CN106681104B - Photosensitive resin composition and method for producing same, light shielding film and method for producing same, and liquid crystal display device and method for producing same - Google Patents

Photosensitive resin composition and method for producing same, light shielding film and method for producing same, and liquid crystal display device and method for producing same Download PDF

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Publication number
CN106681104B
CN106681104B CN201610892249.7A CN201610892249A CN106681104B CN 106681104 B CN106681104 B CN 106681104B CN 201610892249 A CN201610892249 A CN 201610892249A CN 106681104 B CN106681104 B CN 106681104B
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light
component
photosensitive resin
resin composition
shielding
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CN106681104A (en
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小野悠树
滑川崇平
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties

Abstract

The invention provides a photosensitive resin composition and a manufacturing method thereof, a shading film and a manufacturing method thereof, a liquid crystal display device and a manufacturing method thereof, which not only maintain shading performance and insulating performance, but also have excellent spacer characteristics such as elastic modulus, deformation, elastic recovery rate and the like, and can obtain fine and good spacer shapes. The photosensitive resin composition of the present invention contains the following components as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin which is a urethane compound obtained by reacting (a) a polyol compound having an ethylenically unsaturated bond in the molecule, (b) a diol compound having a carboxyl group in the molecule, and (c) a diisocyanate compound; (B) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials; and (E) a solvent.

Description

Photosensitive resin composition and method for producing same, light shielding film and method for producing same, and liquid crystal display device and method for producing same
Technical Field
The present invention relates to a photosensitive resin composition for a light-shielding film having a spacer function and a light-shielding film having a spacer function obtained by curing the photosensitive resin composition, and more particularly, to a photosensitive resin composition for forming a black column spacer having both a spacer function and a black matrix function in a liquid crystal display device by photolithography and a cured film thereof. The present invention further relates to a liquid crystal display device using the black column spacer obtained by the hardening. The invention further relates to a method for manufacturing the photosensitive resin composition, the light shielding film and the liquid crystal display device.
Background
In recent years, color Liquid Crystal Display devices (LCDs) have been used in all fields of Liquid Crystal televisions, Liquid Crystal monitors, color Liquid Crystal mobile phones, and the like. Among them, in order to improve the performance of LCDs, improvement is actively performed for the purpose of improving characteristics such as a viewing angle, a contrast ratio, and a response speed, and various panel structures are also being developed in Thin Film Transistor (TFT) -LCDs, which are currently used in large quantities. Regarding the TFT-LCD, the following methods are mainly employed: manufacturing an array substrate and a color filter substrate on which conventional TFTs are formed, respectively, and bonding the two substrates while maintaining a fixed interval by a spacer; however, LCD manufacturing processes are also being developed for the purpose of reducing costs and improving yields. For example, a process for manufacturing a bonded glass substrate has been developed as a substrate facing a TFT of an array substrate in which a color filter is directly formed. The structure formed in this manner is called a Color Filter On Thin Film Transistor (COT) or the like On a TFT. In the COT, various LCD panel structures such as a method of forming a black matrix, which is a boundary of each pixel of red (R), green (G), blue (B), etc., of a color filter layer formed on a TFT, before RGB formation, after RGB formation, or on a glass substrate facing each other, have been studied.
As for spacers that function to keep the thickness of the liquid crystal layer (the distance between the array substrate and the color filter substrate in the case of the conventional method) which is one of factors affecting the performance of the LCD constant, a method of sandwiching ball spacers having a constant particle diameter has been conventionally adopted. However, this method has a problem that the dispersion state of the ball spacers becomes uneven, and the light transmission amount per pixel becomes not constant. To address this problem, a method of forming a column spacer by photolithography is employed. However, the column spacer formed by photolithography is mostly transparent, and such column spacer has the following problems: light incident from an oblique direction affects the electrical characteristics of the TFT, and deteriorates the display quality. In order to solve such a problem, an LCD panel structure using a light-shielding column spacer, which is a light-shielding film having a spacer function formed by photolithography, has been proposed (patent document 1). In COT, a method of forming a so-called Black Column Spacer (BCS) in which a Column Spacer is formed using the same material as that of the Black matrix is also studied (for example, patent document 2).
The light-shielding column spacer needs to have a film thickness of about 2 μm to 7 μm in order to function as a spacer. In addition, it is necessary to form the light-shielding column spacer having a different height at the same time at the position where the TFT is formed and at other positions. Further, the light-shielding column spacer is required to have an appropriate range of elastic modulus, deformation amount, elastic recovery rate, and the like, which function as the spacer (patent document 3). Further, it is also required for the light-shielding column spacer to improve reduction of a hardening component caused by addition of a light-shielding component (colorant) to the spacer, and deterioration of electrical characteristics caused by influence of impurities in the colorant, and the like (patent document 4).
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. Hei 08-234212
[ patent document 2] U.S. patent application publication No. 2009/0303407 specification
[ patent document 3] Japanese patent laid-open No. 2009-031778
[ patent document 4] International publication No. 2013/062011
Disclosure of Invention
[ problems to be solved by the invention ]
Patent document 4 uses a mixed color organic pigment, but does not show the optical density of the light-shielding column spacer. The mixed color organic pigment is effective for lowering the dielectric constant as compared with an inorganic pigment such as carbon black, but is often low in light-shielding property. Further, since the spacers must be formed at the same time and have different heights, the light-shielding column spacer is further required to have mechanical properties such as elastic modulus, deformation amount, and elastic recovery rate. Since the shape and mechanical properties of the spacer are greatly affected by the light-shielding component, it is difficult to design the photosensitive resin composition for the light-shielding film. Therefore, the shape and mechanical properties of the spacer using carbon black, mixed color organic pigments, or the like are still not sufficiently satisfactory, and further improvement is required.
As described above, the light-shielding column spacer is manufactured to have a film thickness of about 2 μm to 7 μm. With the recent miniaturization of liquid crystal display devices, it is desired that light-shielding column spacers be formed into a fine spacer shape even when the film thickness is about 2 μm to 7 μm.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition for a light-shielding film having a spacer function, which has high light-shielding properties and insulation properties, and further has excellent elastic modulus, deformation amount, and elastic recovery rate, a light-shielding film having a spacer function formed using the photosensitive resin composition, and a liquid crystal display device having the light-shielding film as a constituent element.
[ means for solving problems ]
The present inventors have conducted studies to solve the above-mentioned problems of the photosensitive resin composition for a light-shielding film, and as a result, have found that a specific colorant is suitable for a light-shielding component of the intended photosensitive resin composition for a light-shielding film, thereby completing the present invention.
(1) The present invention is a photosensitive resin composition for a light-shielding film having a spacer function, characterized by comprising the following components (A) to (E) as essential components: (A) a polymerizable unsaturated group-containing alkali-soluble resin which is a urethane compound obtained by reacting (a) a polyol compound having an ethylenically unsaturated bond in the molecule, (b) a diol compound having a carboxyl group in the molecule, and (c) a diisocyanate compound; (B) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a light-shielding component selected from at least one of the group consisting of black organic pigments, mixed color organic pigments and light-shielding materials; and (E) a solvent.
(2) The present invention also provides the photosensitive resin composition according to (1), which contains titanium black as the light-shielding component (D).
(3) The present invention also provides the photosensitive resin composition according to (2), wherein the titanium black has an average secondary particle size of 100nm to 300 nm.
(4) The present invention also provides the photosensitive resin composition according to any one of (1) to (3), which comprises a black organic pigment and/or a mixed color organic pigment as the light-shielding component (D), wherein the black organic pigment and/or the mixed color organic pigment has an average secondary particle diameter of 20nm to 500 nm.
(5) The present invention is the photosensitive resin composition according to any one of (1) to (4), wherein the component (B) is contained in an amount of 5 to 400 parts by mass per 100 parts by mass of the component (a), the component (C) is contained in an amount of 0.1 to 30 parts by mass per 100 parts by mass of the total amount of the component (a) and the component (B), and the component (D) is contained in an amount of 5 to 80% by mass in the solid content, when the component other than the component (E) containing the component (B) which becomes the solid content after photo-curing is used as the solid content.
(6) The present invention also provides the photosensitive resin composition according to any one of (1) to (5), wherein the light-shielding film is formed by: the optical density OD is 0.5/mum to 3/mum, and the volume resistivity is 1 x 10 when a voltage of 10V is applied9Omega cm or more, and a dielectric constant of 2 to 10.
(7) The present invention is the photosensitive resin composition according to any one of (1) to (6), which is capable of forming a light-shielding film satisfying at least one of the following conditions (i) to (iii) in a load-unload test using a microhardness tester,
(i) breaking strength of 200mN or more;
(ii) the elastic recovery rate is more than 30%;
(iii) the compression ratio is 40% or less.
(8) The present invention also provides a light-shielding film having a spacer function, which is formed by curing the photosensitive resin composition according to any one of (1) to (7).
(9) In addition, the present invention is a liquid crystal display device comprising the light-shielding film as described in (8) as a Black Column Spacer (BCS).
(10) The present invention is the liquid crystal display device according to (9), further comprising a Thin Film Transistor (TFT).
(11) The present invention also provides a method for producing a photosensitive resin composition for a light-shielding film having a spacer function, comprising preparing a dispersion in which (D) a light-shielding component is dispersed in (E) a solvent, and then adding and mixing (a) an alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond, (C) a photopolymerization initiator, and (E) a solvent; the alkali-soluble resin (A) is a urethane compound obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound (b) having a carboxyl group in the molecule, and a diisocyanate compound (c), and the light-shielding component (D) is one or more components selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material.
(12) Further, the present invention is the method according to (11), wherein the (D) light-screening component comprises titanium black.
(13) The present invention is the method according to (12), wherein the average secondary particle size of the titanium black in the dispersion is 100nm to 300 nm.
(14) The present invention is the method according to any one of (11) to (13), wherein the light-shielding component (D) contains a black organic pigment and/or a mixed color organic pigment, and the average secondary particle diameter of the black organic pigment and/or the mixed color organic pigment in the dispersion is 20nm to 500 nm.
(15) The present invention is also a method for producing a light-shielding film formed on a substrate, comprising applying the photosensitive resin composition according to any one of (1) to (7) to a substrate, and curing the photosensitive resin composition by light irradiation.
(16) The present invention is the method for producing a light-shielding film according to (15), wherein a light-shielding film having a film thickness H1 for setting an optical density of the light-shielding film to 0.5/μm or more and less than 3/μm and a film thickness H2 of the light-shielding film functioning as a spacer is formed so that the film thickness H1 and the film thickness H2 are 0.1 to 2.9 in terms of Δ H ═ H2-H1, when H2 is 2 μm to 7 μm.
(17) Further, the present invention is a method for manufacturing a liquid crystal display device, wherein the light-shielding film manufactured by the method described in (16) is used as a black column spacer.
(18) Further, the present invention is the production method as described in (17), wherein the liquid crystal display device includes a Thin Film Transistor (TFT).
[ Effect of the invention ]
The photosensitive resin composition for a light-shielding film of the present invention contains a specific colorant, and therefore, compared with conventional photosensitive resin compositions, a cured product having excellent elastic modulus, deformation amount, and elastic recovery can be obtained while maintaining light-shielding properties and insulating properties. Further, the photosensitive resin composition for a light-shielding film of the present invention can form a fine spacer shape even if the film thickness is about 2 μm to 7 μm.
Detailed Description
The present invention will be described in detail below.
(A) The alkali-soluble resin containing a polymerizable unsaturated group as the component (a) is a urethane compound obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound (b) having a carboxyl group in the molecule, and a diisocyanate compound (c).
Examples of the polyol compound (a) having an ethylenically unsaturated bond in the molecule used for producing the component (a) include: an epoxy acrylate compound which is a reactant of an epoxy compound having 2 or more alcoholic hydroxyl groups and 2 or more epoxy groups in the molecule and (meth) acrylic acid (which is defined as "acrylic acid and/or methacrylic acid"). Representative examples of the epoxy (meth) acrylate compound include compounds obtained by reacting (meth) acrylic acid with an epoxy compound represented by the general formula (I).
[ solution 1]
Figure BDA0001129824940000061
Wherein, in the general formula (I), R1、R2、R3And R4Independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and X represents-CO-, -SO2-、-C(CF3)2-、-Si(CH3)2-、-CH2-、-C(CH3)2-, -O-, or fluorene-9, 9-diyl or a single bond, and the average value of m is in the range of 0 to 10, preferably 0 to 4.
Bisphenols which provide epoxy compounds of the general formula (I) may be mentioned: bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxy-3, 5-dimethylphenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 4 '-biphenol, 3' -biphenol, and the like. These bisphenols may be used alone or in combination of two or more. Among them, bisphenols in which X in the general formula (I) is propane-2, 2-diyl can be preferably used.
The compound of the general formula (I) is an epoxy compound having (m +2) or more alcoholic hydroxyl groups and 2 glycidyl ether groups, which is obtained by reacting the above-mentioned bisphenol with epichlorohydrin. In this reaction, m is an integer of 0 to 10 in each molecule, and since a plurality of molecules are usually mixed, the average value is 0 to 10 (not limited to an integer), but the average value of m is preferably 0 to 4. If the average value of m exceeds the upper limit, when a photosensitive resin composition is formed using an alkali-soluble resin synthesized using the epoxy compound, the viscosity of the composition becomes too high, and coating cannot be smoothly performed, or alkali solubility cannot be sufficiently imparted, and alkali developability becomes very poor.
Examples of the epoxy compound used for producing the epoxy (meth) acrylate other than the compound of the general formula (I) include: the compound of the general formula (I) is a group of compounds in which a benzene ring is hydrogenated to a cyclohexane ring, or a group of epoxy compounds obtained by reacting a phenol compound having 2 or more phenolic hydroxyl groups in a molecule with epichlorohydrin.
Examples of the epoxy compound obtained by reacting a phenol compound having 2 or more phenolic hydroxyl groups in the molecule with epichlorohydrin include compounds of the general formula (II).
[ solution 2]
Figure BDA0001129824940000071
Wherein in the general formula (II), Y and Z represent a benzene skeleton, a naphthalene skeleton or a biphenyl skeleton, and G represents a glycidyl group. l represents 1 or 2, and n represents a number of 1 to 5 in average.
The epoxy equivalent of the epoxy compound used in the epoxy (meth) acrylate is preferably 100 to 500, and when the epoxy equivalent is less than 100, the molecular weight when the (a) polymerizable unsaturated group-containing alkali-soluble resin is formed is small, and film formation may become difficult, and the film may become brittle. When the epoxy equivalent exceeds 500, the content of the polymerizable unsaturated group per 1 molecule becomes small, and the sensitivity as a photosensitive resin cannot be sufficiently obtained.
The diol compound (b) having a carboxyl group in the molecule used for producing the component (a) is not particularly limited as long as it has 2 alcoholic hydroxyl groups and 1 or more carboxyl groups in the molecule, and dimethylolpropionic acid and dimethylolbutyric acid can be preferably used. Further, a reaction product of a trifunctional or higher polyhydric alcohol compound and a polybasic acid anhydride, and the like can be mentioned. These diol compounds having a carboxyl group may be used alone or in combination of two or more.
Next, the diisocyanate compound (c) used for producing the component (a) is not particularly limited as long as it has 2 isocyanate groups in the molecule, but in order to form a urethane compound excellent in flexibility and the like, it is preferable to use: benzene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, norbornane-dicyanate methyl ester, and the like, and among these compounds, isophorone diisocyanate or trimethylhexamethylene diisocyanate can be preferably used. These compounds may be used alone, or two or more compounds may be used simultaneously.
When the component (a) is a diol compound having an ethylenically unsaturated bond, the composition of each of the components (a), (b), and (c) in the production of the component (a) is preferably such that the molar ratio [ (a) + (b) ]/(c) is 1 to 5. When the molar ratio is less than 1, an isocyanate group remains at the terminal of the compound obtained by the reaction, and there is a concern of gelation, and therefore, it is not preferable, and when the molar ratio exceeds 5, the molecular weight of the obtained alkali-soluble resin containing a polymerizable unsaturated group becomes small, and there are problems that sensitivity cannot be sufficiently obtained when a photosensitive resin composition is formed, or stickiness occurs when a film is formed.
Further, the component (a) may be formed by replacing a part of the component (b) with a diol compound (d) having no ethylenically unsaturated bond or carboxyl group in the molecule. (d) Examples of the components include: aliphatic diol compounds such as (poly) ethylene glycol, (poly) propylene glycol, 1, 4-butanediol, and 1, 6-hexanediol, and alicyclic diols such as cyclohexane-1, 4-diol and cyclohexane-1, 4-dimethanol.
The reaction conditions for the component (A) are such that a predetermined amount of the components (a) and (b) and, if necessary, the component (d) are added to a solvent having no solvent or having no alcoholic hydroxyl group (for example, glycol ethers produced from ethylene glycol, esters such as propylene glycol monomethyl ether acetate and butyl cellosolve acetate), and the mixture is stirred in a reactor, and after the component (c) is slowly added, the reaction is carried out at a reaction temperature of 40 to 120 ℃ for a reaction time of about 5 to 60 hours, whereby an alkali-soluble resin having an ethylenically unsaturated bond as the component (A) is obtained.
For example, when the component (a) is an epoxy (meth) acrylate obtained by reacting an epoxy compound represented by the general formula (I) with (meth) acrylic acid, the basic skeleton of the obtained alkali-soluble resin having an ethylenically unsaturated bond can be represented by the general formulae (III) and (IV). The alkali-soluble resin obtained in this case is a resin in which the two structures are bonded substantially irregularly, and may contain a skeleton having a partially different structure.
[ solution 3]
Figure BDA0001129824940000081
Wherein, in the general formula (III), R5Independently represents a hydrogen atom or a methyl group, J represents a residue other than an epoxy group of an epoxy compound, L represents a residue other than an isocyanate group of a diisocyanate compound, and p represents a number of 10 to 100.
[ solution 4]
Figure BDA0001129824940000082
Wherein in the general formula (IV), L represents a residue except an isocyanate group of a diisocyanate compound, M represents a C1-5 tertiary alkyl group, and q represents a number of 10-100.
Further, the acid value of the component (a) can be adjusted by reacting the acid anhydride (e) with the terminal alcoholic hydroxyl group remaining in the ethylenically unsaturated group-containing alkali-soluble resin obtained in the reaction.
Examples of the acid anhydride (e) for adjusting the acid value include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrotrimellitic anhydride, hexahydrotrimellitic anhydride, and the like.
(A) The weight average molecular weight (Mw) of the alkali-soluble resin (2) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is usually 2000 to 50000, preferably 5000 to 20000. When the weight average molecular weight is less than 2000, the adhesiveness of the pattern during alkali development may decrease, and when the weight average molecular weight exceeds 50000, the developability may significantly decrease.
The acid value of the alkali-soluble resin (A) is preferably in the range of 80mgKOH/g to 120 mgKOH/g. If this value is less than 80mgKOH/g, residues tend to remain during alkali development, and if it exceeds 120mgKOH/g, the penetration of the alkali developing solution becomes too fast, causing peeling development, which is not preferable. In addition, only one kind of the alkali-soluble resin (a) containing a polymerizable unsaturated group may be used, or a mixture of two or more kinds may be used.
Then, (B) the photopolymerizable monomer having at least 1 ethylenically unsaturated bond may be exemplified by: (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxyhexyl (meth) acrylate, or ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, and mixtures thereof, Or (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyhydric alcohols such as pentaerythritol and dipentaerythritol, vinylbenzyl ether compounds of polyhydric phenols such as phenol novolak, and addition polymers of divinyl compounds such as divinylbenzene. These photopolymerizable monomers (B) having at least 1 ethylenically unsaturated bond may be used alone or in combination of two or more. The photopolymerizable monomer (B) having at least 1 ethylenically unsaturated bond does not have a free carboxyl group.
The blending ratio of the component (B) is preferably 5 to 400 parts by mass, more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the component (A). When the blending ratio of the component (B) is more than 400 parts by mass relative to 100 parts by mass of the component (A), a hardened product after photo-curing becomes brittle, and the solubility in an alkali developing solution is lowered due to a low acid value of a coating film in an unexposed portion, resulting in a problem that the edge of a pattern is jagged and unclear. On the other hand, if the blending ratio of the component (B) is less than 5 parts by mass with respect to 100 parts by mass of the component (a), the ratio of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and further, since the acid value of the resin component is high, the solubility of the exposed portion in an alkali developer is improved, and therefore, there is a concern that the following problems occur: the formed pattern becomes thinner than the target line width, or the pattern is easily peeled off.
Examples of the photopolymerization initiator of component (C) include: acetophenone compounds such as acetophenone, 2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoprophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylbenzone, benzophenone compounds such as benzophenone, 2-chlorobenzophenone and p, p' -bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, and biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbisimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole and 2, 4, 5-triarylbiimidazole, halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1, 3, 4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1, 3, 4-oxadiazole, 2, 4, 6-tris (trichloromethyl) -1, 3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1, halomethyl-s-triazine compounds such as 3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -, 2- (O-benzoyloxime), 1- (4-phenylmercaptophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylmercaptophenyl) butane-1, 2-dione-2-oxime-O-acetate, 1- (4-methylmercaptophenyl) butane-1-ketoxime-O-acetate, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] -, O-acetyloxime, methanone, (2-methylphenyl) (7-nitro-9, 9-dipropyl-9H-fluoren-2-yl) -, acetyloxime, ethanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl ] -, 1- (O-acetyloxime), ethanone, 1- (-9, 9-dibutyl-7-nitro-9H-fluoren-2-yl) -, o-acyloxime compounds such as 1-O-acetyloxime, sulfur compounds such as benzyldimethylketal, thioxanthone, 2-chlorothianthrone, 2, 4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, anthraquinones such as 2-ethylanthrone, octamethylanthrone, 1, 2-benzoanthraquinone and 2, 3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and the like. Among them, O-acyloxime compounds are preferably used from the viewpoint of easily obtaining a photosensitive resin composition for a light-shielding film with high sensitivity. These photopolymerization initiators (C) may be used alone or in combination of two or more. In the present invention, the photopolymerization initiator is used as meaning including a sensitizer.
These photopolymerization initiators and sensitizers may be used alone or in combination of two or more. Further, although it does not act as a photopolymerization initiator or a sensitizer by itself, a compound capable of increasing the ability of the photopolymerization initiator or the sensitizer may be added by combined use. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which are effective when used in combination with benzophenone.
The amount of the photopolymerization initiator of component (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass of the total of component (A) and component (B). When the blending ratio of the component (C) is less than 0.1 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the following problems may occur: the sensitivity is too strong, the pattern line width becomes coarse with respect to the pattern mask, and a faithful line width cannot be reproduced with respect to the mask, or the pattern edge is not sharp with jaggies.
(D) The component (B) is a light-shielding component selected from black organic pigments, mixed color organic pigments and light-shielding materials, and is preferably excellent in insulation properties, heat resistance, light resistance and solvent resistance. Examples of the black organic pigment include: perylene black (perylene black), aniline black (aniline black), cyanine black (cyanine black), lactam black (lactam black), and the like. The mixed color organic pigment may be one prepared by mixing two or more pigments selected from red, blue, green, violet, yellow, cyanine, magenta, and the like to simulate a black color. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, and titanium black. These (D) light-shielding components may be used alone or in combination of two or more.
The light-shielding material is preferably titanium black in terms of its good light-shielding properties, elastic modulus, deformation amount, and elastic recovery rate. In the case of using titanium black, a black organic pigment and/or a mixed color organic pigment may be used in combination for the purpose of further improving the insulation property. When the inorganic light-shielding material and the organic pigment are used together as described above, the blending ratio of [ light-shielding material/(black organic pigment and/or mixed color organic pigment) ] is preferably 90/10 to 10/90, more preferably 70/30 to 30/70 in terms of mass ratio. The light-shielding film having a spacer function and having desired characteristics such as light-shielding properties and insulating properties can be obtained by combining the light-shielding material and the organic pigment and blending the components at a ratio. For the purpose of controlling chromaticity of the light-shielding film in order to make the light-shielding film achromatic, an organic pigment other than black is not necessarily added as a single color for the purpose of making the color black by pseudo color mixing.
The titanium black used in the present invention is a titanium-containing black inorganic pigment represented by titanium suboxide, titanium oxynitride, or the like, and among these inorganic pigments, those exhibiting high insulating properties can be preferably used. The preparation method of the titanium black comprises the following steps: a method of heating a mixture of titanium dioxide and metallic titanium in a reducing gas atmosphere to reduce the mixture (Japanese patent laid-open No. 49-5432); a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in an atmosphere of a reducing gas containing hydrogen (Japanese patent laid-open No. Sho 57-205322); a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese patent laid-open publication Nos. Sho 60-65069 and Sho 61-201610); a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and the resultant is reduced at high temperature in the presence of ammonia (Japanese patent laid-open publication No. Sho 61-201610); but is not limited to these methods.
In addition, these titanium-containing black inorganic pigments may be obtained by coating the surface of inorganic particles with an organic compound or an inorganic compound. Examples of organic compounds for coating are: polyhydric alcohols, alkanolamines or derivatives thereof, organosilicon compounds (silicones, silane-based coupling agents, etc.), higher fatty acids or metal salts thereof, organometallic compounds (titanium-based coupling agents, aluminum-based coupling agents, etc.), and the like. On the other hand, examples of the inorganic compound used for coating include: aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, antimony compounds, and the like. As a method for coating the surface of the titanium-containing particles, the method described in Japanese patent laid-open No. 2006-206891 and the like can be used.
Examples of commercially available titanium black include: titanium blacks 12S, 13M-T and 13M-C, UF8 manufactured by Mitsubishi material, and tirak (tirak) D manufactured by gibberellin formation ("tirak D" is a registered trademark of the company).
The organic pigment used in the present invention may be any known compound without any particular limitation, and is preferably processed into fine particles and has a specific surface area of 50m by the Brunauer-Emmett-Teller (BET) method2(ii) more than g. Specific examples thereof include: azo (azo) pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, vat pigments, perylene pigments, perinone pigments, quinophthalone pigments, perylene pigments, and mixtures thereofKetone (quinophthalone) pigments, diketopyrrolopyrrole (diketopyrrolopyrrole) pigments, thioindigo (thioindigo) pigments and the like, and specific examples thereof include those named by the color index (c.i.) described below, but are not limited thereto.
C.i. pigment red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.;
c.i. pigment orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;
pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.;
c.i. pigment green 7, 36, 58, etc.;
c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, 80, etc.;
c.i. pigment violet 19, 23, 37, and the like.
Examples of the solvent for component (E) include: alcohols such as methanol, ethanol, N-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol, terpenes such as α -terpineol and β -terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, glycol ethers such as ethyl acetate, butyl acetate, ethyl lactate, and 3-methoxybutyl acetate, Esters such as 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; by dissolving and mixing these solvents, a composition in a uniform solution state can be formed. In order to have the required properties such as coatability, two or more of these solvents may be used.
Further, it is preferable that these light-shielding components are dispersed in a solvent together with the dispersant (F) in advance to form a light-shielding dispersion, and then the dispersion is formulated into a photosensitive resin composition for a light-shielding film. Since the solvent to be dispersed is a part of the component (E), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and the like can be suitably used as exemplified for the component (E). The blending ratio of the light-shielding component (D) for forming the light-shielding dispersion is preferably within a range of 5 to 80% by mass relative to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. The solid component is a component other than the component (E) in the composition. The solid component also includes a component (B) which becomes a solid component after photo-curing. If the amount is less than 5% by mass, the desired light-shielding property cannot be set. If the content exceeds 80 mass%, the content of the photosensitive resin which originally becomes the binder decreases, and therefore, there arises a problem that not only the developing property is impaired, but also the film forming ability is impaired.
The average particle diameter (hereinafter referred to as "average secondary particle diameter") of the light-shielding component in the light-shielding dispersion, which is measured by a laser diffraction/scattering particle diameter analyzer, is preferably as follows. The titanium black preferably has an average secondary particle diameter of 100 to 300nm when the titanium black is used, and the dispersed particles preferably have an average secondary particle diameter of 20 to 500nm when the black organic pigment and/or the mixed-color organic pigment and/or the monochromatic organic pigment are used. In the photosensitive resin composition for a light-shielding film prepared by blending these light-shielding dispersions, it is preferable that the light-shielding components have the same average secondary particle diameter.
In addition, in the light-shielding dispersion liquid, (F) a dispersant is used for stably dispersing the light-shielding component, but for this purpose, known dispersants such as various polymer dispersants can be used. Examples of the dispersant include, but are not limited to, known compounds (such as those sold under the names of dispersants, dispersion wetting agents, and dispersion accelerators) conventionally used for pigment dispersion, and include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersion aids), and the like. Particularly preferred is a cationic polymer-based dispersant which has a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amino group, a secondary amino group or a tertiary amino group as an adsorption site for a pigment, and has an amine value of 1mgKOH/g to 100mgKOH/g and a number average molecular weight of 1 thousand to 10 ten thousand. The amount of the dispersant to be blended is 1 to 30% by mass, preferably 2 to 25% by mass, based on the light-shielding component.
Further, when a photosensitive resin composition for a light-shielding film is formed by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of component (a) in addition to the dispersant in the preparation of the light-shielding dispersion, it is possible to form a photosensitive resin composition in which exposure sensitivity is easily maintained at a high sensitivity, adhesiveness at the time of development is good, and a problem of residue is difficult to occur. (A) The amount of the component (b) to be blended is preferably 2 to 20% by mass, more preferably 5 to 15% by mass, in the light-shielding dispersion. If the amount of the component (A) is less than 2% by mass, the effect of co-dispersion such as improvement in sensitivity, improvement in adhesion, and reduction in residue cannot be obtained. When the content is 20% by mass or more, the viscosity of the light-shielding dispersion is high particularly when the content of the light-shielding material is large, and uniform dispersion is difficult or requires a long time, and it becomes difficult to obtain a photosensitive resin composition for obtaining a coating film in which a light-shielding component is uniformly dispersed.
The light-shielding dispersion obtained in the above manner can be mixed with the component (a) (when the component (a) is co-dispersed in the preparation of the light-shielding dispersion, the remaining component (a), the component (B), the component (C), and the remaining component (E) to form the photosensitive resin composition for a light-shielding film.
In the photosensitive resin composition of the present invention, additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant may be blended as necessary. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone (hydroquinone), hydroquinone monomethyl ether (hydroquinone), pyrogallol (pyrogallol), tert-butyl catechol (tert-butyl alcohol), phenothiazine (phenothiazine), hindered phenol (hindered phenol) compounds, and the like, and plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like, and the filler includes: glass fiber, silica, mica, alumina, etc., and the defoaming agent or leveling agent may be exemplified by: silicone, fluorine, and acrylic compounds. In addition, the surfactants may be exemplified by: fluorine-based surfactants, silicone-based surfactants, and the like, and examples of the coupling agent include: silane coupling agents such as 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.
The photosensitive resin composition of the present invention may be used in combination with another resin component which is polymerized or cured by heat. The other resin component is preferably (G) an epoxy resin or epoxy compound having 2 or more epoxy groups, and examples thereof include: 3, 3 ', 5, 5 ' -tetramethyl-4, 4 ' -biphenol-type epoxy resin, bisphenol a-type epoxy resin, bisphenol fluorene-type epoxy resin, phenol novolac-type epoxy resin, 3, 4-epoxycyclohexenylmethyl-3, 4-epoxycyclohexene carboxylate, 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, epoxy silicone resin, and the like. These additional components may be used alone or in combination of two or more.
The photosensitive resin composition of the present invention contains the components (A) to (E) as main components. The solid content preferably contains components (a) to (D) in a total amount of 70 mass%, preferably 80 mass% or more. (E) The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 60 to 90% by mass.
The photosensitive resin composition for a light-shielding film of the present invention is excellent as a photosensitive resin composition for forming a light-shielding film having a spacer function, for example. The light-shielding film having the spacer function is formed by photolithography as described below. The following methods may be mentioned: first, the photosensitive resin composition for a light-shielding film of the present invention is applied to a substrate, followed by solvent drying (prebaking), and then a photomask is placed on the film obtained in the above manner, and ultraviolet rays are irradiated to cure the exposed portion, and further, development is performed in which the unexposed portion is eluted using an aqueous alkali solution to form a pattern, and further, post-baking (thermal baking) is performed as post-drying.
The substrate may be a transparent substrate, or may be a substrate other than a transparent substrate such as an alignment film formed on a pixel, a planarization film on a pixel, or a planarization film on a pixel after forming pixels such as RGB. The light-shielding film having the spacer function is formed on any substrate, and is different depending on the design of the liquid crystal display device.
Examples of the transparent substrate on which the photosensitive resin composition is applied include a glass substrate and a transparent electrode formed by depositing or patterning Indium Tin Oxide (ITO) or gold on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like). The method of applying the solution of the photosensitive resin composition on the transparent substrate may be any method using a roll coater, a landed coater, a slit coater, a rotary coater, or the like, in addition to the known solution dipping method and spraying method. By these methods, after coating to a desired thickness, the solvent is removed (prebaking), whereby a coating film is formed. The prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent used, and are, for example, carried out at a temperature of 60 to 110 ℃ for 1 to 3 minutes.
The exposure after the prebaking is performed by an ultraviolet exposure apparatus, and only the resist in a portion corresponding to the pattern is exposed to light by exposure through a photomask. The photosensitive resin composition in the coating film is photo-cured by exposure using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp, with the exposure apparatus and the exposure irradiation conditions appropriately selected.
The alkali development after the exposure is performed for the purpose of removing the resist of the unexposed portion, and a desired pattern is formed by the development. The developer suitable for the alkali development includes, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, and the like, and particularly preferably a weakly alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate, and the development is performed at a temperature of 23 to 28 ℃.
After the development, it is preferable to perform a heat treatment (post-baking) at a temperature of 180 to 250 ℃ for 20 to 60 minutes. The post baking is performed for the purpose of improving adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate, or the like, as in the case of the prebaking. The patterned light-shielding film of the present invention is formed through the above-described steps of the photolithography method.
According to the method, a light-shielding film having an Optical Density (OD) of 0.5 to 3/μm, preferably 1.5 to 2.5/μm, can be formed. In addition, according to the method, the volume resistivity at the time of applying the voltage of 10V is formed to be 1 × 109Omega cm or more, preferably 1X 1012A light-shielding film of not less than Ω · cm. Further, according to the method, a light-shielding film having a dielectric constant of 2 to 10, preferably 2 to 8, and particularly preferably 3 to 6 can be formed. Further, according to the above method, a light-shielding film having a breaking strength of 200mN or more, an elastic recovery of 30% or more, and a compressibility of 40% or less can be formed in a mechanical property test. The light-shielding film formed by the method can be used as a column spacer of a liquid crystal display device, preferably as a black column spacer.
Further, according to the above method, the light-shielding film having the film thickness H1 for setting the optical density of the light-shielding film to 0.5/μm or more and less than 3/μm and the film thickness H2 of the light-shielding film functioning as a spacer can be formed simultaneously with the light-shielding film having the film thickness H1 and the film thickness H2, respectively, in which Δ H is 0.1 to 2.9 in H2-H1, when H2 is 2 to 7 μm. The cured film formed by the method can be used as a column spacer of a liquid crystal display device, preferably as a black column spacer. The cured film having Δ H in the above range allows the black column spacers having different heights to be formed at a time from the same material, and thus the liquid crystal display device can be manufactured more efficiently. In this case, for example, the cured film having the film thickness H2 may function as a spacer, and the cured film having the film thickness H1 may function as a black matrix. Further, Δ H is necessary because: when the film functioning as the black matrix is formed to have the same thickness as the film functioning as the spacer, the liquid crystal layer is divided into pixels, which may not only prevent the free flow of the liquid crystal layer but also reduce the yield of the liquid crystal display device when the liquid crystal layer is filled.
The liquid crystal display device including the light-shielding film or the cured film is preferably a TFT-LCD provided with a thin film transistor.
The liquid crystal display device including the light-shielding film or the cured film has high light-shielding properties and insulating properties, has a spacer function excellent in elastic modulus, deformation amount, and elastic recovery, and can be formed into a fine spacer shape even when the film thickness is about 2 to 7 μm.
[ examples ]
Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.
First, an example of synthesizing the polymerizable unsaturated group-containing alkali-soluble resin (a) of the present invention will be described. Evaluation of the resin in the synthesis example was performed in the following manner.
[ solid content concentration ]
1g of the resin solution obtained in synthesis example was immersed in a glass filter [ weight: w0(g)]In (1), carry outWeighing [ W ]1(g)]According to the weight [ W ] of the mixture after heating at 160 ℃ for 2hr2(g)]The calculation is made by the following equation.
The solid content concentration (wt%) was 100 × (W)2-W0)/(W1-W0)
[ acid value ]
The resin solution was dissolved in dioxane and titrated with 1/10N-KOH aqueous solution using a potentiometric titrator (product name COM-1600 manufactured by Hei Marsh industries, Ltd.).
[ molecular weight ]
Gel Permeation Chromatography (GPC) with the trade name HLC-8220GPC manufactured by eastern cao (thigh), solvent: tetrahydrofuran, column: TSKgelSuperH-2000(2 pieces) + TSKgelSuperH-3000(1 piece) + TSKgelSuperH-4000(1 piece) + TSKgelSuperH-H5000 (1 piece) [ manufactured by Tosoh ], temperature: 40 ℃, speed: 0.6ml/min, and the weight average molecular weight (Mw) was determined as a value converted from standard polystyrene [ PS-oligomer set manufactured by Tosoh (Strand).
[ measurement of average Secondary particle diameter ]
The average secondary particle size was measured by a particle size distribution meter (macchian (Microtrac) MT-3000, manufactured by japan ltd.) by a laser diffraction scattering method for a solution in which the light-shielding dispersion was diluted with a solvent (in this example, Propylene Glycol Monomethyl Ether Acetate (PGMEA)) to have a light-shielding component concentration of about 0.1 mass%.
[ Synthesis example 1]
In a 500mL four-necked flask equipped with a reflux condenser, 105.7g (0.29mol) of a bisphenol a type epoxy compound (product name YD-128, epoxy equivalent 182, manufactured by seiko epoxy manufacturing company), 41.8g (0.58mol) of acrylic acid, 1.52g of Triphenylphosphine (TPP), and 40.0g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were added, and the mixture was stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product.
Then, 16.9g (0.13mol) of dimethylolpropionic acid and 96g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 ℃. Then, 61.8g (0.28mol) of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 6.2g (0.04mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was stirred at 90 to 95 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -1. The resin solution thus obtained had a solid content of 63.2 wt%, an acid value (in terms of solid content) of 40mgKOH/g, and Mw according to GPC analysis was 11540.
[ Synthesis example 2]
In a 500mL four-necked flask equipped with a reflux condenser, 104.2g (0.29mol) of bisphenol a type epoxy compound (product name YD-128, epoxy equivalent 182, manufactured by seiki iron-au chemical corporation), 41.2g (0.57mol) of acrylic acid, 1.50g of TPP, and 40.0g of PGMEA were added, and the mixture was stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product.
Then, 23.1g (0.17mol) of dimethylolpropionic acid and 98g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 ℃. Then, 68.0g (0.31mol) of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours to obtain an alkali-soluble resin solution (A) -2 containing a polymerizable unsaturated group. The resin solution thus obtained had a solid content of 63.3 wt%, an acid value (in terms of solid content) of 41mgKOH/g, and Mw was 11210 by GPC analysis.
[ Synthesis example 3]
In a 500mL four-necked flask equipped with a reflux condenser, 104.2g (0.29mol) of bisphenol a type epoxy compound (product name YD-128, epoxy equivalent 182, manufactured by seiki iron-au chemical corporation), 41.2g (0.57mol) of acrylic acid, 1.50g of TPP, and 40.0g of PGMEA were added, and the mixture was stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product.
Then, 17.4g (0.13mol) of dimethylolpropionic acid and 84g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 ℃. Then, 61.8g (0.28mol) of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 21.0g (0.14mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was stirred at 90 to 95 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -3. The resin solution thus obtained had a solid content of 66.6 wt%, an acid value (in terms of solid content) of 61mgKOH/g, and Mw according to GPC analysis was 11860.
[ Synthesis example 4]
In a 500mL four-necked flask equipped with a reflux condenser, 105.7g (0.29mol) of bisphenol a type epoxy compound (product name YD-128, epoxy equivalent 182, manufactured by seiki iron-au chemical corporation), 41.8g (0.58mol) of acrylic acid, 1.52g of TPP, and 40.0g of PGMEA were added, and the mixture was stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product.
Then, 16.9g (0.13mol) of dimethylolpropionic acid and 96g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 ℃. Then, 58.5g (0.28mol) of trimethylhexamethylene diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 6.2g (0.04mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was stirred at 90 to 95 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -4. The resin solution thus obtained had a solid content of 62.9% by weight, an acid value (in terms of solid content) of 41mgKOH/g, and Mw according to GPC analysis was 11950.
[ Synthesis example 5]
In a 500mL four-necked flask equipped with a reflux condenser, 104.2g (0.29mol) of bisphenol a type epoxy compound (product name YD-128, epoxy equivalent 182, manufactured by seiki iron-au chemical corporation), 41.2g (0.57mol) of acrylic acid, 1.50g of TPP, and 40.0g of PGMEA were added, and the mixture was stirred at 100 to 105 ℃ for 12 hours to obtain a reaction product.
Subsequently, 4.0g (0.03mol) of dimethylolpropionic acid, 11.8g (0.10mol) of 1, 6-hexanediol and 84g of PGMEA were added to the obtained reaction product, and the temperature was raised to 45 ℃. Then, 61.8g (0.28mol) of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After the completion of the dropwise addition, the mixture was stirred at 75 to 80 ℃ for 6 hours. Further, 21.0g (0.14mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was stirred at 90 to 95 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -5. The resin solution thus obtained had a solid content of 66.5 wt%, an acid value (in terms of solid content) of 38mgKOH/g, and Mw according to GPC analysis was 12220.
[ comparative Synthesis example 1]
51.65g (0.60mol) of methacrylic acid, 38.44g (0.38mol) of methyl methacrylate, 38.77g (0.22mol) of benzyl methacrylate, 5.91g of azobisisobutyronitrile and 370g of diethylene glycol dimethyl ether were added to a 1000ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, and the mixture was stirred under a nitrogen stream at 80 to 85 ℃ for 8 hours to polymerize the compound. 39.23g (0.28mol) of glycidyl methacrylate, 1.44g of TPP, and 0.055g of 2, 6-di-tert-butyl-p-cresol were added to the flask, and the mixture was stirred at 80 to 85 ℃ for 16 hours to obtain an alkali-soluble resin solution (A) -6. The resin solution thus obtained had a solid content of 32% by mass, an acid value (in terms of solid content) of 110mgKOH/g, and Mw, as determined by GPC analysis, of 18100.
(polymerizable unsaturated group-containing alkali-soluble resin)
(A) -1 component: the alkali-soluble resin solution obtained in Synthesis example 1
(A) -2 components: the alkali-soluble resin solution obtained in Synthesis example 2
(A) -3 components: the alkali-soluble resin solution obtained in Synthesis example 3
(A) -4 components: the alkali-soluble resin solution obtained in Synthesis example 4
(A) -5 components: the alkali-soluble resin solution obtained in Synthesis example 5
(A) -6 components: the alkali-soluble resin solution obtained in the comparative Synthesis example 1
(photopolymerizable monomer)
(B) The method comprises the following steps A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon chemical Co., Ltd., trade name DPHA)
(photopolymerization initiator)
(C) The method comprises the following steps Ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime) (manufactured by BASF corporation, Irgacure OXE02)
(light-blocking Dispersion pigment)
(D) -1: 20.0% by mass of titanium black (product name 13M-C, manufactured by Mitsubishi materials Co., Ltd.) and 5.0% by mass of a dispersant (solid content: 25.0%, average particle diameter of titanium black: 188nm)
(D) -2: 15.0% by mass of a black pigment (Irgaphor S100CF, manufactured by BASF corporation, Brilliant fragrance) and 4.5% by mass of a PGMEA dispersion of a polymer dispersant (the solid content: 19.5%, the average secondary particle diameter of the black pigment: 241nm)
(D) -3: 7.0 mass% of c.i. pigment orange 64 (manufactured by BASF), 3.0 mass% of c.i. pigment violet 23 (manufactured by Clariant), 7.0 mass% of c.i. pigment blue 15: 6 (manufactured by Clariant corporation), 4.0 mass% of a polymer dispersant, 2.0 mass% of a sulfonated azo dispersion aid, and 2.0 mass% of a PGMEA dispersion of a benzyl methacrylate/methacrylic acid copolymer (solid content: 25.0%)
(D) -4: 20.0% by mass of carbon black, 5.0% by mass of a polymeric dispersant (25.0% as a solid content, and 162nm as an average secondary particle diameter of carbon black)
(solvent)
(E)-1：PGMEA
(E) -2: acetic acid 3-methoxy-3-methyl-1-butyl ester
(surfactant)
(H) The method comprises the following steps PGMEA solution of BYK-330 (manufactured by BYK-Chemie Co., Ltd.) (solid content: 1.0%)
The photosensitive resin compositions of examples 1 to 11 and comparative examples 1 to 2 were prepared by blending the above-mentioned blend components in the proportions shown in tables 1 and 2. All numerical values in tables 1 and 2 represent parts by mass. In addition, (E) -1 in the column of the solvent is the amount of PGMEA (same as (E) -1) in the resin solution not including the unsaturated group (polymerizable unsaturated group-containing alkali-soluble resin solution) and PGMEA (same as (E) -1) in the light-shielding dispersion.
[ Table 1]
Figure BDA0001129824940000221
[ Table 2]
Figure BDA0001129824940000231
[ evaluation ]
The photosensitive resin compositions for light-shielding films of examples 1 to 11 and comparative examples 1 to 2 were used to perform the following evaluations. The evaluation results are shown in tables 3 and 4.
< developing Property >
Each of the photosensitive resin compositions thus obtained was coated on a glass substrate having a thickness of 1.2mm using a spin coater so that the film thickness after the thermal curing treatment became 3.0. mu.m, and prebaked at 90 ℃ for 1 minute. Then, the photomask was closely contacted with the photomask at a wavelength of 365nm and an illuminance of 30mW/cm2Irradiating with an ultra-high pressure mercury lamp to irradiate at least 100mJ/cm2The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the exposed glass substrate was developed with 0.05% aqueous potassium hydroxide at 24 ℃ and 0.1MPa for 60 seconds to remove the unexposed portions of the coating film. Then, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, to obtain a cured film of the photosensitive resin composition.
The formation of thin lines in the obtained cured film pattern was confirmed by an optical microscope, and evaluated in the following 3 stages.
O: having a pattern with an L/S of 10 μm/10 μm or more without residue
And (delta): having a pattern with an L/S of 30 μm/30 μm or more without residue
X: no pattern with L/S less than 50 μm/50 μm is formed, or bottom curl of pattern or residue is significant
< optical Density >
Each of the photosensitive resin compositions thus obtained was coated on a glass substrate having a thickness of 1.2mm using a spin coater so that the film thickness after the thermal curing treatment became 1.1. mu.m, and prebaked at 90 ℃ for 1 minute. Then, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, to obtain a cured film of the photosensitive resin composition. The optical density of the obtained cured film was measured by a densitometer using Macbeth (Macbeth), and evaluated as an optical density per unit film thickness.
< volume resistivity >
Each of the photosensitive resin compositions thus obtained was applied to a portion excluding electrodes on a glass substrate having a thickness of 1.2mm, on which Cr was deposited, using a spin coater so that the film thickness after the thermal curing treatment became 3.5 μm, and prebaked at 90 ℃ for 1 minute. Then, the cured film of the photosensitive resin composition was obtained by heat curing treatment at 230 ℃ for 30 minutes using a hot air dryer. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring volume resistivity. Then, the volume resistivity at an applied voltage of 1V to 10V was measured using an electrometer ("model 6517A" manufactured by Keithley). The volume resistivity at the time of applying 10V was shown in tables 3 and 4, which were measured under the condition that the voltage was maintained for 60 seconds at each applied voltage in the 1V stage.
< dielectric constant >
Each of the photosensitive resin compositions thus obtained was applied to a portion excluding electrodes on a glass substrate having a thickness of 1.2mm, on which Cr was deposited, using a spin coater so that the film thickness after the thermal curing treatment became 3.5 μm, and prebaked at 90 ℃ for 1 minute. Then, the cured film of the photosensitive resin composition was obtained by heat curing treatment at 230 ℃ for 30 minutes using a hot air dryer. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring dielectric constant. Then, the capacitance was measured at a frequency of 1Hz to 100000Hz using an electrometer ("model 6517A" manufactured by Keithley), and the dielectric constant was calculated from the capacitance.
< Half Tone (HT) characteristics of spacer >
Each of the photosensitive resin compositions thus obtained was coated on a glass substrate having a thickness of 1.2mm using a spin coater so that the film thickness after the thermal curing treatment became 3.0. mu.m, and prebaked at 90 ℃ for 1 minute. Then, a photomask having a dot pattern was brought into close contact with the photomask, and the wavelength was 365nm and the illuminance was 30mW/cm2Irradiating with an ultra-high pressure mercury lamp to irradiate 5mJ/cm2～100mJ/cm2The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the exposed glass substrate was developed with 0.05% aqueous potassium hydroxide at 24 ℃ and 0.1MPa for 60 seconds to remove the unexposed portions of the coating film. Then, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, to obtain a cured film of the photosensitive resin composition.
The spacer had a halftone characteristic that the exposure amount was calculated to be 5mJ/cm2And 100mJ/cm2The difference in height (Δ H) of the lower spacers was evaluated in the following 4 stages.
O: Δ H is 1.0 μm to 2.0 μm
And (delta): Δ H is 0.1 μm to 2.9 μm
X: case where Δ H is less than 0.1 μm or more than 2.9 μm
< compression Rate, elastic recovery Rate, fracture Strength of spacer >
Each of the photosensitive resin compositions thus obtained was coated on a glass substrate having a thickness of 1.2mm using a spin coater so that the film thickness after the thermal curing treatment became 3.0. mu.m, and prebaked at 90 ℃ for 1 minute. Then, the mask having the dot pattern was brought into close contact with the mask, and the wavelength was 365nm and the illuminance was 30mW/cm2Irradiating with an ultra-high pressure mercury lamp to irradiate at least 100mJ/cm2The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the exposed glass substrate was developed with 0.05% aqueous potassium hydroxide at 24 ℃ and 0.1MPa for 60 seconds to remove the unexposed portions of the coating film. Then, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, to obtain a cured film of the photosensitive resin composition.
The spacer characteristics of the obtained hardened film pattern were evaluated using an ultra-fine durometer (manufactured by Fisher Instruments, Fisher thickness gauge (fischer) HM2000 xpp). A100 μm square plane indenter was pressed at a load rate of 5.0mN/sec, and a load was applied to 50mN, and then the load was removed at a load removal rate of 5.0mN/sec, thereby preparing a displacement curve.
The compressibility was calculated from the following equation, assuming that the displacement amount of a load at 50mN under load was L1.
Compression rate (%). L1/height of spacer × 100
The elastic recovery rate was calculated from the following equation, where L1 represents the displacement amount at 50mN of the load under load, and L2 represents the displacement amount at load shedding.
Elastic recovery (%) - (L1-L2)/L1X 100
The breaking strength was evaluated using an ultra-micro durometer (manufactured by Fisher Instruments, inc., Fisher thickness gauge (fischer) HM2000 xpp). The load at break of the spacer was measured by pushing a 100 μm square plane indenter at a load speed of 5.0mN/sec until the load reaches 300mN, and evaluated in the following 4 stages.
O: a breaking strength of 300mN or more
And (delta): a breaking strength of 200mN or less
X: a breaking strength of 100mN or less
< shape of spacer >
Each of the photosensitive resin compositions thus obtained was coated on a glass substrate having a thickness of 1.2mm using a spin coater so that the film thickness after the thermal curing treatment became 3.0. mu.m, and prebaked at 90 ℃ for 1 minute. Then, a photomask having a dot pattern was brought into close contact with the photomask, and the wavelength was 365nm and the illuminance was 30mW/cm2Irradiating with an ultra-high pressure mercury lamp to irradiate at least 100mJ/cm2The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.
Then, the exposed glass substrate was developed with 0.05% aqueous potassium hydroxide at 24 ℃ and 0.1MPa for 60 seconds to remove the unexposed portions of the coating film. Then, a heat curing treatment was performed at 230 ℃ for 30 minutes using a hot air dryer, to obtain a cured film of the photosensitive resin composition.
The shape of the spacer was evaluated by the internal angle (taper angle) of the spacer end using a scanning electron microscope. The taper angle was ^ x when the angle was 70 ° or more and 90 ° or less, ^ o when the angle was 50 ° or more and less than 70 °, Δ when the angle was 50 ° or less, and ×, when the angle was 90 ° or more.
[ Table 3]
Figure BDA0001129824940000261
[ Table 4]
Figure BDA0001129824940000271
From the results of examples 1 to 11 and comparative examples 1 to 2, it is understood that the spacer characteristics such as light-shielding property, dielectric constant, and elastic recovery rate can be improved while maintaining the volume resistivity by using titanium black for the light-shielding material (D). In particular, by using titanium black in combination with a black organic pigment or a mixed color organic pigment, it is possible to complement the drawbacks of various light shielding materials without deteriorating the properties of the spacer such as the elastic recovery rate, and to have the combined effects of the light shielding property, the volume resistivity, and the dielectric constant.

Claims (14)

1. A photosensitive resin composition for a light-shielding film having a spacer function, characterized in that: contains the following components (A) to (E) as essential components:
(A) a polymerizable unsaturated group-containing alkali-soluble resin which is a urethane compound obtained by reacting (a) a polyol compound having an ethylenically unsaturated bond in the molecule, (b) a diol compound having a carboxyl group in the molecule, and (c) a diisocyanate compound;
(B) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond;
(C) a photopolymerization initiator;
(D) a light-shielding component comprising lactam black; and
(E) a solvent.
2. The photosensitive resin composition according to claim 1, further comprising a mixed color organic pigment as the light-shielding component (D), wherein the average secondary particle diameter of the lactam black and/or the mixed color organic pigment is 20nm to 500 nm.
3. The photosensitive resin composition according to claim 1, wherein
The component (B) is contained in an amount of 5 to 400 parts by mass per 100 parts by mass of the component (A),
the component (C) is contained in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B), and when a component other than the component (E) containing the component (B) which becomes a solid component after photo-curing is used as the solid component, the component (D) is contained in an amount of 5 to 80% by mass based on the solid component.
4. The photosensitive resin composition according to claim 1, which can form a light-shielding film comprising: the optical density OD is 0.5/mum to 3/mum, and the volume resistivity is 1 x 10 when a voltage of 10V is applied9Omega cm or more, and a dielectric constant of 2 to 10.
5. The photosensitive resin composition according to claim 1, wherein the light-shielding film satisfying at least one of the following (i) to (iii) is formed in a load-unload test using a microhardness tester,
(i) breaking strength of 200mN or more;
(ii) the elastic recovery rate is more than 30%;
(iii) the compression ratio is 40% or less.
6. A light-shielding film having a spacer function, characterized in that: the photosensitive resin composition according to any one of claims 1 to 5, which is cured.
7. A liquid crystal display device comprising the light-shielding film according to claim 6 as a black column spacer.
8. The liquid crystal display device according to claim 7, further comprising a thin film transistor.
9. A method for producing a photosensitive resin composition for a light-shielding film having a spacer function, comprising preparing a dispersion in which (D) a light-shielding component is dispersed in (E) a solvent, and then adding (A) an alkali-soluble resin having a polymerizable unsaturated group, (B) a photopolymerizable monomer having at least 1 ethylenically unsaturated bond, (C) a photopolymerization initiator, and (E) a solvent to the dispersion and mixing them; and is
The alkali-soluble resin (A) is a urethane compound obtained by reacting a polyol compound (a) having an ethylenically unsaturated bond in the molecule, a diol compound (b) having a carboxyl group in the molecule, and a diisocyanate compound (c),
the light-shielding component (D) contains a lactam black component.
10. The method for producing a photosensitive resin composition according to claim 9, wherein the light-shielding component (D) further contains a mixed color organic pigment, and the average secondary particle diameter of the lactam black and/or the mixed color organic pigment in the dispersion is 20nm to 500 nm.
11. A method for producing a light-shielding film formed on a substrate, comprising applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate, and curing the photosensitive resin composition by light irradiation.
12. The method for manufacturing a light-shielding film according to claim 11, wherein a light-shielding film having a film thickness of H1 for setting an optical density of the light-shielding film to 0.5/μm or more and less than 3/μm and a film thickness of H2 of the light-shielding film functioning as a spacer is formed simultaneously with a film thickness of H1 and a film thickness of H2, wherein Δ H is 0.1 to 2.9 in H2-H1, when H2 is 2 to 7 μm.
13. A method of manufacturing a liquid crystal display device, comprising: the light-shielding film manufactured by the manufacturing method of a light-shielding film according to claim 12 is used as a black column spacer.
14. The method for manufacturing a liquid crystal display device according to claim 13, wherein: the liquid crystal display device includes a thin film transistor.
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