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CN110088681B - Negative photosensitive resin composition - Google Patents

Negative photosensitive resin composition Download PDF

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Publication number
CN110088681B
CN110088681B CN201780079323.6A CN201780079323A CN110088681B CN 110088681 B CN110088681 B CN 110088681B CN 201780079323 A CN201780079323 A CN 201780079323A CN 110088681 B CN110088681 B CN 110088681B
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Prior art keywords
ink
compound
resin composition
photosensitive resin
negative photosensitive
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CN201780079323.6A
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CN110088681A (en
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张娜
川岛正行
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AGC Inc
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Asahi Glass 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/125—Active-matrix OLED [AMOLED] displays including organic TFTs [OTFT]

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optics & Photonics (AREA)

Abstract

Provided is a negative photosensitive resin composition which has high developing adhesion of a partition wall, has good ink repellency on the upper surface, and has sufficiently little development residue at an opening for dot formation. A negative photosensitive resin composition comprising: an alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) comprising a multifunctional low-molecular-weight compound (B1) having an acid group and 2 or more photocurable functional groups in 1 molecule, an ink repellent (C) having an acid group and a fluorine atom and having an acid value of 10 to 100mgKOH/g, a photopolymerization initiator (D), and a solvent (E).

Description

Negative photosensitive resin composition
Technical Field
The present invention relates to a negative photosensitive resin composition.
Background
In the production of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays, and Thin Film solar cells, a method of pattern-printing an organic layer such as a light-emitting layer as dots by an Inkjet (IJ) method is sometimes used. In the above method, a partition wall is provided along the outline of a dot to be formed, ink containing a material of an organic layer is injected into a partition (hereinafter, also referred to as an "opening") surrounded by the partition wall, and the partition is dried and/or heated, thereby forming a dot of a desired pattern.
In pattern printing using an Inkjet (IJ) method, in order to prevent mixing of ink between adjacent dots and to uniformly apply the ink in dot formation, it is necessary for the upper surface of the partition wall to have ink repellency. On the other hand, the opening for forming dots surrounded by the partition wall, including the side surface of the partition wall, needs to have ink affinity. Therefore, in order to obtain a partition wall having ink repellency on the upper surface, the following method is known: partition walls corresponding to a dot pattern are formed by photolithography including steps of coating film formation, exposure, and development using a negative photosensitive resin composition containing an ink repellent.
In the partition wall formed using such a negative photosensitive resin composition, if a residue of the composition (hereinafter, also referred to as "development residue") is present in the opening after development, the wet spread of the ink supplied to the opening by the IJ method may be insufficient thereafter. Further, as a method for reducing the development residue in the opening portion, there is a method of adjusting the negative photosensitive resin composition to a composition that is easily removed by the developer, but in this method, there is a problem that the ink repellency of the upper surface of the partition wall cannot be sufficiently maintained.
For example, patent document 1 describes a photosensitive composition for a partition wall of an active-drive organic electroluminescent element, which contains: component (A): an ethylenically unsaturated compound; (B) component (A): a photopolymerization initiator; (C) component (A): an alkali-soluble binder having an ethylenically unsaturated group in a side chain; and (D) component: a liquid repellent comprising a fluorine-based compound having an ethylenically unsaturated group in a side chain; (E) component (A): a fluorine-based surfactant and/or a silicone-based surfactant.
Patent document 1 describes the following: the examples of the components other than the alkali-soluble binder, for example, the component (a) and the component (D), in which carboxylic acid is introduced, can improve the developability. According to the examples, when a carboxylic acid is introduced into the component (a), both the developing property and the ink repellency are achieved, but when a carboxylic acid-introduced liquid repellent (component (D)) is used, sufficient ink repellency cannot be obtained even when the developing property is good.
Thus, in patent document 1, although the ink repellency of the upper surface of the partition wall and the ink wettability of the opening portion can be achieved at the same time by the composition, the ink repellency of the upper surface of the partition wall and the ink wettability of the opening portion that can sufficiently cope with the optical element with higher accuracy cannot be achieved.
Patent document 2 describes the following technique: for the application by UV/O 3 An ink repellent in a method of removing development residue by irradiation is improved in solubility in a developer by introducing an acidic group into the ink repellent. However, when the ink repellent according to patent document 2 is used for the negative photosensitive resin composition, it is difficult to say that the ink repellent is sufficient in terms of ink repellency and development adhesion, as in the case of patent document 1.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-165396
Patent document 2: international publication No. 2014/046210
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a negative photosensitive resin composition which has high development adhesion of a partition wall, has good ink repellency on the upper surface, and has sufficiently little development residue at an opening for dot formation.
Means for solving the problems
The present invention has the following configuration.
[1] A negative photosensitive resin composition comprising: an alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) comprising a multifunctional low-molecular-weight compound (B1) having an acid group and 2 or more photocurable functional groups in 1 molecule, an ink-repellent agent (C) having an acid group and a fluorine atom and having an acid value of 10 to 100mgKOH/g, a photopolymerization initiator (D), and a solvent (E).
[2] The negative photosensitive resin composition according to [1], wherein the multifunctional low molecular weight compound (B1) has 4 or more photocurable functional groups.
[3] The negative photosensitive resin composition according to [1] or [2], wherein the multifunctional low molecular weight compound (B1) has a dipentaerythritol skeleton.
[4] The negative-type photosensitive resin composition according to any one of [1] to [3], wherein the content of fluorine atoms in the ink-repellent agent (C) is 5 to 55% by mass.
[5] The negative-type photosensitive resin composition according to any one of [1] to [4], wherein the ink-repellent agent (C) contains a photocurable functional group.
[6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the crosslinking agent (B) further contains a crosslinking agent (B2) having 2 or more photocurable functional groups in 1 molecule and having no acidic group.
[7] The negative photosensitive resin composition according to [6], wherein the polyfunctional low-molecular weight compound (B1) is contained in a proportion of 10 to 90 parts by mass with respect to 100 parts by mass of the total of the polyfunctional low-molecular weight compound (B1) and the crosslinking agent (B2).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a negative photosensitive resin composition can be provided in which the partition wall has high development adhesion and good ink repellency on the upper surface, and in which the amount of development residue at the opening for dot formation is sufficiently small.
Drawings
Fig. 1A is a process diagram schematically illustrating a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1B is a process diagram schematically illustrating a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1C is a process diagram schematically illustrating a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1D is a process diagram schematically illustrating a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 2A is a process diagram schematically illustrating a method for manufacturing an optical element according to an embodiment of the present invention.
Fig. 2B is a process diagram schematically illustrating a method for manufacturing an optical element according to an embodiment of the present invention.
Detailed Description
In the present specification, the following terms are used in the following meanings, respectively.
"(meth) acryloyl" is a generic term for "methacryloyl" and "acryloyl". (meth) acryloyloxy, (meth) acrylic acid and (meth) acrylic esters are also used herein.
The group represented by the formula (x) is sometimes abbreviated as group (x).
The compound represented by the formula (y) may be abbreviated as compound (y).
Here, the formulae (x) and (y) represent arbitrary chemical formulae.
"resin mainly composed of a certain component" or "resin mainly composed of a certain component" means: the proportion of this component is 50% by mass or more relative to the total resin amount.
"side chain" means: in the polymer in which the main chain is composed of repeating units formed of carbon atoms, groups other than hydrogen atoms or halogen atoms are bonded to the carbon atoms constituting the main chain.
The "total solid content of the photosensitive resin composition" means: the component for forming a cured film described later among the components contained in the photosensitive resin composition was determined from a residue obtained by heating the photosensitive resin composition at 140 ℃ for 24 hours to remove the solvent. The total solid content may be calculated from the charged amount.
A film formed from a cured product of a composition containing a resin as a main component is referred to as a "resin cured film".
A film obtained by applying the photosensitive resin composition is referred to as a "coating film", and a film obtained by drying the coating film is referred to as a "dried film". The film obtained by curing the "dried film" is a "resin cured film". The "resin cured film" may be simply referred to as a "cured film".
The resin cured film may be in the form of a partition wall formed in a shape that partitions a predetermined region into a plurality of sections. For example, the following "ink" is injected into the partition partitioned by the partition, that is, the opening surrounded by the partition, to form "dots".
"ink" is a term collectively referring to liquids having optical and/or electrical functionality after drying, curing, and the like. In organic EL elements, quantum dot displays, TFT arrays, and thin-film solar cells, dots as various constituent elements are sometimes pattern-printed by an Inkjet (IJ) method using an ink for forming the dots. The "ink" includes inks used in the above-described applications.
"ink repellency" means: the ink has properties of repelling the ink described above, and has both water repellency and oil repellency. The ink repellency can be evaluated by, for example, a contact angle when the ink is dropped. The "ink affinity" is a property opposite to the ink repellency, and can be evaluated by the contact angle when the ink is dropped similarly to the ink repellency. Alternatively, the ink affinity can be evaluated by evaluating the degree of wetting extension of the ink (wetting extension of the ink) when the ink is dropped, with a predetermined criterion.
The "dot" represents the smallest area of the optical element that can be modulated by light. In an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell, 1 dot =1 pixel in black-and-white display, and for example, 3 dots (R (red), G (green), B (blue), and the like) =1 pixel in color display.
"percentage (%) indicates% by mass unless otherwise specified.
Embodiments of the present invention will be described below.
[ negative photosensitive resin composition ]
The negative photosensitive resin composition of the present invention contains: an alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) comprising a multifunctional low-molecular-weight compound (B1) having an acid group and 2 or more photocurable functional groups in 1 molecule, an ink-repellent agent (C) having an acid group and a fluorine atom and having an acid value of 10 to 100mgKOH/g, a photopolymerization initiator (D), and a solvent (E).
The negative photosensitive resin composition of the present invention contains a multifunctional low molecular weight compound (B1) having an acid group as a crosslinking agent (B), and uses the ink repellent (C) having a predetermined acid value in combination, whereby a partition wall having high development adhesion, good ink repellency on the upper surface, and sufficiently small development residue at the opening can be formed. When such a partition wall is used for an optical element, for example, for an organic EL element, for a quantum dot display, for a TFT array, or for a thin film solar cell, dots can be formed with high accuracy due to good ink coatability by the IJ method or the like, and an optical element with high sensitivity can be manufactured.
The negative photosensitive resin composition of the present invention contains, in addition to the above essential components, a crosslinking agent (B2) having no acidic group and other optional components as necessary. The respective components are explained below.
(alkali-soluble resin (A))
The alkali-soluble resin (a) is an alkali-soluble resin having a photocurable functional group. As the alkali-soluble resin (a), a photosensitive resin having an acid group and an olefinic double bond in 1 molecule is preferable. Since the alkali-soluble resin (a) has an olefinic double bond in the molecule, an exposed portion of the negative photosensitive resin composition is polymerized by radicals generated from the photopolymerization initiator (D), and at the same time, is crosslinked by the crosslinking agent (B), and is cured to form a cured film.
The exposed portion sufficiently cured in this way is not easily removed by an alkaline developer (hereinafter also simply referred to as "developer"). In addition, since the multifunctional low molecular weight compound (B1) contained in the alkali-soluble resin (a) and the crosslinking agent (B) has an acidic group in the molecule, the non-exposed portion of the uncured negative photosensitive resin composition can be selectively removed by the developer. As a result, the cured film can be formed into a partition wall having a shape that partitions a predetermined region into a plurality of sections.
Examples of the acidic group include: carboxyl group, phenolic hydroxyl group, sulfo group and phosphate group, these can be used alone 1 or a combination of 2 or more.
The photocurable functional group is preferably an olefinic double bond. Examples of the olefinic double bond include: and double bonds having addition polymerizability such as (meth) acryloyl, allyl, vinyl, vinyloxy, and vinyloxyalkyl groups. These may be used alone in 1 kind or in combination of 2 or more kinds. Some or all of the hydrogen atoms in the olefinic double bond may be substituted with an alkyl group such as a methyl group.
Examples of the alkali-soluble resin (a) having an ethylenic double bond include: a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond; and a resin (A-2) in which an acidic group and an olefinic double bond are introduced into an epoxy resin. These may be used alone in 1 kind or in combination of 2 or more kinds. As such an alkali-soluble resin (a), the resin described in the specification of WO2014/084279 can be used.
As the alkali-soluble resin (A), the above-mentioned resin (A-2) is preferably used from the following points: an aspect in which peeling of the cured film during development can be suppressed and a high-resolution dot pattern can be obtained; the linearity of the pattern when the dots are linear is good; and a smooth cured film surface is easily obtained. The good linearity of the pattern means that the obtained partition wall has no defect or the like in the edge and is linear.
Examples of the resin (A-1) include resins obtained by reacting 2-acryloyloxyethyl isocyanate or the like with a copolymer of acrylic acid, 2-hydroxy methacrylate and other monomers.
Further, there may be mentioned: urethane resins such as unsaturated group-containing urethane resins as component (A) of Japanese patent application laid-open No. 2001-33960, urethane compounds as component (E) of Japanese patent application laid-open No. 2003-268067, and reactive urethane compounds as component (A) of Japanese patent application laid-open No. 2010-280812.
Specific examples thereof include: a resin obtained by reacting a bifunctional epoxy resin with a compound having a double bond and a hydroxyl group obtained by reacting acrylic acid, a diol compound having a carboxyl group such as dimethylolpropionic acid, a diisocyanate compound such as trimethylhexamethylene diisocyanate, and a polybasic acid anhydride such as glycidyl methacrylate or phthalic anhydride as an optional component.
Examples of the bifunctional epoxy resin include: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, trisphenolmethane-type epoxy resin, epoxy resin having a naphthalene skeleton, epoxy resin having a biphenyl skeleton, and fluorenyl-substituted bisphenol a-type epoxy resin.
In particular, when a urethane resin is used, flexibility can be imparted, alkali resistance is also good, and dispersion stability in a developer is also good, which is preferable.
As the resin (a-2), bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, trisphenol methane type epoxy resins, epoxy resins having a naphthalene skeleton, epoxy resins having a biphenyl skeleton, fluorene group-substituted bisphenol a type epoxy resins, and resins obtained by introducing an acidic group and an olefinic double bond into each of the epoxy resins described in jp 2006-84985 a are preferable.
More preferred are bisphenol a epoxy resins, bisphenol F epoxy resins, epoxy resins having a biphenyl skeleton, fluorene-substituted bisphenol a epoxy resins, and resins obtained by introducing an acidic group and an olefinic double bond into each of the epoxy resins described in jp 2006-84985 a.
Among them, bisphenol a type epoxy resins, bisphenol F type epoxy resins, epoxy resins having a biphenyl skeleton, and fluorenyl-substituted bisphenol a type epoxy resins are particularly preferable. In the case of these resins, the interaction with the photopolymerization initiator (D) is improved, and the adhesion to the substrate is improved.
The number of the ethylenic double bonds in 1 molecule of the alkali-soluble resin (a) is preferably 3 or more on average, and particularly preferably 6 or more on average. When the number of the olefinic double bonds is not less than the lower limit of the above range, the alkali solubility of the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller amount of exposure.
The mass-average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.0X 10 3 ～20×10 3 Particularly preferably 2X 10 3 ～15×10 3 . The number average molecular weight (Mn) is preferably 500 to 13X 10 3 Particularly preferably 1.0X 10 3 ～10×10 3 . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when they are not more than the upper limit of the above range, developability is good.
In the present specification, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are values measured by gel permeation chromatography using polystyrene as a standard substance unless otherwise specified.
The acid value of the alkali-soluble resin (A) is preferably from 10 to 300mgKOH/g, and particularly preferably from 10 to 150mgKOH/g. When the acid value of the alkali-soluble resin (a) is in the above range, the negative photosensitive composition can be developed well.
The alkali-soluble resin (a) contained in the negative photosensitive resin composition may be used singly in 1 kind or in combination in 2 or more kinds.
The content of the alkali-soluble resin (a) in the total solid content of the negative photosensitive resin composition is preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass. When the content ratio is within the above range, the negative photosensitive resin composition is excellent in photocurability and developability.
(crosslinking agent (B))
The crosslinking agent (B) contains a multifunctional low-molecular-weight compound (B1) having an acidic group and 2 or more photocurable functional groups in 1 molecule, and preferably further contains a crosslinking agent (B2) having 2 or more photocurable functional groups in 1 molecule and having no acidic group (hereinafter also referred to as "non-acidic crosslinking agent (B2)"). Since the crosslinking agent (B) has 2 or more photocurable functional groups in 1 molecule, it reacts with the photocurable functional groups of the alkali-soluble resin (a) by the action of the photopolymerization initiator (D). The negative photosensitive resin composition of the present invention containing these components is a cured film which is sufficiently cured by crosslinking with the crosslinking agent (B) upon polymerization of the alkali-soluble resin (a) by exposure to light.
< multifunctional Low molecular weight Compound (B1) >)
The multifunctional low-molecular-weight compound (B1) is a monomer having 1 molecule thereof with an acidic group and 2 or more photocurable functional groups. The term "low-molecular-weight compound" in the present invention refers to a concept that is opposite to a so-called high-molecular-weight substance (resin). In the present specification, "low molecular weight compound" is used in a concept including "monomer", "dimer", "trimer", and "oligomer". In the present specification, the term "low molecular weight compound" means a compound having a mass average molecular weight (Mw) of less than 1000.
The mass average molecular weight (Mw) of the multifunctional low-molecular weight compound (B1) is preferably 300 or more and less than 1000, more preferably 500 or more and less than 800. The number average molecular weight (Mn) is preferably 300 or more and less than 1000, and particularly preferably 500 or more and less than 800. When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are in the above ranges, the alkali solubility and the developability are good.
The photocurable functional group of the multifunctional low-molecular-weight compound (B1) is preferably the same kind of photocurable functional group as the photocurable functional group of the alkali-soluble resin (a), and specifically, an olefinic double bond is preferred. The number of the photocurable functional groups in 1 molecule of the multifunctional low-molecular-weight compound (B1) may be 2 or more, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. The greater the number of photocurable functional groups, the higher the curability of the coating film surface, and the better the stability of the ink repellency of the surface of the obtained partition wall.
Examples of the acidic group of the multifunctional low-molecular-weight compound (B1) include: carboxyl group, phenolic hydroxyl group, sulfo group and phosphate group, these can be used alone 1 or a combination of 2 or more. The number of the acidic groups in the molecule of the multifunctional low-molecular-weight compound (B1) 1 may be 1 or more, preferably 1 to 2, and more preferably 1.
Examples of the multifunctional low-molecular-weight compound (B1) include: an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, an olefinic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a hydroxyl compound having a (meth) acryloyl group, and the like, and a compound having an acidic group introduced so that 2 or more unsaturated bonds (olefinic double bonds) remain.
The polyfunctional low molecular weight compound (B1) is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is preferably a polyfunctional low molecular weight compound having an acid group obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with an aromatic carboxylic anhydride or a non-aromatic carboxylic anhydride, and more preferably a polyfunctional low molecular weight compound having an acid group obtained by reacting a non-aromatic carboxylic anhydride.
Examples of the aliphatic polyhydroxy compound in the ester of the unsaturated carboxylic acid and the aliphatic polyhydroxy compound having an acid group introduced thereinto include compounds having 3 or more hydroxyl groups, such as trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, and tetrapentaerythritol. Examples of the unsaturated carboxylic acid include: (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and the like.
Among the esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, the aliphatic polyhydroxy compounds are preferably pentaerythritol and/or dipentaerythritol, particularly preferably dipentaerythritol. As the unsaturated carboxylic acid, (meth) acrylic acid is preferable, and acrylic acid is more preferable.
Specific examples of the aromatic carboxylic anhydride for introducing an acid group into the ester include phthalic anhydride, and specific examples of the non-aromatic carboxylic anhydride include: tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, of which succinic anhydride is preferred.
Among the polyfunctional low-molecular-weight compounds (B1), examples of the compound obtained by reacting an ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid with an aromatic carboxylic acid anhydride include 2,2,2-triacryloxymethylethyl phthalate having a structure in which 3 hydroxyl groups of pentaerythritol are substituted with acryloyloxy groups and the remaining 1 hydroxyl group is ester-bonded to, for example, phthalic acid.
As the multifunctional low-molecular weight compound (B1), a compound having a dipentaerythritol skeleton is preferable. As the compound having a dipentaerythritol skeleton, for example, preferred are: a compound in which 5 hydroxyl groups of dipentaerythritol are substituted with (meth) acryloyloxy groups and the remaining 1 hydroxyl group is ester-bonded to, for example, succinic acid, thereby introducing an acidic group.
The acid value of the polyfunctional low-molecular weight compound (B1) is preferably from 10 to 100mgKOH/g, more preferably from 20 to 95mgKOH/g. When the acid value of the polyfunctional low-molecular weight compound (B1) is not less than the lower limit, the negative photosensitive composition can obtain more favorable solubility in a developer, and when the acid value is not more than the upper limit, the production and handling properties become favorable, sufficient polymerizability can be ensured, and the curability such as surface smoothness of the obtained coating film also becomes favorable.
In the negative photosensitive resin composition, the polyfunctional low-molecular weight compound (B1) may be used alone in 1 kind or in combination with 2 or more kinds. When the multifunctional low-molecular-weight compound (B1) is used in the form of a mixture of 2 or more species, the acid value of the mixture is preferably within the above range.
< non-acidic crosslinking agent (B2) >)
The crosslinking agent (B) may contain a crosslinking agent (B2) having 2 or more photocurable functional groups in 1 molecule and having no acidic group, that is, a non-acidic crosslinking agent (B2), in addition to the multifunctional low-molecular-weight compound (B1). By using the multifunctional low-molecular-weight compound (B1) and the non-acidic crosslinking agent (B2) in combination, the acid value and the number of photocurable functional groups of the entire crosslinking agent (B) can be easily adjusted, and a balance between the action of improving the curability of the negative photosensitive resin composition at the time of exposure and the action of improving the solubility of the negative photosensitive resin composition in a developer can be easily obtained.
As the non-acidic crosslinking agent (B2), the same kind of photocurable functional group as that of the alkali-soluble resin (a) is preferable as the photocurable functional group having 2 or more groups in 1 molecule, and specifically, an olefinic double bond is preferable. The number of the photocurable functional groups in 1 molecule of the non-acidic crosslinking agent (B2) may be 2 or more, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. The higher the number of photocurable functional groups, the higher the curability of the coating film surface, and the better the stability of the ink repellency of the upper surface of the obtained partition wall. The molecular weight of the non-acidic crosslinking agent (B2) may be the same as that of the multifunctional low-molecular-weight compound (B1) including the preferred embodiments.
Specific examples of the non-acidic crosslinking agent (B2) include compounds having no acidic group in the polyfunctional low-molecular weight compound (B1), and esters of aliphatic polyhydric compounds and unsaturated carboxylic acids are preferable.
More specifically, the non-acidic crosslinking agent (B2) includes: HDI (hexamethylene diisocyanate) is bonded to diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptaacrylate, tetrapentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, ethoxylated isocyanuric acid tri (meth) acrylate, tris- (2-acryloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, dipentaerythritol pentaacrylate to form a monomer (decafunctional) having a urethane skeleton, urethane acrylate, and the like.
In the negative photosensitive resin composition, 1 or more of the non-acidic crosslinking agents (B2) may be used alone or in combination.
The content of the crosslinking agent (B) in the entire solid content of the negative photosensitive resin composition is preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass. When the crosslinking agent (B) is composed of only the polyfunctional low-molecular weight compound (B1), the acid value of the crosslinking agent (B) is in the same range as the acid value of the polyfunctional low-molecular weight compound (B1). When the crosslinking agent (B) contains both the multifunctional low-molecular weight compound (B1) and the non-acidic crosslinking agent (B2), the acid value of the crosslinking agent (B) is preferably from 10 to 80mgKOH/g, more preferably from 15 to 70mgKOH/g.
The content of the multifunctional low-molecular weight compound (B1) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content ratio of the multifunctional low-molecular weight compound (B1) is in the above range, the negative photosensitive resin composition is excellent in photocurability and developability.
When the negative photosensitive resin composition contains the non-acidic crosslinking agent (B2) as the crosslinking agent (B), the content of the non-acidic crosslinking agent (B2) in the entire solid content of the composition is preferably 0.1 to 50% by mass, and more preferably 1.0 to 40% by mass.
In this case, the ratio of the multifunctional low-molecular weight compound (B1) to 100 parts by mass of the total of the multifunctional low-molecular weight compound (B1) and the non-acidic crosslinking agent (B2) is preferably 10 to 90 parts by mass, and more preferably 15 to 70 parts by mass. By setting the ratio of the multifunctional low-molecular-weight compound (B1) to the non-acidic crosslinking agent (B2) as described above, the acid value and the number of photocurable functional groups of the entire crosslinking agent (B) can be easily adjusted, and a balance between the photocurability and developability of the negative photosensitive resin composition can be easily obtained.
As the crosslinking agent (B), a commercially available crosslinking agent in the form of a mixture of the multifunctional low-molecular weight compound (B1) and the non-acidic crosslinking agent (B2), for example, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinic acid ester mixture of dipentaerythritol pentaacrylate, and the like can also be used.
Further, if necessary, a monomer of the multifunctional low molecular weight compound (B1) and/or a monomer of the non-acidic crosslinking agent (B2) may be used in combination with the above mixture.
(ink repellent (C))
The ink repellent (C) has an acid group and a fluorine atom, and has an acid value of 10 to 100mgKOH/g. By having a fluorine atom, the ink-repellent agent (C) is provided with a property of migrating to the upper surface (upper surface migration) and an ink-repellency in the process of forming a cured film using the negative photosensitive resin composition containing the ink-repellent agent (C). By using the ink repellent (C), the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink repellent (C) is densely present (hereinafter, also referred to as "ink repellent layer"), and the ink repellency is imparted to the upper surface of the cured film.
The ink-repellent agent (C) has an acid group, and when the acid value is not less than the lower limit value, the ink-repellent agent (C) has good solubility in a developer, similarly to other components such as the alkali-soluble resin (a) and the crosslinking agent (B) contained in the negative photosensitive resin composition. Thus, the negative photosensitive resin composition in the unexposed portion can be easily removed by the developer, and the developability is good. On the other hand, when the acid value of the ink repellent (C) is not more than the upper limit, the ink repellent layer formed on the upper layer of the cured film and the resin layer on the lower layer are sufficiently adhered to each other, and therefore, the cured film is hardly affected by the developer, and can exhibit high ink repellency even after development.
The acid value of the ink-repellent agent (C) is preferably from 20 to 100mgKOH/g, more preferably from 25 to 80mgKOH/g, and still more preferably from 30 to 60mgKOH/g.
From the viewpoint of surface migration and ink repellency, the content of fluorine atoms in the ink repellent (C) is preferably 5 to 55% by mass, more preferably 10 to 55% by mass, even more preferably 12 to 40% by mass, and particularly preferably 14 to 30% by mass. When the fluorine atom content of the ink repellent (C) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and when it is not more than the upper limit, compatibility with other components in the negative photosensitive resin composition becomes good.
The ink repellent (C) is preferably a compound having a photocurable functional group, particularly an ethylenic double bond. By having the ink-repellent agent (C) have an olefinic double bond, a radical acts on the olefinic double bond of the ink-repellent agent (C) which migrates to the upper surface, and crosslinking based on (co) polymerization of the ink-repellent agents (C) with each other or with other components having an olefinic double bond contained in the negative photosensitive resin composition can be achieved.
Thus, in the production of a cured film obtained by curing the negative photosensitive resin composition, the fixation of the ink repellent (C) to the upper layer portion of the cured film, that is, to the ink repellent layer can be improved. The negative photosensitive resin composition of the present invention can sufficiently fix the ink-repellent agent (C) in the ink-repellent layer even when the exposure amount at the time of exposure is low. The case where the ink repellent (C) has an ethylenic double bond is as described above. When the ink repellent (C) does not have an ethylenic double bond, the photocurable component mainly composed of the alkali-soluble resin (a) present around the ink repellent (C) is sufficiently cured, whereby the ink repellent (C) can be sufficiently fixed.
Examples of the ink repellent (C) include: an ink repellent (C1) composed of a compound whose main chain is a hydrocarbon chain and which has a side chain having an acidic group and a side chain containing a fluorine atom. As the ink repellent (C), an ink repellent (C2) composed of a partial hydrolysis condensate of a hydrolyzable silane compound containing a hydrolyzable silane compound having an acidic group and a hydrolyzable silane compound having a fluorine atom can also be used.
The ink-repellent agent (C1) and the ink-repellent agent (C2) may be used alone or in combination. The negative photosensitive resin composition of the present invention is particularly preferably used with the ink-repellent agent (C1) from the viewpoint of exhibiting higher ink repellency. In addition, in the case where ultraviolet/ozone resistance is required, the ink repellent (C2) is preferably used.
< ink repellent (C1) >)
The ink repellent (C1) is a compound having a hydrocarbon chain as a main chain and having a side chain having an acidic group and a side chain containing a fluorine atom. The mass-average molecular weight (Mw) of the ink-repellent agent (C1) is preferably 1.0X 10 4 ～15×10 4 More preferably 1.2X 10 4 ～13×10 4 Particularly preferably 1.4X 10 4 ～12×10 4 . When the mass average molecular weight (Mw) is not less than the lower limit, the ink repellent (C1) is likely to migrate to the upper surface when a cured film is formed using the negative photosensitive resin composition. When the amount is less than the upper limit, the amount of residue at the opening is preferably small.
As the acidic group in the side chain having an acidic group, there can be mentioned: carboxyl group, phenolic hydroxyl group, sulfo group and phosphate group, these can be used alone 1 or a combination of 2 or more. In the ink repellent (C1), the portion other than the acidic group in the side chain having the acidic group is not particularly limited.
The side chain containing a fluorine atom which the ink repellent (C1) has is preferably a side chain composed of a fluoroalkyl group optionally containing an etheric oxygen atom and/or a side chain having a fluoroalkyl group optionally containing an etheric oxygen atom.
The fluoroalkyl group may be linear or branched.
Specific examples of the fluoroalkyl group containing no etheric oxygen atom include the following structures.
-CF 3 、-CF 2 CF 3 、-CF 2 CHF 2 、-(CF 2 ) 2 CF 3 、-(CF 2 ) 3 CF 3 、-(CF 2 ) 4 CF 3 、-(CF 2 ) 5 CF 3 、-(CF 2 ) 6 CF 3 、-(CF 2 ) 7 CF 3 、-(CF 2 ) 8 CF 3 、-(CF 2 ) 9 CF 3 、-(CF 2 ) 11 CF 3 、-(CF 2 ) 15 CF 3 。
Specific examples of the fluoroalkyl group containing an etheric oxygen atom include the following structures.
-CF(CF 3 )O(CF 2 ) 5 CF 3 、
-CF 2 O(CF 2 CF 2 O) r1 CF 3 、
-CF(CF 3 )O(CF 2 CF(CF 3 )O) r2 C 6 F 1 3、
and-CF (CF) 3 )O(CF 2 CF(CF 3 )O) r3 C 3 F 7 。
In the above formula, r1 is an integer of 1 to 8, r2 is an integer of 1 to 4, and r3 is an integer of 1 to 5.
Specific examples of the hydrocarbon chain constituting the main chain of the ink repellent (C1) include: tong (Chinese character of 'tong')Main chain obtained by polymerization of monomer having olefinic double bond, from-Ph-CH 2 A novolac-type main chain composed of repeating units of- (wherein, "Ph" represents a benzene skeleton.), and the like.
The ink repellent (C1) may further comprise 1 or more kinds of side chains selected from the group consisting of a side chain having an ethylenic double bond and a side chain having an oxyalkylene group. An olefinic double bond and an oxyalkylene group may be contained in 1 side chain. In addition, an olefinic double bond and/or an oxyalkylene group may be contained in the side chain containing the above acidic group.
The ink repellent (C1) may contain a side chain such as a dimethylsiloxane chain, an alkyl group, a glycidyl group, an isobornyl group, an isocyanate group, or a trialkoxysilyl group.
The main chain of the ink repellent (C1) is represented by-Ph-CH 2 In the case of the novolac-type main chain composed of the repeating units of (a) and (b), a polymer in which a side chain having a fluorine atom and a side chain having an acidic group are bonded to the benzene skeleton (Ph) constituting the main chain, and further a side chain having an ethylenic double bond and an oxyalkylene side chain are optionally bonded is generally used as the ink repellent (C1). Each side chain may be bonded to the same benzene skeleton (Ph), and may be bonded to different benzene skeletons (Ph). The number of side chains bonded to one benzene skeleton (Ph) is preferably 1.
The adjustment of the acid value in the ink-repellent agent (C1) can be easily performed by adjusting the proportion of the side chain having an acidic group introduced into the main chain of the hydrocarbon chain of the ink-repellent agent (C1). Similarly, the content of the fluorine atom in the ink repellent (C1) can be easily adjusted by adjusting the proportion of the side chain having a fluorine atom introduced into the main chain of the hydrocarbon chain of the ink repellent (C1).
< ink repellent (C2) >)
The ink repellent (C2) is a partial hydrolysis condensate of a mixture of hydrolyzable silane compounds (hereinafter also referred to as "mixture (M)").
The mixture (M) contains as essential components: a hydrolyzable silane compound having a fluoroalkylene group and/or fluoroalkyl group and a group in which a hydrolyzable group is bonded to a silicon atom (hereinafter, also referred to as "hydrolyzable silane compound (s 1)"); and a hydrolyzable silane compound (hereinafter also referred to as "hydrolyzable silane compound (s 2)") which contains a group having an acidic group and a group in which a hydrolyzable group is bonded to a silicon atom and does not contain a fluorine atom, and the mixture (M) optionally contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s 1) and the hydrolyzable silane compound (s 2).
As the hydrolyzable silane compound optionally contained in the mixture (M), a hydrolyzable silane compound in which 4 hydrolyzable groups are bonded to a silicon atom (hereinafter also referred to as "hydrolyzable silane compound (s 3)") is preferable.
Specific examples of the hydrolyzable silane compound (s 1) include the following compounds.
F(CF 2 ) 4 CH 2 CH 2 Si(OCH 3 ) 3 、
F(CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 、
F(CF 2 ) 6 CH 2 CH 2 CH 2 Si(OCH 3 ) 3 、
F(CF 2 ) 8 CH 2 CH 2 Si(OCH 3 ) 3 、
F(CF 2 ) 3 OCF(CF 3 )CF 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 、
F(CF 2 ) 2 O(CF 2 ) 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 。
(CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 4 CH 2 CH 2 Si(OCH 3 ) 3 、
(CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 、
(CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 6 CH 2 CH 2 CH 2 Si(OCH 3 ) 3 、
(CH 3 O) 3 SiCH 2 CH 2 (CF 2 ) 2 OCF 2 (CF 3 )CFO(CF 2 ) 2 OCF(CF 3 )CF 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 。
Among them, F (CF) is particularly preferable 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 And F (CF) 2 ) 3 OCF(CF 3 )CF 2 O(CF 2 ) 2 CH 2 CH 2 Si(OCH 3 ) 3 。
The content of the hydrolyzable silane compound (s 1) in the mixture (M) is preferably such that the content of fluorine atoms in the partially hydrolyzed condensate obtained from the mixture is 5 to 55% by mass. More preferably 10 to 55% by mass, still more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. When the content ratio of the hydrolyzable silane compound (s 1) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and when it is not more than the upper limit, compatibility with other hydrolyzable silane compounds in the mixture becomes good.
The acidic group of the hydrolyzable silane compound (s 2) is preferably a carboxyl group, a phenolic hydroxyl group or a sulfo group. Specific examples of the hydrolyzable silane compound (s 2) include the following compounds.
(1) The compounds represented by the following formula (c-2 a) are specifically compounds represented by the following formula (c-2 a-1), the following formula (c-2 a-2), the following formula (c-2 a-3), the following formula (c-2 a-4), the following formula (c-2 a-5), and the following formula (c-2 a-6), respectively.
Figure BDA0002101829690000171
R 22 Is of the formula-R 25 -COOH or-COO-R 25 OOC-R 25 -COOH (here, R) 25 To representA 2-valent hydrocarbon group having 1 to 10 carbon atoms, a single bond, or a phenylene group. ) The groups shown. R 22 is-COO-R 25 OOC-R 25 In the case of — COOH, the developer solubility of the ink repellent (C2) is further improved, the opening residue is reduced, and the ink wet spreading by the IJ method is further favorable, which is preferable.
R 21 is-COOR 24 (Here, R is 24 Represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. ) A group represented by the formula, -COO- (C) 2 H 4 O) i -(C 3 H 6 O) j -(C 4 H 8 O) k -R 28 (Here, R is 28 Represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, i represents 0 to 100, j represents 0 to 100, k represents an integer of 0 to 100, and i + j + k is 2 to 100. When there are a plurality of oxyalkylene units, the order is arbitrary. ) Or a phenyl group in which a hydrogen atom is optionally substituted by a hydrocarbon group having 1 to 10 carbon atoms. R 21 is-COO- (C) 2 H 4 O) i -(C 3 H 6 O) j -(C 4 H 8 O) k -R 28 In the case of (C2), the dispersion stability and storage stability of the ink repellent are improved.
Q 2 Is a 2-valent hydrocarbon group having 1 to 10 carbon atoms.
X 2 Is a hydrolyzable group, 3X 2 May be different from or the same as each other. X 2 Methoxy or ethoxy is preferred.
m is an integer of 0 or more, and n is an integer of 1 or more.
Figure BDA0002101829690000181
Figure BDA0002101829690000191
X 2 M, n and i are the same as those of the formula (c-2 a).
(2) Specifically, the reaction product of the cyclic carboxylic anhydride and the hydrolyzable silane compound having an amino group is a compound represented by the following formula (c-2 b-1) or (c-2 b-2).
Figure BDA0002101829690000201
X 2 The same as in the formula (c-2 a).
(3) Specifically, the reaction product of an olefinic double bond, a compound having a hydroxyl group or a carboxyl group or a derivative thereof, and a hydrosilane is a compound represented by the following formula (c-2 c-1) or (c-2 c-2).
HO(CF 3 ) 2 C(CH 2 ) 3 SiX 2 3 (c-2c-1)
Figure BDA0002101829690000202
X 2 The same as in the formula (c-2 a).
The content ratio of the hydrolyzable silane compound (s 2) in the mixture (M) is such that the acid value of the partially hydrolyzed condensate obtained from the mixture becomes 10 to 100mgKOH/g. The acid value of the partially hydrolyzed condensate is preferably from 20 to 100mgKOH/g, more preferably from 25 to 80mgKOH/g, and still more preferably from 30 to 60mgKOH/g.
When the content of the hydrolyzable silane compound (s 2) is not less than the lower limit of the above range, the obtained negative photosensitive resin composition has good solubility in a developer. Thus, the negative photosensitive resin composition in the unexposed portion can be easily removed by the developer, and the developability is good. On the other hand, when the acid value of the ink repellent (C) is not more than the upper limit, the ink repellent layer formed on the upper layer of the cured film and the resin layer on the lower layer of the cured film are sufficiently adhered to each other, hardly affected by the developer, remain even after development, and can exhibit high ink repellency.
Specific examples of the hydrolyzable silane compound (s 3) include the following compounds.
Si(OCH 3 ) 4 、Si(OC 2 H 5 ) 4 、
Si(OCH 3 ) 4 Partial hydrolysis condensate of,
Si(OC 2 H 5 ) 4 The partial hydrolysis condensate of (a).
The content of the hydrolyzable silane compound (s 3) in the mixture (M) is preferably 0.01 to 5 mol, and particularly preferably 0.05 to 4 mol, based on 1 mol of the hydrolyzable silane compound (s 1). When the content ratio is not less than the lower limit of the above range, the film forming property of the ink repellent (C2) is good, and when the content ratio is not more than the upper limit, the ink repellency of the ink repellent (C2) is good.
The mixture (M) may optionally further contain 1 or 2 or more hydrolyzable silane compounds other than the hydrolyzable silane compounds (s 1) to (s 3). Examples of the hydrolyzable silane compound preferably contained in the mixture (M) include the following hydrolyzable silane compound (s 4), hydrolyzable silane compound (s 5) and hydrolyzable silane compound (s 6). The mixture (M) is preferably a hydrolyzable silane compound (s 4).
A hydrolyzable silane compound (s 4); a hydrolyzable silane compound which contains a group having an olefinic double bond and a group in which a hydrolyzable group is bonded to a silicon atom and does not contain a fluorine atom.
A hydrolyzable silane compound (s 5); a hydrolyzable silane compound having a mercapto group or a thioether group, a hydrolyzable silyl group, and no fluorine atom.
A hydrolyzable silane compound (s 6); a hydrolyzable silane compound having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom.
Specific examples of the hydrolyzable silane compound (s 4) include the following compounds.
CH 2 ＝C(CH 3 )COO(CH 2 ) 3 Si(OCH 3 ) 3 、
CH 2 ＝C(CH 3 )COO(CH 2 ) 3 Si(OC 2 H 5 ) 3 、
CH 2 ＝CHCOO(CH 2 ) 3 Si(OCH 3 ) 3 、
CH 2 ＝CHCOO(CH 2 ) 3 Si(OC 2 H 5 ) 3 、
[CH 2 ＝C(CH 3 )COO(CH 2 ) 3 ]CH 3 Si(OCH 3 ) 2 、
[CH 2 ＝C(CH 3 )COO(CH 2 ) 3 ]CH 3 Si(OC 2 H 5 ) 2 、
CH 2 ＝CHSi(OCH 3 ) 3 、
CH 2 ＝CHC 6 H 4 Si(OCH 3 ) 3 。
The content of the hydrolyzable silane compound (s 4) in the mixture (M) is preferably 0.1 to 5 moles, and particularly preferably 0.5 to 4 moles with respect to 1 mole of the hydrolyzable silane compound (s 1). When the content ratio is not less than the lower limit of the above range, the upper surface migration of the ink-repellent agent (C2) is good, the fixation of the ink-repellent agent (C2) to the ink-repellent layer including the upper surface after the upper surface migration is good, and further, the storage stability of the ink-repellent agent (C2) is good. When the amount is less than the upper limit, the ink repellency of the ink repellent (C2) is good.
Specific examples of the hydrolyzable silane compound (s 5) include: HS- (CH) 2 ) 3 -Si(OCH 3 ) 3 、HS-(CH 2 ) 3 -Si(CH 3 )(OCH 3 ) 2 Bis- [3- (triethoxysilyl) propyl ] silane]-tetrasulfide.
The content of the hydrolyzable silane compound (s 5) in the mixture (M) is preferably 0 to 2.0 mol, and particularly preferably 0 to 1.5 mol, based on 1 mol of the hydrolyzable silane compound (s 1). When the content ratio is not less than the lower limit of the above range, the upper surface migration of the ink-repellent agent (C2) is good, the fixation of the ink-repellent agent (C2) to the ink-repellent layer including the upper surface after the upper surface migration is good, and further, the storage stability of the ink-repellent agent (C2) is good. When the amount is less than the upper limit, the ink repellency of the ink repellent (C2) is good.
Specific examples of the hydrolyzable silane compound (s 6) include the following compounds.
(CH 3 ) 3 -Si-OCH 3 、(CH 3 CH 2 ) 3 -Si-OC 2 H 5 、(CH 3 ) 3 -Si-OC 2 H 5 、(CH 3 CH 2 ) 3 -Si-OCH 3 、(CH 3 ) 2 -Si-(OCH 3 ) 2 、(CH 3 ) 2 -Si-(OC 2 H 5 ) 2 、(CH 3 CH 2 ) 2 -Si-(OC 2 H 5 ) 2 、(CH 3 CH 2 ) 2 -Si-(OCH 3 ) 2 、Ph-Si(OC 2 H 5 ) 3 、Ph-Si(OCH 3 ) 3 、C 10 H 21 -Si(OCH 3 ) 3 . In the formula, ph represents a phenyl group.
The content of the hydrolyzable silane compound (s 6) in the mixture (M) is preferably 0 to 1.0 mol, and particularly preferably 0 to 0.08 mol, based on 1 mol of the hydrolyzable silane compound (s 1). When the content ratio is not less than the lower limit of the above range, the storage stability is good. When the amount is less than the upper limit, the ink coatability of the dot portion is good.
Examples of other hydrolyzable silane compounds include the following compounds: a hydrolyzable silane compound (s 7) having an epoxy group and a hydrolyzable silyl group and containing no fluorine atom; a hydrolyzable silane compound (s 8) having an oxyalkylene group and a hydrolyzable silyl group and containing no fluorine atom; a hydrolyzable silane compound (s 9) having a thioether group and a hydrolyzable silyl group and containing no fluorine atom; a hydrolyzable silane compound (s 10) having a urea group and a hydrolyzable silyl group and containing no fluorine atom; and a hydrolyzable silane compound (s 11) having an amino group and a hydrolyzable silyl group and containing no fluorine atom.
Examples of the hydrolyzable silane compound (s 7) include: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane, examples of the hydrolyzable silane compound (s 8) include: CH (CH) 3 O(C 2 H 4 O) k Si(OCH 3 ) 3 (trimethoxy silane containing a polyoxyethylene group) (here, k is, for example, about 10.), and examples of the hydrolyzable silane compound (s 9) include: examples of the hydrolyzable silane compound (s 10) of bis (triethoxysilylpropyl) tetrasulfide include: examples of the 3-ureidopropyltriethoxysilane compound as the hydrolyzable silane compound (s 11) include: n-phenyl-3-aminopropyltrimethoxysilane.
In particular, when the ink repellent (C2) contains the hydrolyzable silane compound (s 8), the dispersion stability and storage stability of the ink repellent (C2) are preferably improved. In particular, when the ink repellent (C2) contains the hydrolyzable silane compound (s 9), it is preferable that the ink repellency is easily exhibited even at a low exposure amount.
As an example of the ink repellent (C2), a partial hydrolysis-condensation product of a mixture (M) containing a hydrolyzable silane compound (s 1) of n1, a hydrolyzable silane compound (s 2) of n2, a hydrolyzable silane compound (s 3) of n3, a hydrolyzable silane compound (s 4) of n4, a hydrolyzable silane compound (s 5) of n5, and a hydrolyzable silane compound (s 6) of n6 can be cited. Here, n1 to n6 represent the mole fraction of each structural unit with respect to the total molar amount of the structural units. N1 > 0, n2 > 0, n3 > 0, n4 > 0, n5 > 0, n6 > 0, n1+ n2+ n3+ n4+ n5+ n6=1.
n1: n2: n3 is in accordance with the charging composition of the hydrolyzable silane compound (s 1), (s 2), (s 3), (s 4), (s 5) and (s 6) in the mixture (M). The molar ratio of each component is designed based on the balance of the effects of each component.
In the amount in which the fluorine atom content in the ink repellent (C2) falls within the above preferred range, n1 is preferably 0.02 to 0.4.
In the amount in which the acid value of the ink-repellent agent (C2) falls within the above range, n2 is preferably 0.003 to 0.03.
n3 is preferably from 0 to 0.98, particularly preferably from 0.05 to 0.6.
n4 is preferably from 0 to 0.4, particularly preferably from 0 to 0.27.
n5 is preferably from 0 to 0.1, particularly preferably from 0 to 0.07.
n6 is preferably from 0 to 0.2, particularly preferably from 0 to 0.15.
The mass-average molecular weight (Mw) of the ink-repellent agent (C2) is preferably 500 or more, preferably less than 1X 10 6 Particularly preferably 5X 10 3 The following. When the mass average molecular weight (Mw) is not less than the lower limit, the ink repellent (C2) is likely to migrate to the upper surface when a cured film is formed using the negative photosensitive resin composition. When the content is less than the upper limit, the content of the opening residue is preferably reduced. The mass average molecular weight (Mw) of the ink repellent (C2) can be adjusted by the production conditions.
The ink repellent (C2) can be produced by subjecting the above-mentioned mixture (M) to hydrolysis and condensation reaction by a known method. In this reaction, a basic catalyst such as sodium hydroxide or tetramethylammonium hydroxide (TMAH), an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, or an organic acid such as acetic acid, oxalic acid, or maleic acid can be used as a catalyst. In addition, a known solvent can be used in the above reaction. The ink-repellent agent (C2) obtained in the above reaction may be blended in the negative photosensitive resin composition together with a solvent in the form of a solution.
The content ratio of the ink repellent (C) in the total solid components in the negative photosensitive resin composition is: in the partition wall obtained using the same, the surface satisfies the content ratio of the above-described characteristics. The content also depends on the kind of the ink-repellent agent (C) used, but specifically, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass. When the content ratio is not less than the lower limit of the above range, the upper surface of the cured film formed from the negative photosensitive resin composition has excellent ink repellency. When the content is not more than the upper limit of the above range, the adhesion between the cured film and the substrate is good.
(photopolymerization initiator (D))
The photopolymerization initiator (D) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, and a compound which generates radicals by light is preferable.
Examples of the photopolymerization initiator (D) include: alpha-diketones such as methyl phenylglyoxylate, 9,10-phenanthrenequinone; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and the like; benzophenones such as benzophenone, 4,4 '-bis (dimethylamino) benzophenone, 4,4' -bis (diethylamino) benzophenone, and the like; acetophenones such as acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2' -dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone; aminobenzoic acids such as ethyl 2-dimethylaminobenzoate and ethyl 4-dimethylaminobenzoate (n-butoxy) ethyl; halides such as 2-chloroacetophenone and trihalomethylphenylsulfone; acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; peroxides such as di-tert-butyl peroxide; oxime esters such as 1- [4- (phenylthio) phenyl ] -1,2-octanedione 2- (O-benzoyloxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), and aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, N-butylamine, N-methyldiethanolamine, and diethylaminoethylmethacrylate.
Of the photopolymerization initiators (D), benzophenones, aminobenzoic acids, and aliphatic amines are preferred because they exhibit a sensitizing effect when used together with other radical initiators.
As the photopolymerization initiator (D), preferred are: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 1- [4- (phenylthio) phenyl ] -1,2-octanedione 2- (O-benzoyl oxime), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyl oxime), or 2,4-diethylthioxanthone. Furthermore, combinations of these with benzophenones, for example 4,4' -bis (diethylamino) benzophenone, are particularly preferred. The photopolymerization initiator (D) may be used alone in 1 kind or in combination of 2 or more kinds.
The content of the photopolymerization initiator (D) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 15% by mass. When the content ratio is within the above range, the negative photosensitive resin composition is excellent in photocurability and developability.
(solvent (E))
The negative photosensitive resin composition of the present invention contains the solvent (E) to reduce the viscosity, and the negative photosensitive resin composition can be easily applied to the surface of the substrate. As a result, a coating film of the negative photosensitive resin composition having a uniform film thickness can be formed. As the solvent (E), a known solvent can be used. The solvent (E) may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the solvent (E) include: alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent oils, water, and the like. Among them, at least 1 solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable, and at least 1 solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N-dimethyl isobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-N-butoxy-N, N-dimethylpropionamide, and 2-propanol is more preferable.
In particular, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N-dimethyl isobutyramide, 3-methoxy-N, N-dimethylpropionamide, and 3-N-butoxy-N, N-dimethylpropionamide have a boiling point of 150 ℃ or higher, and thus, uneven coating tends to be suppressed.
When the solvent (E) contains water, the content of water is preferably 10% by mass or less of the entire solvent (E). When the content is within the above range, the unevenness of the pattern substrate formed of the partition wall formed of the cured film obtained from the negative photosensitive resin composition of the present invention can be reduced. The content of water is more preferably 1 to 10% by mass. When the amount is within the above range, the dispersion stability of the composition is good.
The content of the solvent (E) in the negative photosensitive resin composition is preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and particularly preferably 50 to 90% by mass, based on the total amount of the composition. The amount of the crosslinking agent (B) is preferably 0.1 to 3000% by mass, and more preferably 0.5 to 2000% by mass, based on 100% by mass of the total of the alkali-soluble resin (a) and the crosslinking agent (B).
(other Components)
(thiol Compound (G))
The thiol compound (G) optionally contained in the negative photosensitive resin composition of the present invention is a compound having 2 or more mercapto groups in 1 molecule. When the negative photosensitive resin composition of the present invention contains a thiol compound (G), the following so-called ene-thiol reaction occurs: the radical of the thiol compound (G) is generated by the radical generated from the photopolymerization initiator (D) at the time of exposure, and acts on the ethylenic double bond of the alkali-soluble resin (a), the crosslinking agent (B), and other components contained in the negative photosensitive resin composition. Unlike the case of radical polymerization of general olefinic double bonds, the ene-thiol reaction has the following advantages: the polymer is free from reaction inhibition by oxygen, has high chain transfer properties, and is crosslinked simultaneously with polymerization, so that the shrinkage rate of the polymer when cured is low, and a uniform network can be easily obtained.
When the negative photosensitive resin composition of the present invention contains the thiol compound (G), it can be sufficiently cured even with a low exposure amount as described above, and particularly, it can be sufficiently photocured in the upper layer portion including the upper surface of the partition wall which is easily inhibited from reaction by oxygen, and therefore, it is possible to impart good ink repellency to the upper surface of the partition wall.
The thiol compound (G) preferably contains 2 to 10 mercapto groups, more preferably 2 to 8 mercapto groups, and still more preferably 2 to 5 mercapto groups in 1 molecule. From the viewpoint of storage stability of the negative photosensitive resin composition, 3 are particularly preferable.
The molecular weight of the thiol compound (G) is not particularly limited. The mercapto equivalent represented by [ molecular weight/number of mercapto groups ] in the thiol compound (G) is preferably 40 to 1000, more preferably 40 to 500, and particularly preferably 40 to 250, from the viewpoint of curability at low exposure.
Specific examples of the thiol compound (G) include: tris (2-mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutanoate), trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, dipentaerythritol hexamercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, dipentaerythritol hexa (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutanoate), pentaerythritol tetrakis (3-mercaptobutanoate), dipentaerythritol hexa (3-mercaptobutanoate), trimethylolpropane tris (2-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -52 zxft 52-triazine-2,4,6 (1H, 3H, 5H) -trione, triphenolmethanetris (3-mercaptopropionate), triphenolmethanetris (3-mercaptobutanoate), trimethylolethane tris (3-mercaptobutanoate), 3425-trimercaptobutyrate, and the like. The thiol compound (G) may be used alone in 1 kind or in combination of 2 or more kinds.
When the negative photosensitive resin composition contains the thiol compound (G), the content ratio thereof is preferably such that the mercapto group is in an amount of 0.0001 to 1 mol, more preferably 0.0005 to 0.5 mol, and particularly preferably 0.001 to 0.5 mol, based on 1 mol of the ethylenic double bond in the entire solid content in the negative photosensitive resin composition. The amount of the alkali-soluble resin (a) is preferably 0.1 to 1200 mass%, more preferably 0.2 to 1000 mass%, based on 100 mass% of the alkali-soluble resin (a). When the content ratio of the thiol compound (G) is in the above range, the negative photosensitive resin composition is excellent in photocurability and developability even with a low exposure amount.
(phosphoric acid Compound (H))
The negative photosensitive resin composition of the present invention may optionally contain a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate, a transparent electrode material such as ITO, or the like.
The phosphoric acid compound (H) is not particularly limited as long as it can improve the adhesion of the cured film to a substrate, a transparent electrode material, or the like, and is preferably a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule.
As the phosphoric acid compound having an ethylenically unsaturated double bond in the molecule, a phosphoric acid (meth) acrylate compound, that is, a compound having at least an O = P structure derived from phosphoric acid and an ethylenically unsaturated double bond derived from a (meth) acrylic compound, that is, a (meth) acryloyl group, in the molecule, and a vinyl phosphate compound are preferable.
Examples of the phosphoric acid (meth) acrylate compound used in the present invention include: mono (2- (meth) acryloyloxyethyl) acid phosphate, bis (2-acryloyloxyethyl) acid phosphate, tris ((meth) acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) hexanoate acid phosphate, and the like.
As the phosphoric acid compound (H), in addition to a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule, phenylphosphonic acid or the like can be used.
The negative photosensitive resin composition of the present invention may contain 1 compound classified into the above-mentioned phosphate compound (H) alone, or may contain 2 or more compounds.
When the negative photosensitive resin composition contains the phosphoric acid compound (H), the content thereof is preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, based on the total solid content in the negative photosensitive resin composition. The amount of the alkali-soluble resin (A) is preferably 0.01 to 200% by mass, more preferably 0.1 to 100% by mass, based on 100% by mass of the alkali-soluble resin (A). When the content ratio of the phosphoric acid compound (H) is within the above range, the obtained cured film has good adhesion to a substrate or the like.
The negative photosensitive resin composition of the present invention may further contain 1 or more other additives selected from the group consisting of a polymerization inhibitor, a thermal crosslinking agent, a polymeric dispersant, a dispersion aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, and a shrinkage preventing agent, as necessary.
The negative photosensitive resin composition of the present invention can be obtained by mixing the above components in predetermined amounts. The negative photosensitive resin composition of the present invention can exhibit an effect particularly when used for forming a cured film or a partition wall used in an optical device, for example, an organic EL device, a quantum dot display, a TFT array, or a thin film solar cell. When the negative photosensitive resin composition of the present invention is used, a partition wall having good ink repellency on the upper surface and good development adhesion to a substrate can be produced, and the amount of development residue in the opening partitioned by the partition wall is sufficiently small.
[ partition wall ]
The partition wall of the present invention is formed in a shape of dividing the surface of the substrate into a plurality of sections for forming dots, and is formed of the cured film of the negative photosensitive resin composition of the present invention. The partition wall can be obtained, for example, as follows: the negative photosensitive resin composition of the present invention is applied to the surface of a base material such as a substrate, and if necessary, dried to remove a solvent or the like, and then a portion to be a partition for dot formation is masked and exposed to light and developed. The unexposed portion is removed by masking by development, and an opening corresponding to the partition for dot formation is formed together with the partition.
As described above, the partition wall according to the embodiment of the present invention has excellent ink repellency on the upper surface and excellent development adhesion to the substrate, and the amount of development residue is sufficiently small at the opening portions partitioned by the partition wall. Thus, when the ink is used for an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell manufactured by the IJ method, a remarkable effect is exhibited that the ink is uniformly applied to the opening and dots can be formed with high accuracy.
An example of a method for manufacturing a partition wall according to an embodiment of the present invention will be described below with reference to fig. 1A to 1D, but the method for manufacturing a partition wall is not limited to the following. The following production method is described in the case where the negative photosensitive resin composition contains the solvent (E).
As shown in fig. 1A, a negative photosensitive resin composition is applied to the entire one main surface of the substrate 1 to form a coating film 21. At this time, the ink repellent (C) is dissolved and uniformly dispersed in the entire coating film 21. In fig. 1A, the ink repellent (C) is schematically shown, and is not actually present in such a particle shape.
Subsequently, as shown in fig. 1B, the coating film 21 is dried to form a dried film 22. Examples of the drying method include heat drying, drying under reduced pressure, and heat drying under reduced pressure. Although it depends on the kind of the solvent (E), the heating temperature is preferably 50 to 120 ℃ in the case of heat drying
In this drying process, the ink repellent (C) migrates to the upper layer portion of the drying film. Even when the negative photosensitive resin composition does not contain the solvent (E), the migration of the upper surface of the ink repellent (C) can be similarly realized in the coating film.
Next, as shown in fig. 1C, the dry film 22 is irradiated with light and exposed through a photomask 30 having a mask portion 31 having a shape corresponding to the opening surrounded by the partition wall. The film obtained by exposing the dried film 22 to light is referred to as an exposed film 23. In the exposed film 23, the exposed portion 23A is photocured, and the unexposed portion 23B is in the same state as the dried film 22.
Examples of the light to be irradiated include visible light; ultraviolet rays; extreme ultraviolet light; krF excimer laser, arF excimer laser, and F 2 Excimer laser, kr 2 Excimer laser, krAr excimer laser and Ar 2 Excimer laser such as excimer laser; x-rays; electron beam, etc
The light to be irradiated is preferably light having a wavelength of 100 to 600nm, more preferably light having a wavelength of 300 to 500nm, and particularly preferably light including i-ray (365 nm), h-ray (405 nm) or g-ray (436 nm). In addition, light of 330nm or less can be cut off as necessary.
Examples of the exposure method include batch exposure over the entire surface, scanning exposure, and the like. The exposure may be performed in a plurality of times for the same position. In this case, the exposure conditions for the plural times may be the same or different.
The exposure dose is preferably, for example, 5 to 1000mJ/cm in any of the above exposure modes 2 More preferably 5 to 500mJ/cm 2 More preferably 5 to 300mJ/cm 2 Particularly preferably 5 to 200mJ/cm 2 Most preferably 5 to 50mJ/cm 2 . The exposure amount may be determined according to the wavelength of the irradiated light, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the likeIs suitable for optimization.
The exposure time per unit area is not particularly limited, and is designed according to the exposure power of the exposure apparatus used, the required exposure amount, and the like. In the case of scanning exposure, the exposure time is determined from the scanning speed of light. The exposure time per unit area is usually about 1 to 60 seconds.
Next, as shown in fig. 1D, development using an alkali developer is performed to form the partition wall 4 composed only of the portion corresponding to the exposure portion 23A of the exposure film 23. The opening 5 surrounded by the partition wall 4 is a portion of the exposed film 23 where the unexposed portion 23B has been present, and fig. 1D shows a state where the unexposed portion 23B is removed by development. Since the negative photosensitive resin composition has acidic groups in the alkali-soluble resin (a), the crosslinking agent (B), and the ink-repellent agent (C), the composition is easily dissolved and removed in the unexposed area 23B by an alkali developer, and the composition hardly remains in the opening 5. On the other hand, the partition wall 4 which is a cured product of the negative photosensitive resin composition is excellent in development adhesion, and therefore, sufficiently adheres to the substrate 1 even after development.
In the partition wall 4 shown in fig. 1D, the uppermost layer including the upper surface thereof is an ink-repellent layer 4A. When the ink-repellent agent (C) does not have a side chain having an ethylenic double bond, the ink-repellent agent (C) is present directly in a high concentration in the uppermost layer at the time of exposure to light to form an ink-repellent layer. Upon exposure, the alkali-soluble resin (a) present around the ink repellent (C), the thiol compound (G) optionally contained, and the other photocurable component are firmly photocured, and the ink repellent (C) is fixed in the ink repellent layer.
When the ink repellent (C) has a side chain having an ethylenic double bond, the ink repellents (C) are photocured together with each other and/or the alkali-soluble resin (a), the thiol compound (G) optionally contained, and other photocuring components to form an ink repellent layer 4A in which the ink repellents (C) are firmly bonded.
In any case, the following is the case: on the lower side of the ink-repellent layer 4A, the main alkali-soluble resin (a) and the thiol compound (G) optionally contained, and the other photocurable component are photocured to form a layer 4B containing almost no ink-repellent agent (C).
Conventionally, when the ink repellent has an acidic group, there is a problem that the ink-repellent layer formed on the uppermost layer of the partition wall is easily removed at the time of development. In the present invention, by using the ink-repellent agent (C) having an acid value limited to a predetermined range, dissolution and removal by an alkaline developer can be easily performed in a non-exposed portion during development, and the ink-repellent layer 4A formed on the uppermost layer of the partition wall 4 is hardly affected by the alkaline developer and remains. In addition, the ink-repellent agent (C) is sufficiently fixed in the partition wall including the ink-repellent layer 4A and the lower layer 4B thereof, and thus hardly migrates to the opening portion at the time of development.
After development, the partition walls 4 may be further heated. The heating temperature is preferably 130 to 250 ℃. The solidification of the partition wall 4 becomes stronger by heating. In addition, the ink-repellent agent (C) is more firmly fixed within the ink-repellent layer 4A.
The thus obtained resin cured film of the present invention and the partition wall 4 have good ink repellency of the upper surface even when exposed to light at a low exposure amount. In addition, with respect to the partition wall 4, there is almost no ink repellent (C) at the opening 5 after development, and uniform coating property of ink at the opening 5 can be sufficiently ensured.
In order to more reliably obtain the ink affinity of the opening 5, the substrate 1 with the partition wall 4 may be subjected to ultraviolet/ozone treatment after the heating to remove development residue and the like of the negative photosensitive resin composition that may be present in the opening 5.
The partition wall formed of the negative photosensitive resin composition of the present invention has a width of, for example, preferably 100 μm or less, and particularly preferably 20 μm or less. The distance between adjacent partition walls (the width of the pattern) is preferably 300 μm or less, and particularly preferably 100 μm or less. The height of the partition wall is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 10 μm.
When the partition wall formed of the negative photosensitive resin composition of the present invention is formed to have the above-described width, the edge portion has few irregularities and is excellent in linearity. In particular, when the resin (a-2) obtained by introducing an acid group and an olefinic double bond into an epoxy resin as an alkali-soluble resin is used, the development of high linearity in the partition wall is remarkable. Thus, even a fine pattern can be formed with high accuracy. Such high-precision patterning is useful as a partition wall for an organic EL element in particular.
The partition wall of the present invention can be used as a partition wall having an opening as an ink injection region when pattern printing is performed by the IJ method. When the partition wall of the present invention is used in a state in which the opening portion thereof is aligned with the desired ink injection region in pattern printing by the IJ method, the upper surface of the partition wall has good ink repellency, and therefore, it is possible to prevent ink from being injected into the ink injection region, which is an undesired opening portion, over the partition wall. Further, since the ink has good wet spreading properties in the opening surrounded by the partition wall, the ink can be uniformly printed in a desired area without causing a void or the like.
When the partition wall of the present invention is used, as described above, pattern printing by the IJ method can be performed precisely. Therefore, the partition wall of the present invention is useful as a partition wall of an optical element, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, having a plurality of dots and a partition wall located between adjacent dots on a surface of a substrate on which the dots are formed by the IJ method.
[ optical element ]
The organic EL element, the quantum dot display, the TFT array, or the thin-film solar cell, which is the optical element of the present invention, is an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell having a plurality of dots and the partition wall of the present invention located between the adjacent dots on the surface of the substrate. For the optical element (organic EL element, quantum dot display, TFT array, or thin film solar cell) of the present invention, it is preferable to form dots by the IJ method.
The organic EL element has a structure in which a light-emitting layer of an organic thin film is sandwiched between an anode and a cathode, and the partition wall of the present invention can be used for a partition wall for partitioning an organic light-emitting layer, a partition wall for partitioning an organic TFT layer, a partition wall for partitioning a coating-type oxide semiconductor, and the like.
In addition, the organic TFT array element refers to an element as follows: the plurality of dots are arranged in a matrix shape in a plan view, and pixel electrodes and TFTs as switching elements for driving the pixel electrodes are provided at each dot, and an organic semiconductor layer is used as a semiconductor layer of a channel layer including the TFTs. The organic TFT array element can be provided as a TFT array substrate in an organic EL element, a liquid crystal element, or the like, for example.
In the optical element according to the embodiment of the present invention, for example, an organic EL element, an example in which dots are formed in an opening by the IJ method using the partition wall obtained as described above will be described below. The method for forming dots in an optical element such as an organic EL element according to the present invention is not limited to the following.
Fig. 2A and 2B schematically illustrate a method of manufacturing an organic EL element using the partition wall 4 formed on the substrate 1 illustrated in fig. 1D described above. Here, the partition wall 4 on the substrate 1 is formed so that the opening 5 matches the dot pattern of the organic EL element to be manufactured.
As shown in fig. 2A, ink 10 is dropped from the ink jet head 9 to the opening 5 surrounded by the partition wall 4, and a predetermined amount of the ink 10 is injected into the opening 5. As the ink, ink known as an organic EL element can be appropriately selected and used in accordance with the function of the dot.
Next, depending on the type of ink 10 used, a treatment such as drying and/or heating is performed to remove the solvent and cure the ink, thereby obtaining an organic EL element 12 in which desired dots 11 are formed so as to be adjacent to the partition walls 4 as shown in fig. 2B.
The optical element (organic EL element, quantum dot display, TFT array, or thin-film solar cell) according to the embodiment of the present invention is an optical element (organic EL element, quantum dot display, TFT array, or thin-film solar cell) having dots formed with high accuracy by using the partition wall of the present invention, whereby ink can be uniformly wet-spread without unevenness in the opening portions partitioned by the partition wall during the manufacturing process.
The organic EL element can be manufactured as follows, for example, but is not limited thereto.
A light-transmissive electrode such as tin-doped indium oxide (ITO) is formed on a light-transmissive substrate such as glass by sputtering or the like. The light-transmissive electrode is patterned as necessary.
Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in a plan view along the outline of each point by a photolithography method including coating, exposure, and development. Next, materials for the hole injection layer, the hole transport layer, the light-emitting layer, the hole blocking layer, and the electron injection layer were applied to the opening for dot formation by the IJ method, and then dried, and these layers were sequentially stacked. The kind and number of organic layers formed in the dot forming openings are appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
The quantum dot display can be manufactured as follows, for example, but is not limited thereto.
A light-transmissive electrode such as ITO is formed on a light-transmissive substrate such as glass by a sputtering method or the like. The light-transmissive electrode may be patterned as desired. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in a plan view along the outline of each point by a photolithography method including coating, exposure, and development. Next, materials for the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer were applied to the inside of the dot formation openings by the IJ method, and then dried, and these layers were sequentially stacked. The kind and number of organic layers formed in the dot forming openings are appropriately designed. Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
Further, the optical element according to the embodiment of the present invention can be applied to, for example, a blue light conversion type quantum dot display manufactured as described below.
The negative photosensitive resin composition of the present invention is used to form partition walls in a lattice shape in a plan view along the outline of each point on a transparent substrate such as glass. Next, in the opening for dot formation, a nanoparticle solution for converting blue light into green light, a nanoparticle solution for converting blue light into red light, and a blue color ink as needed are applied by the IJ method and dried to produce a device. By using a light source emitting blue as a backlight and using the above-described components as a substitute for a color filter, a liquid crystal display excellent in color reproducibility can be obtained.
The TFT array can be manufactured as follows, for example, but is not limited thereto.
A gate electrode of aluminum, an alloy thereof, or the like is formed on a translucent substrate of glass or the like by sputtering or the like. The gate is patterned as desired.
Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like. A source electrode and a drain electrode may be formed on the gate insulating film. The source electrode and the drain electrode can be formed by forming a metal thin film of aluminum, gold, silver, copper, an alloy thereof, or the like by vacuum evaporation or sputtering, for example. As a method of patterning the source electrode and the drain electrode, the following methods can be cited: after the metal thin film is formed, a resist layer is applied, exposed, and developed, and the resist layer is left on the portion where the electrode is to be formed, and then the exposed metal is removed with phosphoric acid, aqua regia, or the like, and finally the resist layer is removed.
In addition, when forming a metal thin film of gold or the like, there is a method of: after a metal thin film is formed by applying a resist layer in advance, exposing and developing the resist layer to leave the resist layer in a portion where an electrode is not to be formed, the metal thin film is removed together with the photoresist layer. The source electrode and the drain electrode may be formed by an ink jet method or the like using a metal nano-colloid such as silver or copper. Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in plan view along the outline of each point by a photolithography method including coating, exposure, and development.
Next, a semiconductor solution was applied to the opening for dot formation by the IJ method, and the solution was dried to form a semiconductor layer. As the semiconductor solution, an organic semiconductor solution or an inorganic coating type oxide semiconductor solution may be used. The source electrode and the drain electrode may be formed by an ink-jet method or the like after the semiconductor layer is formed. Finally, a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 9 are examples, and examples 10 to 16 are comparative examples.
Each measurement was performed by the following method.
[ number average molecular weight (Mn) and Mass average molecular weight (Mw) ]
Gel Permeation Chromatography (GPC) of several kinds of monodisperse polystyrene polymers having different polymerization degrees, which are commercially available as standard samples for molecular weight measurement, was measured using a commercially available GPC measurement apparatus (manufactured by Tosoh corporation, apparatus name: HLC-8320 GPC). A calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time (retention time).
Each sample was diluted to 1.0 mass% with tetrahydrofuran, passed through a 0.5 μm filter, and then subjected to GPC measurement using the above-mentioned apparatus. Using the calibration curve, the number average molecular weight (Mn) and the mass average molecular weight (Mw) of the sample were determined by computer analysis of the GPC spectrum.
[ PGMEA contact Angle ]
PGMEA droplets were placed on 3 positions of the measurement surface on the base material according to JIS R3257 "wettability test method for substrate glass surface" by the static drop method, and each PGMEA droplet was measured. The drop size was 2. Mu.L/drop, and the measurement was carried out at 20 ℃. The contact angle was determined from the average of 3 measurements (n = 3). Note that PGMEA is an abbreviation of propylene glycol monomethyl ether acetate.
Abbreviations for the compounds used in the respective examples are as follows.
(alkali-soluble resin (A))
A-1: a resin solution (solid content: 70% by mass, acid value: 60mgKOH/g, mass average molecular weight: 9.2X 10) obtained by reacting a cresol novolak type epoxy resin with acrylic acid, followed by reaction with 1,2,3,6-tetrahydrophthalic anhydride, and purifying the resin having an acryloyl group and a carboxyl group introduced thereto with hexane 3 )。
A-2: a polyurethane compound solution (solid content 65 mass%, acid value 79.32 mgKOH/g) obtained by reacting RE-310S (bifunctional bisphenol-A epoxy resin, epoxy equivalent: 184.0 g/eq, manufactured by Japan chemical Co., ltd.) with acrylic acid, followed by dimethylolpropionic acid and trimethylhexamethylene diisocyanate, and finally with glycidyl methacrylate, as described in example 1 (paragraph 0045) of Japanese patent application laid-open No. 2003-268067.
(multifunctional Low molecular weight Compound (B1))
B1-1:2,2,2-triacrylate-yloxymethylethylphthalic acid (acid number 87mgKOH/g, molecular weight 446).
B1-2: succinic acid ester of dipentaerythritol pentaacrylate (acid value 92mgKOH/g, molecular weight 612).
(non-acidic crosslinking agent (B2))
B2-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
(raw Material for ink repellent (C1))
C6FMA：CH 2 ＝C(CH 3 )COOCH 2 CH 2 (CF 2 ) 6 F
MAA: methacrylic acid
2-HEMA: 2-Hydroxyethyl methacrylate
V-65: (2,2' -azobis (2,4-dimethylvaleronitrile))
n-DM: n-dodecyl mercaptan
BEI:1,1- (bisacryloxymethyl) ethyl isocyanate.
DBTDL: dibutyl tin dilaurate
TBQ: tert-butyl p-benzoquinone
MEK: 2-butanone
(raw Material for ink repellent (C2))
A compound (cx-1) corresponding to the compound (s 1): f (CF) 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 (produced by a known method).
Starting materials for Compound (cx-21) and Compound (cx-22) corresponding to Compound (s 2)
AC: acrylic acid
MMA: methacrylic acid methyl ester
AIBN: azobisisobutyronitrile (AIBN)
V-65: (2,2' -azobis (2,4-dimethylvaleronitrile))
3-mercaptopropyltrimethoxysilane
PGME: propylene glycol monomethyl ether
A compound (cx-3) corresponding to the compound (s 3): si (OC) 2 H 5 ) 4 。
A compound (cx-4) corresponding to the compound (s 4): CH (CH) 2 ＝CHCOO(CH 2 ) 3 Si(OCH 3 ) 3 。
A compound (cx-51) corresponding to the compound (s 5): SH (CH) 2 ) 3 Si(OCH 3 ) 3 。
A compound (cx-52) corresponding to the compound (s 5): bis- [3- (triethoxysilyl) propyl ] -tetrasulfide
A compound (cx-6) corresponding to the compound (s 6): (CH) 3 ) 3 SiOCH 3 。
(photopolymerization initiator (D))
D-1: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one.
D-2:4,4' -bis (diethylamino) benzophenone.
(solvent (E))
E-1: PGME: propylene glycol monomethyl ether.
E-2: PGMEA: propylene glycol monomethyl ether acetate.
E-3: EDGAC: diethylene glycol monoethyl ether acetate.
E-4: DMIB: n, N-dimethyl isobutyramide.
[ Synthesis of ink repellent (C) ]
The ink repellents (C1-1), the ink repellents (C2-1) to (C2-3) used in the examples and the ink repellents (Cf-1) to (Cf-3) used in the comparative examples were synthesized as follows.
(Synthesis example 1 Synthesis of ink repellent (C1-1))
To an internal volume of 1000cm equipped with a stirrer 3 Into an autoclave of (2A) were charged 415.1g of MEK, 81.0g of C6FMA, 18.0g of MAA, 81.0g of 2-HEMA, 5.0g of polymerization initiators V-65 and 4.7g of n-DM4, and polymerization was carried out at 50 ℃ for 24 hours while stirring under a nitrogen atmosphere, and further at 70 ℃ for 5 hours to inactivate the polymerization initiators, thereby obtaining aA solution of the copolymer is obtained. The number average molecular weight of the copolymer was 5540, and the mass average molecular weight was 13200.
Next, the mixture was poured into a 300cm inner volume equipped with a stirrer 3 130.0g, BEI33.5g, DBTDL0.13g, and TBQ1.5g of the copolymer solution were charged into the autoclave, and reacted at 40 ℃ for 24 hours while stirring, thereby synthesizing a crude polymer. Hexane was added to the obtained solution of the crude polymer to carry out reprecipitation purification, followed by vacuum drying, whereby 65.6g of an ink repellent (C1-1) was obtained. Then, the resulting solution was diluted with PGMEA to obtain a PGMEA solution of the ink-repellent agent (C1-1) (concentration of the ink-repellent agent (C1-1): 10% by mass, hereinafter also referred to as "ink-repellent agent (C1-1) solution").
The ink repellent (C1-1) had a number average molecular weight (Mn) of 7540, a mass average molecular weight (Mw) of 16200, a fluorine atom content of 14.1 (mass%), a C = C content of 3.79 (mmol/g), and an acid value of 35.7 (mgKOH/g).
( Synthesis example 2: synthesis of hydrolyzable silane Compound (cx-21) )
To 50cm equipped with a stirrer and a thermometer 3 Into the three-necked flask of (1) was charged 0.40g of 3-mercaptopropyltrimethoxysilane, 2.06g of MMA, 1.48g of AC1, 0.05g of V-65 and 35.59g of PGME35, and the mixture was stirred at 60 ℃ for 12 hours. It was confirmed by gas chromatography that the peaks of the starting materials, 3-mercaptopropyltrimethoxysilane, MMA and AC, disappeared to obtain a PGME solution (concentration: 10 mass%) of the hydrolyzable silane compound (cx-21).
(Synthesis example 3 preparation of ink repellent (C2-1))
To 50cm equipped with a stirrer 3 Into the three-necked flask of (1) was charged 0.35g of the compound (cx-1), 1.03g of a PGME solution of the compound (cx-21), 0.56g of the compound (cx-3) and 0.63g of the compound (cx-4), to obtain a mixture of hydrolyzable silane compounds. Subsequently, 6.67g of PGME6 was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.76g of a 1% aqueous hydrochloric acid solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of an ink-repellent agent (C2-1) (concentration of the ink-repellent agent (C2-1): 10% by mass, hereinafter also referred to as "ink-repellent agent (C2-1) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-1) was 1105, the mass average molecular weight (Mw) was 2082, the content of fluorine atoms was 18.2 (mass%), the content of C = C was 2.69 (mmol/g), and the acid value was 32.8 (mgKOH/g).
Synthesis example 4 preparation of ink repellent (C2-2) liquid)
To 50cm of the vessel equipped with a stirrer 3 Into the three-necked flask of (1) was charged 0.38g of the compound (cx-1), 1.09g of a PGME solution of the compound (cx-21), 0.59g of the compound (cx-3), 0.44g of the compound (cx-4), 0.05g of the compound (cx-6) and 0.22g of the compound (cx-51), to obtain a mixture of hydrolyzable silane compounds. Subsequently, 6.37g of PGME6 was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.85g of a 1% aqueous hydrochloric acid solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of an ink-repellent agent (C2-2) (concentration of the ink-repellent agent (C2-2): 10% by mass, hereinafter also referred to as "ink-repellent agent (C2-2) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-2) was 945, the mass average molecular weight (Mw) was 1944, the content of fluorine atoms was 18.2 (mass%), the content of C = C was 1.73 (mmol/g), and the acid value was 31.6 (mgKOH/g).
( Synthesis example 5: synthesis of hydrolyzable silane Compound (cx-22) )
To 50cm of a vessel equipped with a stirrer and a thermometer 3 Into the three-necked flask was charged 0.40g of 3-mercaptopropyltrimethoxysilane, 1.00g of MMA, 2.20g of AC2.03g, 0.03g of AIBN and 31.50g of PGME31, and the mixture was stirred at 60 ℃ for 12 hours. It was confirmed by gas chromatography that the peaks of the starting materials, 3-mercaptopropyltrimethoxysilane, MMA and AC, disappeared to obtain a PGME solution (concentration: 10 mass%) of the hydrolyzable silane compound (cx-22).
Synthesis example 6 preparation of ink repellent (C2-3) solution
To 50cm equipped with a stirrer 3 Into a three-necked flask of (2) was charged 0.38g of compound (cx-1) and 0.90 g of a PGME solution of compound (cx-22)g. 0.28g of the compound (cx-3), 0.21g of the compound (cx-4), 0.06g of the compound (cx-6), and 0.33g of the compound (cx-52) gave a mixture of hydrolyzable silane compounds. Next, PGME6.88g was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.47g of a 1% aqueous hydrochloric acid solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of an ink-repellent agent (C2-3) (concentration of the ink-repellent agent (C2-3): 10% by mass, hereinafter also referred to as "ink-repellent agent (C2-3) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (C2-3) was 1330, the mass average molecular weight (Mw) was 2980, the content of fluorine atoms was 23.1 (mass%), the content of C = C was 1.05 (mmol/g), and the acid value was 50.3 (mgKOH/g).
Synthesis example 7 preparation of ink repellent (Cf-1)
To 50cm of the vessel equipped with a stirrer 3 Into the three-necked flask of (1), 0.22g of the compound (cx-1), 4.27g of the compound (cx-22), 0.36g of the compound (cx-3) and 0.40g of the compound (cx-4) were charged to obtain a mixture of hydrolyzable silane compounds. Subsequently, pgme4.22g was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.53g of a 1% aqueous hydrochloric acid solution was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of the ink-repellent agent (Cf-1) (concentration of the ink-repellent agent (Cf-1): 10% by mass, hereinafter also referred to as "ink-repellent agent (Cf-1) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-1) was 1130, the mass average molecular weight (Mw) was 2170, the content of fluorine atoms was 11.4 (mass%), the content of C = C was 1.76 (mmol/g), and the acid value was 227.1 (mgKOH/g).
Synthesis example 8 preparation of ink repellent (Cf-2)
To 50cm of the vessel equipped with a stirrer 3 Into a three-necked flask of (1) was charged 0.38g of the compound (cx-1) and the compound (cx-3)) 0.55g of the compound (cx-4), 0.41g of the compound (cx-6), and 0.21g of the compound (cx-51) were added to prepare a mixture of hydrolyzable silane compounds. Subsequently, PGME7.52g was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.81g of a 1% aqueous hydrochloric acid solution was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of an ink-repellent agent (Cf-2) (concentration of the ink-repellent agent (Cf-2): 10% by mass, hereinafter also referred to as "ink-repellent agent (Cf-2) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-2) was 678, the mass average molecular weight (Mw) was 745, the fluorine atom content was 20.0 (mass%), and the content of C = C was 1.76 (mmol/g). The ink repellent (Cf-2) has no acidic group and therefore has an acid value of 0 (mgKOH/g).
Synthesis example 9 preparation of ink repellent (Cf-3)
To 50cm of the vessel equipped with a stirrer 3 Into the three-necked flask of (1), 0.38g of the compound (cx-1), 0.31g of the compound (cx-3), 0.23g of the compound (cx-4), 0.06g of the compound (cx-6) and 0.34g of the compound (cx-52) were charged to obtain a mixture of hydrolyzable silane compounds. Subsequently, PGME6.43g was added to the mixture as a raw material solution.
To the obtained raw material solution, 0.50g of a 1% aqueous hydrochloric acid solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain a PGME solution of the ink-repellent agent (Cf-3) (concentration of the ink-repellent agent (Cf-3): 10% by mass, hereinafter also referred to as "ink-repellent agent (Cf-3) solution").
After the completion of the reaction, the components of the reaction solution were measured by gas chromatography, and it was confirmed that each compound as a raw material was not more than the detection limit. The number average molecular weight (Mn) of the obtained ink repellent (Cf-3) was 1030, the mass average molecular weight (Mw) was 1520, the content of fluorine atoms was 24.3 (mass%), and the content of C = C was 1.19 (mmol/g). The ink-repellent agent (Cf-3) has no acidic group and therefore has an acid value of 0 (mgKOH/g).
[ example 1: production of negative photosensitive resin composition and production of cured film (partition wall) ]
(production of negative photosensitive resin composition)
At 200cm 3 The (C1-1) solution obtained in Synthesis example 1 (0.25 g), 16.07g A-1 (11.25 g of solid content, EDGAC as residual solvent), 6.25g B1-1, 5.00g B2-1, 1.50g D-1, 0.75g D-2, 70.18g E-1 were placed in the stirring vessel of (1), and stirred for 5 hours to prepare a negative photosensitive resin composition. Table 1 shows the solid content concentration (mass%) of the negative photosensitive resin composition, the composition (mass%) of the solid content in the negative photosensitive resin composition, the composition (mass%) of the solvent, and the ratio (mass%) of the multifunctional low-molecular weight compound (B1) to the total of the multifunctional low-molecular weight compound (B1) and the non-acidic crosslinking agent (B2).
(production of cured film 1)
A10 cm square ITO substrate (a glass substrate on which Indium-Tin-Oxide (Indium-Tin-Oxide) was formed) was ultrasonically cleaned in ethanol for 30 seconds, and then subjected to UV/O for 5 minutes 3 And (6) processing. UV/O 3 The treatment used PL2001N-58 (SEN ENGINEERING CO., LTD.) (manufactured by LTD.) as UV/O 3 A generating device. The light quantity (light output) was 10mW/cm in terms of 254nm 2 . All UV/O described below 3 The treatment uses the device.
The surface of the cleaned ITO substrate was coated with the negative photosensitive resin composition using a spin coater, and then dried on a hot plate at 100 ℃ for 2 minutes to form a dried film having a thickness of 2.4 μm. The obtained dried film was irradiated with light of an exposure amount (exposure output) of 25mW/cm in terms of 365nm over the entire surface thereof through a photomask having an opening pattern (the opening (exposure portion) was formed by repeating patterns of 1,2,3, 4, 5, 6, 7, 8, 9,10, 12, 14, 16, 18, 20, 30, 40, and 50 μm × 1000 μm (the interval between patterns was 50 μm)) in a range of 20mm × 20mm 2 UV light of the ultra-high pressure mercury lamp of (1). During exposure, light below 330nm was cut off. The separation distance between the dry film and the photomask was set to 50 μm. In each example, exposure conditions: the exposure time was 6 seconds and the exposure amount was 150mJ/cm 2 。
Next, the ITO substrate after the exposure treatment was immersed in a 0.4 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds to be developed, and the unexposed portions were washed with water and dried. Subsequently, the substrate was heated at 230 ℃ for 60 minutes on a hot plate, thereby obtaining an ITO substrate having a cured film (partition wall) 1 having a pattern corresponding to the opening pattern of the photomask.
(production of cured film 2)
Further, a dry film of the negative photosensitive resin composition was formed on the surface of the ITO substrate in the same manner as described above, and the exposure amount was 150mJ/cm under the same exposure conditions as described above, using a photomask (the size of the light-shielding portion: 100. Mu. M.times.200. Mu.m, and the width of the opening (exposure portion): 20 μm, in which a lattice pattern was repeated in a range of 20 mm.times.20 mm) 2 The dried film was exposed to light, developed under the same conditions as those described above, and heated on a hot plate at 230 ℃ for 60 minutes, thereby obtaining an ITO substrate with a cured film 2 in a pattern in which dot portions (100. Mu. M.times.200 μm) were surrounded by partition walls having a line width of 20 μm.
[ examples 2 to 16]
In example 1, a negative photosensitive resin composition, a resin cured film, and a partition wall were produced in the same manner except that the composition of the negative photosensitive resin composition was changed to the composition shown in table 1 or table 2.
(evaluation)
The negative photosensitive resin compositions, the resin cured films, and the partition walls obtained in examples 1 to 16 were evaluated as follows. The results are shown in the lower column of table 1 or table 2.
< ink repellency of the upper surface of the partition wall >
The exposure amount of the resin cured film 1 was measured to be 150mJ/cm by the above-mentioned method 2 The water contact angle of the upper surface of the partition wall obtained.
Very good: the contact angle is more than 40 degrees
O: the contact angle is more than 30 degrees and less than 40 degrees
X: contact angle lower than 30 °
< IJ coatability >)
Inside the point surrounded by the partition wall of the ITO substrate having the resin cured film 2 described above, 1% of a cyclohexylbenzene solution 20pl of TPD (triphenyldiamine) was dropped using an IJ apparatus (manufactured by LaboJET 500 MICROJET Corporation). The spread of the dried product inside the dried spots was confirmed. The following criteria were used for the determination.
O: spread evenly within the spot and the material is sent to the end of the dividing wall.
X: not expanded within the dots.
< development adhesion >
The photomask (opening (exposure part) 1,2,3, 4, 5, 6, 7, 8, 9,10, 12, 14, 16, 18, 20, 30, 40, 50 μm × 1000 μm) having the opening pattern of the resin cured film 1 was observed with a microscope at an exposure dose of 150mJ/cm 2 The partition wall obtained in the above-mentioned case was judged based on the following criteria
O: lines with a mask width of less than 10 μm remain.
And (delta): the remaining lines were 10 μm or more and less than 20 μm.
X: the wires of 20 to 50 μm are left.
X: there is no line pattern.
[ Table 1]
Figure BDA0002101829690000441
[ Table 2]
Figure BDA0002101829690000451
As shown in table 1, in the negative photosensitive resin compositions corresponding to examples 1 to 9 of examples, by selecting the crosslinking agent (B) and the ink-repellent agent (C), a partition wall pattern having good liquid repellency at the upper part of the partition wall, good IJ coatability in the dot surrounded by the partition wall, and high definition can be formed.
Industrial applicability
The negative photosensitive resin composition of the present invention can be suitably used as a composition for forming a partition wall in pattern printing by the IJ method in an organic EL device, a quantum dot display, a TFT array, or a thin film solar cell.
The partition wall of the present invention can be used in an organic EL device as a partition wall (bank) for pattern-printing an organic layer such as a light-emitting layer by the IJ method, or as a partition wall (bank) for pattern-printing a quantum dot layer, a hole transport layer, or the like in a quantum dot display by the IJ method. The partition wall of the present invention can be used as a partition wall for pattern printing of a conductor pattern or a semiconductor pattern by the IJ method in a TFT array. The partition wall of the present invention can be used, for example, as a partition wall for patterning an organic semiconductor layer, a gate electrode, a source electrode, a drain electrode, a gate wiring, a source electrode wiring, and the like of a TFT, which are a channel layer, by the IJ method.
Description of the reference numerals
1 … substrate, 21 … coating film, 22 … dried film, 23 … exposed film, 23a … exposed portion, 23B … non-exposed portion, 4 … partition wall, 4a … ink repellent layer, 5 … open portion, 31 … shielded portion, 30 … photomask, 9 … inkjet head, 10 … ink, 11 … dot, 12 … organic EL element.

Claims (7)

1. A negative photosensitive resin composition comprising: an alkali-soluble resin (A) having a photocurable functional group, a crosslinking agent (B) comprising a multifunctional low-molecular-weight compound (B1) having an acid group and 3 or more photocurable functional groups in 1 molecule and having a mass average molecular weight Mw of 300 or more and less than 1000, an ink repellent (C) having an acid group and a fluorine atom and having an acid value of 10 to 100mgKOH/g, a photopolymerization initiator (D), and a solvent (E).
2. The negative photosensitive resin composition according to claim 1, wherein the multifunctional low molecular weight compound (B1) has 4 or more photocurable functional groups.
3. The negative photosensitive resin composition according to claim 1 or 2, wherein the polyfunctional low molecular weight compound (B1) has a dipentaerythritol skeleton.
4. The negative photosensitive resin composition according to claim 1 or 2, wherein the content of fluorine atoms in the ink-repellent agent (C) is 5 to 55 mass%.
5. The negative photosensitive resin composition according to claim 1 or 2, wherein the ink-repellent agent (C) comprises a photocurable functional group.
6. The negative photosensitive resin composition according to claim 1 or 2, wherein the crosslinking agent (B) further comprises a crosslinking agent (B2) having 2 or more photocurable functional groups in 1 molecule and having no acidic group.
7. The negative photosensitive resin composition according to claim 6, wherein the polyfunctional low-molecular weight compound (B1) is contained in a proportion of 10 to 90 parts by mass relative to 100 parts by mass of the total of the polyfunctional low-molecular weight compound (B1) and the crosslinking agent (B2) having 2 or more photocurable functional groups in 1 molecule and no acidic group.
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