastic deformation against a local load.

  The radiation-sensitive composition for forming a spacer of a liquid crystal display device that solves the above problems includes (I) an alkali-soluble resin, (II) a polyfunctional monomer, (III) a photopolymerization initiator, (IV) a blocked isocyanate, and (V ) A radiation-sensitive composition for forming a spacer of a liquid crystal display device comprising a solvent.

  According to the present invention, a radiation-sensitive composition for forming a spacer of a liquid crystal display device that does not generate gravity unevenness and low-temperature bubbles even by a liquid crystal dropping method using a vacuum press method and does not generate display unevenness due to a local load. It can be provided.

  Hereinafter, the radiation-sensitive composition for forming a spacer, the method for producing a substrate for a liquid crystal display device and the substrate for a liquid crystal display device of the present invention will be described in detail.

  In the present invention, the radiation includes visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.

  The radiation-sensitive composition of the present invention is characterized by comprising (I) an alkali-soluble resin, (II) a polyfunctional monomer, (III) a photopolymerization initiator, (IV) a blocked isocyanate, and (V) a solvent. .

  Below, the structural component of the radiation sensitive composition for spacer formation is demonstrated in detail.

  The (I) alkali-soluble resin in the present invention is not particularly limited as long as it is soluble in an alkaline aqueous solution among resins generally used in color filters, and any resin can be used. For example, various resins such as acrylic resin, alkyd resin, melamine resin, polyvinyl alcohol, polyamide, polyamideimide, polyimide, polyimide precursor, and the like can be used. Among resins that can be dissolved in an alkaline aqueous solution, an acrylic resin having a carboxyl group or a polyimide precursor such as polyamic acid is preferable in that a pattern can be easily formed by development or etching. In particular, it is more preferable to use an acrylic resin having a carboxyl group as the resin because a radiation-sensitive composition in which columnar spacer formation can be made relatively simple by adding a photopolymerization initiator and a polymerizable monomer.

The acrylic polymer having a carboxyl group that can be used in the present invention is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like.
These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like can be mentioned. Not shall. In particular, a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene is measured by weight average molecular weight (Mw, measured by gel permeation chromatography, standard Resin having an acid value of 60 to 140 (mg KOH / g) is 90,000 to 100,000, more preferably 15,000 to 40,000, and the solubility and alkali in the solvent. It is preferable from the viewpoint of solubility in a developer. Outside this range, the solubility in a solvent and the solubility in an alkali developer are lowered, which is not preferable.

  Further, when an acrylic resin having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of patterning is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic resin can be obtained by addition-reacting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer. Specific examples of the acrylic resin having an ethylenically unsaturated group in the side chain include copolymers described in Japanese Patent No. 3120476 and JP-A-8-262221. In particular, an acrylic resin having an ethylenically unsaturated group in the side chain, a polymer having a weight average molecular weight (Mw) of 9000 to 100,000 and an acid value of 60 to 130 (mg KOH / g) is a photosensitive property, with respect to an ester solvent. Most preferable from the viewpoints of solubility and solubility in an alkali developer. Furthermore, in these acrylic resins, a resin containing a hydroxyl group in a part of the side chain is more preferable in view of reactivity with isocyanate.

  The (II) polyfunctional monomer in the present invention is not particularly limited as long as it has two or more ethylenically unsaturated groups in the molecule. Bisphenol A diglycidyl ether (meth) acrylate, poly (meth) Acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester, propylene oxide phthalate anhydride (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, Oligomers such as rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di Ricidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate or the like can be used. These can be used alone or in combination.

By selecting and combining these (II) polyfunctional monomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, a compound having 3 or more, more preferably 5 or more functional groups in the molecule is desirable.
The addition amount of these (II) polyfunctional monomers is not particularly limited, but is 30 to 70% by mass with respect to the total amount of (I) alkali-soluble resin and (II) polyfunctional monomer. preferable.

  The (III) photopolymerization initiator in the present invention is not particularly limited, and is a benzophenone compound, an acetophenone compound, an oxanthone compound, an imidazole compound, a benzothiazole compound, a benzoxazole compound, a triazine compound, or a phosphorus compound. Or well-known things, such as inorganic type photoinitiators, such as titanate, can be used. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethyla Nthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole Examples include dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine. Further, it is preferable to add a sensitizing aid such as an aromatic or aliphatic tertiary amine because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types.

  The amount of (III) photopolymerization initiator added is not particularly limited, but is preferably 1 to 30% by mass with respect to the total amount of (I) alkali-soluble resin and (II) polyfunctional monomer. More preferably, it is 2-15 mass%. The sensitivity increases as the addition amount of the photopolymerization initiator increases. However, when the amount exceeds 30% by mass, the pattern size tends to be too large with respect to the mask size, which is not preferable. On the other hand, if it is less than 1% by mass, it is not preferable because it may be dissolved during development due to insufficient curing.

  In the present invention, by containing (IV) a blocked isocyanate, a radiation-sensitive composition for forming a spacer of a liquid crystal display device that is particularly flexible and capable of following the thermal expansion and contraction of liquid crystals and hardly undergoes plastic deformation is obtained. be able to.

  The (IV) blocked isocyanate in the present invention is a compound that is stable at room temperature, obtained by reacting a compound having a certain type of active hydrogen (blocking agent) with a compound having at least one isocyanate group. Although it does not necessarily limit, in order to improve a crosslinking density, the compound which has two or more isocyanate groups is preferable. As the compound having active hydrogen, a blocked isocyanate resin in which an isocyanate group is blocked with phenols such as phenol, cresol, methyl ethyl ketoxime, and ε-caprolactam, ketoximes, and lactams can be suitably used. As this compound, “Duranate” MFB-60X, MFK-60X, and 17B-60PX manufactured by Asahi Kasei Corporation are commercially available.

  As the (IV) blocked isocyanate in the present invention, a compound represented by the following general formula (1) is particularly preferred from the viewpoint of difficulty in generating display unevenness due to local load.

[Wherein, R ₁ , R ₂ and R ₃ each independently represents an alkylene group, a substituted alkylene group, an alkylene oxide group, an arylene group or a substituted arylene group, and R ₄ , R ₅ and R ₆ are each independently And a residue obtained when a compound having an isocyanate and active hydrogen reacts. ]
The aforementioned “Duranate” MFB-60X and MFK-60X are compounds that can be represented by the general formula (1).

  The amount of (IV) blocked isocyanate used in the present invention is preferably 5 to 80% by mass, preferably 10 to 70% by mass, based on the total amount of (I) alkali-soluble resin and (II) polyfunctional monomer. %, More preferably 15 to 50% by mass. If the amount used is less than 5% by mass, the effect of increasing the flexibility is insufficient and problems such as gravity unevenness and low-temperature foaming are likely to occur. Also, since plastic deformation is likely to occur, display unevenness due to local load is likely to occur. It becomes easy to generate. On the other hand, if it exceeds 80% by mass, the radiation-sensitive component decreases, and patterning with high accuracy becomes impossible.

  The solvent (V) in the present invention is not particularly limited, and ethylene glycol or propylene glycol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, propylene glycol monoethyl ether, or propylene glycol monoethyl ether acetate. , Aliphatic esters such as ethyl acetoacetate, methyl-3-methoxypropionate, 3-methyl-3-methoxybutylacetate, or aliphatic alcohols such as ethanol, 3-methyl-3-methoxybutanol, cyclo Ketones such as pentanone and cyclohexanone, polar amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, β-propiolactone, γ-buty Lactones, .gamma.-valerolactone, .delta.-valerolactone, .gamma.-caprolactone, may be used lactones such as ε- caprolactone. These (V) solvents can be used alone, or two or more kinds of solvents can be appropriately mixed and used.

  Next, a method for producing a substrate for a liquid crystal display device having a spacer formed using the radiation-sensitive composition for forming a spacer in the present invention will be described.

  The substrate for a liquid crystal display device forming the spacer in the present invention is not limited to a color filter substrate manufactured using a transparent substrate such as glass or a polymer film, and may be a drive element side substrate. Here, although an example of the spacer formation method on each board | substrate is given, it is not specifically limited.

  First, a method for forming a spacer on the color filter substrate will be described. The pattern shape of the color filter includes a stripe shape and an island shape, but is not particularly limited. A method for forming a pixel includes a photolithography method, a printing method, an electrodeposition method, and the like, but is not particularly limited. Here, an example of the photolithography method will be described. First, a black matrix is formed in a lattice pattern on a transparent substrate, and red, green, and blue pixels are formed in openings between the lattices. Thereafter, an overcoat is formed as necessary, and a transparent electrode is formed as necessary. Then, the radiation-sensitive composition for spacer formation is applied, dried, exposed, and developed with an alkaline solution for patterning. At this time, the spacer is preferably formed at the non-display portion, that is, above the black matrix.

  Next, a method for forming a spacer on the drive element side substrate will be described. For the spacer formation on the drive substrate side, a colored layer is formed on the surface of the drive substrate, a spacer is formed above the formed black matrix, and a position facing the black matrix formed on the color filter to be bonded. There is a method of forming a spacer on the drive base corresponding to this, but there is no particular limitation. In either method, first, a driving unit such as a thin film transistor is manufactured, and then, depending on the method, red, green, and blue pixels are formed in the black matrix and openings between the lattices. And an overcoat is formed into a film as needed, and also a transparent electrode is formed as needed. Then, the radiation-sensitive composition for spacer formation is applied, dried, exposed, and developed with an alkaline solution for patterning.

(Evaluation methods)
A. The weight average molecular weight column was measured in terms of polystyrene using Shodex KF-804L, 803, 802 (manufactured by Showa Denko KK) and NMP as a solvent.

B. Acid value 15 ml of isopropyl alcohol and 5 ml of toluene were added to 0.5 to 1 g of the polymer solution and stirred to dissolve uniformly, and 1 ml of 0.1 w / v% phenolphthalein ethanol solution was added as an indicator solution. Mole / l KOH aqueous solution was used as a titrant and the solution was dropped using a dropping burette, and the acid value of the solution was measured. Further, 1 g of the polymer solution was dissolved in 4 g of propylene glycol monoethyl ether, and the residual amount when dried at 180 ° C. for 40 minutes was defined as the solid content, and the acid value of the polymer was calculated.

C. Gravity unevenness After the backlight was turned on for 24 hours in the produced liquid crystal display device, the display unevenness was visually evaluated. The ones that showed no unevenness were excellent, the ones that look weak depending on the measurement angle were good, the ones that look weak regardless of the measurement angle were acceptable, and the ones that showed strong unevenness were impossible.

D. Low temperature foaming The above liquid crystal display device was left in a thermostatic layer at -30 ° C for 3, 6, 12 hours and then taken out, and the presence or absence of generation of bubbles was visually evaluated. Excellent if no bubbles are visible after standing for 12 hours, good if bubbles are slightly visible when left for 12 hours, acceptable if bubbles are slightly visible if left for 6 hours Those in which the generation of bubbles when allowed to stand for 3 hours were disabled.

E. Local load tolerance A 10 mmφ metal rod was placed vertically on the manufactured liquid crystal display device, a load of 49.0 N was applied from the top for 15 minutes, and after removing the metal rod, visual evaluation of display unevenness after 5 minutes. Was performed five times at different measurement locations. The case where the unevenness was not visible at all 5 times was excellent, the case where it was weak even once, the case where the unevenness was weak 4 times or more was allowed, and the case where the strong unevenness was visible even once was made impossible.

  The following examples illustrate the present invention more specifically.

  As an example, an example in which an overcoat is formed on a color filter and a spacer is formed in a non-display area above the black matrix is shown, but the method for forming the spacer is not particularly limited. Spacers may be formed in the display area.

(Examples 1-12, Comparative Examples 1-3)
(1) Preparation of alkali-soluble resin solution 1 33 parts by weight of methyl methacrylate, 33 parts by weight of styrene, 34 parts by weight of methacrylic acid, and 3 parts by weight of 2,2′-azobis (2-methylbutyronitrile) And γ-butyrolactone was charged in a 150 weight part polymerization vessel, stirred at 90 ° C. for 2 hours, further raised in liquid temperature to 100 ° C., and allowed to react for 1 hour. Next, 33 parts by weight of glycidyl methacrylate, 1.2 parts by weight of dimethylbenzylamine, and 0.2 parts by weight of p-methoxyphenol were added to the resulting solution and stirred at 90 ° C. for 4 hours. 50 g of γ-BL was added to obtain an alkali-soluble resin solution 1 (solid content: 40% by mass). The acid value of the obtained alkali-soluble resin 1 was 80.0 (mgKOH / g), and the weight average molecular weight (Mw) was 22000.

(2) Preparation of alkali-soluble resin solution 2 23 parts by weight of methyl methacrylate, 33 parts by weight of styrene, 34 parts by weight of methacrylic acid, 10 parts by weight of methacrylic acid-2-hydroxyethyl, and γ-butyrolactone It was synthesized by the same method as the alkali-soluble resin solution 1 except that it was charged in a 150 weight part polymerization vessel.

  The obtained alkali-soluble resin 2 had a solid content of 40% by mass, an acid value of 78.8 (mgKOH / g), and a weight average molecular weight (Mw) of 23,000.

(3) Preparation of alkali-soluble resin solution 3 23 parts by weight of methyl methacrylate, 33 parts by weight of benzyl methacrylate, 34 parts by weight of methacrylic acid, 10 parts by weight of 2-hydroxyethyl methacrylate, and γ- The synthesis was performed in the same manner as in the alkali-soluble resin solution 1 except that 150 parts by weight of butyrolactone was charged in a polymerization vessel.
The obtained alkali-soluble resin 3 had a solid content of 40% by mass, an acid value of 83.2 (mgKOH / g), and a weight average molecular weight (Mw) of 25,000.

(4) Preparation of Radiation Sensitive Composition 1 The following amounts of each material were stirred and mixed at room temperature to obtain radiation sensitive composition 1.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate 17B-60PX (60 wt%)): 8 parts by weight 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 52 parts by weight (5) Preparation of radiation-sensitive composition 2 -It mixed and the radiation sensitive composition 2 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 1 part by weight 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 59 parts by weight (6) Preparation of radiation-sensitive composition 3 -It mixed and the radiation sensitive composition 3 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 2 parts by weight 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 58 parts by weight (7) Preparation of radiation-sensitive composition 4 -It mixed and the radiation sensitive composition 4 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 4 parts by weight 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 56 parts by weight (8) Preparation of radiation-sensitive composition 5 The following amounts of each material were stirred at room temperature. -It mixed and the radiation sensitive composition 5 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 8 parts by weight 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 52 parts by weight (9) Preparation of radiation-sensitive composition 6 The following amounts of each material were stirred at room temperature. -It mixed and the radiation sensitive composition 6 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 12 parts by weight 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 48 parts by weight (10) Preparation of radiation-sensitive composition 7 -It mixed and the radiation sensitive composition 7 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 16 parts by weight 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 44 parts by weight (11) Preparation of radiation-sensitive composition 8 The following amounts of each material were stirred at room temperature. -It mixed and the radiation sensitive composition 8 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 20 parts by weight 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 40 parts by weight (12) Preparation of radiation-sensitive composition 9 The following amounts of each material were stirred at room temperature. -It mixed and the radiation sensitive composition 9 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 22.5 parts by weight Dipentaerythritol pentaacrylate: 6 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 18 parts by weight 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone: 1.5 parts by weight Propylene glycol monoethyl ether: 52 parts by weight (13) Preparation of radiation sensitive composition 10 Were stirred and mixed at room temperature to obtain a radiation-sensitive composition 10.
Alkali-soluble resin solution 1 (solid content 40%): 22.5 parts by weight Dipentaerythritol pentaacrylate: 6 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 21 parts by weight 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone: 1.5 parts by weight Propylene glycol monoethyl ether: 49 parts by weight (14) Preparation of radiation sensitive composition 11 Were stirred and mixed at room temperature to obtain a radiation sensitive composition 11.
Alkali-soluble resin solution 2 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 8 parts by weight 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 52 parts by weight (15) Preparation of radiation-sensitive composition 12 -It mixed and the radiation sensitive composition 12 was obtained.
Alkali-soluble resin solution 3 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight Block isocyanate (manufactured by Asahi Kasei Corporation, Duranate MF-B60X (60 wt%)): 8 parts by weight 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 52 parts by weight (16) Preparation of radiation-sensitive composition 13 The following amounts of each material were stirred at room temperature. -It mixed and the radiation sensitive composition 13 was obtained.
Alkali-soluble resin solution 1 (solid content 40%): 30 parts by weight dipentaerythritol pentaacrylate: 8 parts by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight propylene Glycol monoethyl ether: 60 parts by weight (17) Preparation of radiation-sensitive composition 14 The following amounts of each material were stirred and mixed at room temperature to obtain radiation-sensitive composition 14.
Alkali-soluble resin solution 2 (solid content 40%): 30 parts by weight Dipentaerythritol pentaacrylate: 8 parts by weight 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight Propylene glycol monoethyl ether: 60 parts by weight (18) Preparation of radiation-sensitive composition 15 The following amounts of each material were stirred and mixed at room temperature to obtain radiation-sensitive composition 15.
Alkali-soluble resin solution 3 (solid content 40%): 30 parts by weight dipentaerythritol pentaacrylate: 8 parts by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone: 2 parts by weight (19) Preparation of polyamic acid solution (PAA) 95.1 g of 4,4′-diaminodiphenyl ether and 6.2 g of bis (3-aminopropyl) tetramethyldisiloxane were added to 525 g of γ-butyrolactone and 220 g of N-methyl-2-pyrrolidone. In addition, 144.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 70 ° C. for 3 hours, then 3.0 g of phthalic anhydride was added, and 70 ° C. was further added. For 2 hours to obtain a 25% by weight polyamic acid solution (PAA).

(20) Preparation of polymer dispersant (PD) 161.3 g of 4,4′-diaminobenzanilide, 176.7 g of 3,3′-diaminodiphenylsulfone, and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane Was added together with 2667 g of γ-butyrolactone and 527 g of N-methyl-2-pyrrolidone, 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 70 ° C. for 3 hours. Then, 2.2 g of phthalic anhydride was added, and the mixture was further reacted at 70 ° C. for 2 hours to obtain a polymer dispersant (PD) which was a 20 wt% polyamic acid solution.

(21) Preparation of non-photosensitive black paste 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane Methyl-2-pyrrolidone was reacted as a solvent to obtain a polyimide precursor (polyamic acid) solution.
4.6 g of carbon black “MA100” manufactured by Mitsubishi Kasei Co., Ltd., 24 g of polyimide precursor solution and 61.4 g of N-methylpyrrolidone were dispersed using a homogenizer at 7000 rpm for 30 minutes, and the glass beads were filtered to be non-photosensitive. A black paste was prepared.

(22) Preparation of adjusted dispersion of non-photosensitive color paste 2.88 g of pigment red PR254 (60 wt% of the total pigment, of which) 1.92 g (40 wt%) of pigment red PR177 and 2.67 g of the above polymer dispersant, 81.4 g of γ-butyrolactone was charged together with 90 g of glass beads and dispersed at 7000 rpm for 5 hours using a homogenizer, and then the glass beads were filtered and removed. In this way, a 6% dispersion of pigment PR254 and PR177 was obtained.
A solution obtained by diluting 13.34 g of the above polymer solution with 22.82 g of γ-butyrolactone and 18.80 g of 3-methoxy-3-methyl-1-butanol was added to and mixed with 44.45 g of the dispersion liquid of color paste, and then Bicchemie Surfactant “BYK361” manufactured was added to a solid content of 1000 ppm to obtain a red paste. The pigment / polymer ratio (weight ratio) of this paste is 40/60.
Similarly to the red paste, a green paste having a pigment weight composition of PG7 / PY17 = 65/35 and a pigment / polymer ratio (weight ratio) = 46/54, PB15: 6 / PV23 = 80/20, pigment A blue paste having a polymer ratio (weight ratio) of 28/72 was prepared.
(23) Production of color filter (Production of colored coating film)
First, a black color paste in which carbon black is dispersed in a polyamic acid resin is applied, dried at 120 ° C. for 20 minutes, and a positive photoresist (“OFPR-800” manufactured by Tokyo Ohka Co., Ltd.) is applied thereon. It was applied and dried at 90 ° C. for 10 minutes. Using a UV exposure machine “PLA-501F” manufactured by Canon Inc., exposure was performed at 60 mJ / cm ² (UV intensity of 365 nm) through a chromium photomask. After the exposure, the film was immersed in a developer composed of a 2.25% aqueous solution of tetramethylammonium hydroxide, and development of the photoresist and etching of the colored coating film of the polyimide precursor were simultaneously performed. The photoresist layer that became unnecessary after etching was stripped with acetone. Furthermore, the colored coating film of the polyimide precursor was heat-treated at 240 ° C. for 30 minutes to convert to polyimide. A black matrix pattern was formed as described above. Next, a green paste produced by a spinner was applied, and a green pattern was formed by etching and heat treatment in the same manner as the black matrix pattern. Subsequently, a red paste and a blue paste were applied in the same manner, and a red pattern and a blue pattern were formed by etching and heat treatment to obtain a color filter. The film thicknesses of the red, green, and blue patterns were all 3.5 μm. Further, an overcoat agent “Optomer” (SS6917 + SS0917) manufactured by JSR Corporation was laminated on the obtained color filter by 1 μm.
(24) Formation of columnar spacer Next, the above-mentioned radiation sensitive compositions 1-15 were applied with a spinner, the coating film was dried in an oven at 90 ° C. for 10 minutes, using an ultraviolet exposure machine, through a photomask, The exposure was performed at 120 mJ / cm ² (ultraviolet intensity of 365 nm). Development was performed with a 0.05 wt% potassium hydroxide aqueous solution, and the substrate was heat-treated at 220 ° C. for 10 minutes to form a columnar spacer having a height of 3 μm in a non-display area above the black matrix. Tables 1 and 2 show the radiation-sensitive compositions for spacers used in Examples and Comparative Examples.

(25) Production and evaluation of liquid crystal display device Next, a sealant is applied to the periphery of the color filter substrate, a predetermined amount of liquid crystal is dropped inside the seal with a dispenser, filled with liquid crystal, and then driven in a vacuum. Bonded to the side substrate. Tables 1 and 2 show the results of evaluation of gravity unevenness, low-temperature foaming, and local load resistance of the obtained liquid crystal display device. All the liquid crystal display devices of Examples 1 to 12 were excellent in gravity unevenness, low-temperature foaming, and local load resistance, but the liquid crystal display devices of Comparative Examples 1 to 3 were inferior in any of gravity unevenness, low-temperature foaming, and local load resistance. It was a thing.

Claims (5)

Radiation sensitivity for forming a spacer in a liquid crystal display device comprising (I) an alkali-soluble resin, (II) a polyfunctional monomer, (III) a photopolymerization initiator, (IV) a blocked isocyanate, and (V) a solvent. Composition. The radiation-sensitive composition for forming a spacer of a liquid crystal display device according to claim 1, wherein the (IV) blocked isocyanate has a structure represented by the following general formula (1).

[Wherein, R ₁ , R ₂ and R ₃ each independently represents an alkylene group, a substituted alkylene group, an alkylene oxide group, an arylene group or a substituted arylene group, and R ₄ , R ₅ and R ₆ are each independently And a residue obtained when a compound having an isocyanate and active hydrogen reacts. ] The content of the (IV) blocked isocyanate is 5 to 80% by mass based on the total amount of (I) the alkali-soluble resin and (II) the polyfunctional monomer. A radiation-sensitive composition for forming a spacer of a liquid crystal display device. A step of forming a plurality of columnar spacers in a non-display portion by applying the radiation-sensitive composition for forming a spacer according to any one of claims 1 to 3 on a substrate, drying, exposing, and developing. A method for manufacturing a substrate for a liquid crystal display device. A substrate for a liquid crystal display device manufactured using the manufacturing method according to claim 4.