WO2011081151A1 - Photosensitive composition, partition wall, color filter and organic el element - Google Patents
Photosensitive composition, partition wall, color filter and organic el element Download PDFInfo
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- WO2011081151A1 WO2011081151A1 PCT/JP2010/073603 JP2010073603W WO2011081151A1 WO 2011081151 A1 WO2011081151 A1 WO 2011081151A1 JP 2010073603 W JP2010073603 W JP 2010073603W WO 2011081151 A1 WO2011081151 A1 WO 2011081151A1
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- photosensitive composition
- partition
- side chain
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- 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
- H10K59/122—Pixel-defining structures or layers, e.g. banks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
Definitions
- the present invention relates to a photosensitive composition, a partition using the same, a color filter having the partition, and an organic EL device.
- partition walls between pixels of a color filter partition walls between pixels of an organic EL (Electro-Luminescence) display element, partition walls partitioning each TFT of an organic TFT (Thin Film Transistor) array, partition walls of an ITO electrode of a liquid crystal display element
- a photosensitive composition has attracted attention.
- a barrier rib pattern (which may also serve as a black matrix) is formed using photolithography, and then R (red), G (green), and B (blue) ink is applied to the openings between the partition walls to form pixels.
- an organic EL element after forming a partition pattern using photolithography, a solution such as a hole transport material and a light emitting material is applied to the opening between the partitions using an inkjet method, A pixel having a hole transport layer, a light emitting layer, and the like is formed.
- the upper surface of the partition wall needs to have a property of repelling ink, so-called liquid repellency.
- the opening between the partition walls needs to have a property of getting wet with ink, so-called lyophilic property.
- Patent Document 1 describes a photosensitive resin composition containing a repeating unit having at least a fluorine atom in a side chain and a repeating unit having a polyether structure in a side chain.
- the mass average molecular weight of the fluorine-containing compound described in the examples of Patent Document 1 is 26,000 at the maximum.
- Patent Document 2 discloses a photopolymerizable compound, an ink repellent compound that is a copolymer obtained by copolymerizing at least a fluorine-containing monomer and a monomer containing an alkylene group having an etheric oxygen atom, a photopolymerization initiator, The coloring photosensitive resin composition containing a coloring agent is described.
- the maximum weight average molecular weight of the fluorine-containing copolymer described in the examples of Patent Document 2 is 10,900.
- the required performance of the obtained partition wall that is, good ink repellency at the top of the partition wall, and erosion to the developer Performance such as resistance to the developer not developed, good wetting and spreading of the ink to the opening between the partition walls, etc. are sufficiently obtained, but when using a fluorine-containing resin having no ethylenic double bond, these performances
- the present condition is that the partition which fully satisfy
- the present invention was made in order to solve the problems of the prior art, and although it is an ink repellent component that does not have an ethylenic double bond, it has good ink repellency at the upper part of the partition wall and is not eroded by the developer. Contains an ink repellent component that can impart to the resulting partition the resistance to developer, the property of suppressing the generation of residual film that remains without being developed, and the good ink wetting and spreading property to the opening between the partitions.
- the present invention provides a photosensitive composition, partition walls, a color filter, and an organic EL device having the following configuration.
- a polymer (A) having a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group and having no side chain having an ethylenic double bond;
- a photosensitive composition comprising a photocuring initiator (B) and a binder resin (C), -CFXR f (1)
- X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom.
- the polymer (A) has a mass average molecular weight (Mw (A)) of 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 .
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may be substituted with a fluorine atom;
- R 3 is a hydrogen atom or a carbon number; Represents an organic group of 1 to 10 and n represents an integer of 1 to 200.
- a side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and having a group represented by the general formula (1) and an ethylenic group It is a polymer (A) ′ having no side chain having a double bond, and its mass average molecular weight (Mw (A) ′) is 2.6 ⁇ 10 4 ⁇ Mw (A) ′ ⁇ 20 ⁇ 10. 4.
- the photosensitive composition according to any one of [1] to [7], further comprising a polymer (A) ′ that is 4 .
- the photocuring initiator (B) is a photopolymerization initiator
- the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond.
- the photosensitive composition in any one.
- a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method A color filter characterized by being made.
- the term “photocuring initiator” is used as a general term for compounds that generate active species by light irradiation to initiate the curing reaction of the binder resin (C).
- the polyoxyalkylene group is a divalent group represented by — (RO) p — (R represents an alkylene group, and p represents an integer of 2 or more).
- RO represents an alkylene group, and p represents an integer of 2 or more.
- One end of the polyoxyalkylene group is bonded to the terminal group, and the other end is a bond bonded to the main chain side of the polymer.
- the obtained partition wall has good ink repellency at the top of the partition wall, developer resistance not eroded by the developer, and without development. It is possible to impart the property of suppressing the generation of remaining residual film and the good ink spreading property to the opening between the partition walls.
- a partition wall that is economically advantageous and has good performance, and a color filter and an organic EL device having the partition wall are obtained.
- the (meth) acryloyl group is used as a general term meaning both an acryloyl group and a methacryloyl group.
- (Meth) acrylate is used as a generic term for both acrylate and methacrylate.
- (Meth) acrylic acid is used as a generic term for both acrylic acid and methacrylic acid.
- (Meth) acrylamide is used as a general term for both acrylamide and methacrylamide.
- (Meth) allyl is used as a generic term for both allyl and methallyl.
- the group represented by the general formula (1) is also referred to as a group (1). The same applies to other groups.
- Photosensitive composition of the present invention has a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group, and an ethylenic double bond.
- X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom.
- the photosensitive composition of the present invention is a photosensitive composition comprising the polymer (A), a photocuring initiator (B), and a binder resin (C), and is a binder in a light irradiation portion upon exposure in photolithography or the like. It is a negative photosensitive composition in which the resin (C) is cured by the action of the photocuring initiator (B). In photolithography or the like, a portion that is not irradiated with light (an unexposed portion) is selectively removed during alkali development performed after exposure, and as a result, a partition wall made of a cured product of the photosensitive composition is formed. It is formed.
- the negative photosensitive composition is classified into several types such as a radical curable type and an acid curable type depending on the type of curing, and depending on the type of curing, the photocuring initiator (B) and the binder resin ( A combination of C) is selected.
- the photosensitive composition of the present invention can be applied to any curing type as long as it is a negative photosensitive composition, but is particularly suitable for a radical curable photosensitive composition.
- an embodiment of the photosensitive composition of the present invention will be described using a radical curable photosensitive composition and an acid curable photosensitive composition as examples.
- the photosensitive composition of the present invention is a radical curable type
- the photosensitive composition contains a polymer (A) and a photopolymerization initiator (B) as a photocuring initiator (B).
- Such a radical curable photosensitive composition is a coating film cured product in which the photosensitive resin (C1) is radically polymerized by the action of the photopolymerization initiator (B1) in the light-irradiated portion during exposure in photolithography or the like, and curing is accelerated.
- Each component which the radical curable photosensitive composition concerning this invention contains is demonstrated below.
- Polymer (A) has a side chain having the group represented by the general formula (1), has a polyoxyalkylene group, and does not have a side chain having an ethylenic double bond.
- the mass average molecular weight (Mw (A)) is 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 .
- the polymer (A) Since the polymer (A) has a side chain having the fluorine atom-containing group (1) and has a high molecular weight such that the mass average molecular weight is shown in the above range, the photosensitivity of the present invention on the substrate. When the coating film formed by applying the composition is dried, it tends to move to the vicinity of the surface of the coating film.
- the polymer (A) does not have an ethylenic double bond in the side chain, but has a high molecular weight as in the mass average molecular weight range, so that the photosensitive composition is cured by exposure after drying the coating film. As the film advances, it remains in the vicinity of the surface of the coating film transferred during drying of the coating film and is easily fixed at that position.
- the solubility of the developer is sufficiently ensured by setting the mass average molecular weight within the above range.
- the partition formed by developing the coated film after exposure can exhibit liquid repellency on the top surface, and can also exhibit lyophilicity at the opening between the partitions. It becomes.
- the polymer (A) does not migrate to the openings, and lyophilicity can be maintained in the openings between the partition walls. .
- the polymer (A) has a side chain having a polyoxyalkylene group, the liquid repellency can be maintained even when a jet rinsing step using high-pressure water after the development step is performed.
- the reason why the phenomenon is observed is not necessarily clear, but is considered as follows. Due to the interaction between the polyoxyalkylene group and other components such as the binder resin (C), the so-called anchor effect, the polymer (A) is considered to be less likely to be detached from the coating film surface. In particular, when the jet rinsing step using high-pressure water after the development step is performed, the polymer (A) is easily detached from the surface layer.
- the polymer (A) has a side chain having a polyoxyalkylene group, due to the anchor effect, the polymer (A) tends to remain on the surface of the coating film, and the coating film tends to exhibit liquid repellency. There is. For this reason, when ink is applied to the opening surrounded by the partition wall using the inkjet method, it is possible to suppress the occurrence of color mixing between adjacent openings and the occurrence of white spots in the openings. Moreover, a polymer (A) can suppress generation
- the phenomenon that the remaining film is generated is considered as follows. Since an alkaline developer used for producing barrier ribs or the like by photolithography or the like generally contains a surfactant, bubbles are easily generated in the development process. Moreover, when this bubble adheres to the liquid-repellent surface, it is difficult to remove. Therefore, there is a tendency that the ink repellent component contained in the photosensitive composition remains in the form of a film due to the bubbles adhering to the portion that should be dissolved and removed by the alkaline developer.
- the polymer (A) having a side chain having a polyoxyalkylene group can suppress the generation of the remaining film thus generated.
- the mass average molecular weight (Mw (A)) of the polymer (A) used in the present invention is 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4 . More preferably, 3.0 ⁇ 10 4 ⁇ Mw (A) ⁇ 12 ⁇ 10 4 , still more preferably 3.5 ⁇ 10 4 ⁇ Mw (A) ⁇ 12 ⁇ 10 4 , and particularly preferably, 4.0 ⁇ 10 is a 4 ⁇ Mw (a) ⁇ 10 ⁇ 10 4.
- the mass average molecular weight of the polymer (A) is 2.6 ⁇ 10 4 or less, the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. Does not spread out sufficiently.
- the mass average molecular weight exceeds 20 ⁇ 10 4 , alkali solubility and developability become insufficient.
- the mass average molecular weight (Mw (A)) is in the range of more than 3.0 ⁇ 10 4 and less than 12 ⁇ 10 4 , the liquid repellency is kept high regardless of the type and concentration of alkali and jet rinse conditions. It is preferable because it is easy to sag and has a wide manufacturing margin. Moreover, it is preferable also from the ease of manufacture of a polymer (A).
- the number average molecular weight (Mn (A)) of the polymer (A) is preferably 1.0 ⁇ 10 4 ⁇ Mn (A) ⁇ 15.0 ⁇ 10 4 , and 1.5 ⁇ 10 4 ⁇ It is more preferable that Mn (A) ⁇ 12.0 ⁇ 10 4 , and it is particularly preferable that 2.0 ⁇ 10 4 ⁇ Mn (A) ⁇ 10.0 ⁇ 10 4 .
- the number average molecular weight of the polymer (A) is less than 1.0 ⁇ 10 4 , the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method.
- a mass average molecular weight (Mw) and a number average molecular weight (Mn) mean the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
- a photosensitive composition particularly a photosensitive composition containing a black colorant, may not sufficiently proceed with a curing reaction at the time of exposure, but the polymer (A) that is not immobilized at the time of exposure is exposed to light.
- post-baking which will be described later
- the film may move to the side surfaces of the partition walls or may flow out to the openings between the partition walls.
- the mass average molecular weight of the polymer (A) exceeds 2.6 ⁇ 10 4 , and more preferably the number average molecular weight is 1.0 ⁇ 10 4 or more, the migration / outflow of the polymer (A) during the post-baking It is thought that the phenomenon is suppressed.
- the molecular weight distribution represented by mass average molecular weight (Mw (A)) / number average molecular weight (Mn (A)) is 1.2 or more and 8 or less. Preferably, 1.3 or more and 4 or less are more preferable.
- Mw (A) mass average molecular weight
- Mn (A) number average molecular weight
- the molecular weight distribution in the polymer (A) is within this range, the production process of the polymer (A) can be simplified, which is economically advantageous, and the developability is also good.
- the polymer (A) used for this invention has group (1) containing the fluorine atom shown by the said General formula (1) in a side chain.
- R f when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f may have a halogen atom excluding a fluorine atom. Good. As such a halogen atom, a chlorine atom is preferable.
- the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable.
- R f is a fluoroalkyl group having an etheric oxygen atom
- the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or at the end of the fluoroalkyl group. May be.
- R f in the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have the etheric oxygen atom.
- X is particularly preferably a fluorine atom.
- R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom
- R f is particularly limited as long as it has such a configuration.
- R f specifically, —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 , —CF (CF 3 ) O (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 CF 2 O) p
- R f is carbon atoms, which may have an etheric oxygen atom is 1 to 20 fluoroalkyl group, the R f, a perfluoroalkyl group and an etheric oxygen atom having no etheric oxygen atom A perfluoroalkyl group having an etheric oxygen atom is more preferable.
- the number of carbon atoms is preferably 1 to 11 and particularly preferably 3 to 5.
- a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferable, and a perfluoroalkyl group is particularly preferable.
- the perfluoroalkyl group and the polyfluoroalkyl group include those having an etheric oxygen atom.
- the compound whose X is a hydrogen atom is preferable.
- the group (1) preferably has 4 to 6 carbon atoms.
- Specific examples of such a group (1) include — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 ) 2 OCF 3 , -CF 2 O (CF 2 ) 2 O (CF 2 ) 2 OCF 3 and the like.
- the polymer (A) has 4 to 6 carbon atoms in the side chain (1), the compatibility between the polymer (A) and other components constituting the photosensitive composition can be improved. Can do. Thereby, aggregation of a polymer (A) in the coating film formed by apply
- the number of introduced groups (1) in the side chain having the group (1) is 1.
- the group (1) may be the same or different. That is, the group (1) that the polymer (A) has in the side chain may be only one type or a combination of two or more types.
- the group (1) may be introduced into all side chains, but preferably the polymer (A) so as to have the following fluorine atom content. The ratio of the side chain into which the group (1) is introduced relative to the whole is appropriately adjusted. Specifically, when the polymer (A) is produced by polymerizing the raw material monomer as described later, the blending amount of the monomer having the group (1) with respect to the entire raw material monomer is adjusted.
- the position of introduction of the side chain having the group (1) in the polymer (A) is not particularly limited, and is preferably regular and regularly spaced in a block manner so as to have the following fluorine atom content.
- the side chain which has group (1) in the principal chain which comprises a polymer (A) can be introduce
- the side chain having the group (1) is composed of an alternating copolymer, a block copolymer, and a random copolymer. It may be introduced in any form.
- the polymer (A) is preferably a random copolymer from the viewpoints of production efficiency, intramolecular uniformity of the liquid repellent component, compatibility with components other than the liquid repellent component, and the like.
- the fluorine atom content in the polymer (A) mainly due to the side chain having the group (1) is preferably 20 to 50% by mass, It is more preferably 25 to 42% by mass, and particularly preferably 25 to 35% by mass. If the fluorine atom content in the polymer (A) is less than 20% by mass, sufficient development resistance tends to be not obtained, and as a result, the liquid repellency of the upper surface of the partition wall may be insufficient. . Further, when the fluorine atom content in the polymer (A) exceeds 50% by mass, the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surface of the partition wall becomes insufficient. Sometimes. Furthermore, the adhesion between the partition walls and the substrate may be reduced.
- the fluorine atom content in the polymer (A) is a content mainly derived from the fluorine atom of the group (1) that the polymer (A) has in the side chain.
- the fluorine atom and the group refers to the content of fluorine atoms combined with the fluorine atoms of the polymer (A).
- the polymer (A) used in the present invention has a side chain having a polyoxyalkylene group.
- This polyoxyalkylene group is a polyoxyalkylene group having a repeating unit of an oxyalkylene group having 2 to 4 carbon atoms.
- the content of the polyoxyalkylene group in the polymer (A) used in the present invention is preferably 5 to 60% by mass. More preferably, it is 10 to 55% by mass, and particularly preferably 15 to 50% by mass.
- the liquid repellency may be significantly lowered when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, there is a possibility that a large amount of residual film exists in the partition walls and partition opening portions finally obtained.
- the content of the polyoxyalkylene group exceeds 60% by mass, the liquid repellency may be lowered.
- the polyoxyalkylene group used in the present invention is specifically a group represented by the following general formula (11) (hereinafter sometimes referred to as group (11)).
- group (11) -(R 11 O) m (R 12 O) j R 13 (11)
- R 11 represents an ethylene group
- R 12 represents an alkylene group having 3 or 4 carbon atoms
- R 13 represents a hydrogen atom or an optionally substituted substituent having 1 to 10 carbon atoms.
- m represents an integer of 4 to 100
- j represents an integer of 0 to 100
- m + j is 4 to 100.
- R 11 represents an ethylene group (—CH 2 CH 2 —)
- R 12 represents an alkylene group having 3 or 4 carbon atoms.
- the structure of the alkylene group having 3 or 4 carbon atoms may be a linear structure or a branched structure.
- R 12 is a propylene group (—CH 2 CH (CH 3 ) —), a trimethylene group (—CH 2 CH 2 CH 2 —), an ethylethylene group (—CH 2 CH (CH 2 CH 3 ) —), 1, Examples include 2-dimethylethylene group (—CH (CH 3 ) CH (CH 3 ) —), tetramethylene group (— (CH 2 ) 4 —), and propylene group or tetramethylene group is preferable.
- m represents an integer of 4 to 100
- j represents an integer of 0 to 100, respectively, preferably 50 or less, more preferably 30 or less.
- m / (m + j) which is the ratio of the number of R 11 in the polyoxyalkylene group, is preferably 50 to 100%, more preferably 80 to 100%, and substantially 100%. It is particularly preferred.
- M + j is 4 to 100, preferably 6 to 50, and more preferably 8 to 30.
- (R 11 O) m (R 12 O) j is a group (11) having m (R 11 O) units and j (R 12 O) units.
- the order of bonding between the (R 11 O) unit and the (R 12 O) unit is not particularly limited. That is, in the group (11), m (R 11 O) units and j (R 12 O) units may be bonded alternately, randomly, or in blocks.
- R 13 when R 13 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, the structure is a straight chain structure, a branched structure, a ring structure, a partial ring It may have a structure or the like.
- the substituent include a carboxyl group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms.
- R 13 in the group (11) is preferably a linear or unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.
- the polyoxyalkylene group such as the group (11) in the side chain of the polymer (A) one type may be used alone, or two or more types may be used in combination.
- the introduction of the side chain having the group (11) into the polymer (A) is, as will be described later, when the polymer (A) is produced by polymerizing the raw material monomer.
- the blending amount of the monomer with respect to the whole raw material monomer is appropriately adjusted so that the blending amount can give the effect of improving the developability to the polymer (A) without impairing the effects of the present invention. .
- the polymer (A) contained in the photosensitive composition of the present invention is a side having a functional group corresponding to various purposes in addition to the side chain having the group (1) within the range not impairing the effects of the present invention. It is possible to have chains.
- a functional group introduction into the side chain of the polymer (A) for example, a group having a siloxane bond represented by the following general formula (2) for the purpose of improving ink falling property and UV ozone resistance. (Hereinafter sometimes referred to as group (2)) can be introduced into the side chain of the polymer (A).
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may be substituted with a fluorine atom;
- R 3 is a hydrogen atom or a carbon number; Represents an organic group of 1 to 10 and n represents an integer of 1 to 200.
- R 1 and R 2 may be the same or different for each structural unit.
- R 1 and R 2 are alkyl groups, the preferred carbon number is 1 to 10, and the more preferred carbon number is 1 to 6. These may have a linear structure or a branched structure.
- R 1 and R 2 are cycloalkyl groups, the preferred carbon number is 3 to 10, and the more preferred carbon number is 5 or 6.
- R 1 and R 2 are aryl groups, the preferred carbon number is 6-15, and the more preferred carbon number is 6-10.
- Some or all of the hydrogen atoms of R 1 and R 2 may be substituted with fluorine atoms.
- R 1 and R 2 are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group. or it is preferably phenyl group, and particularly preferably R 1 and R 2 of the total siloxane units are methyl groups.
- R 3 is an organic group having 1 to 10 carbon atoms, R 3 may have a nitrogen atom, an oxygen atom, a fluorine atom, or the like.
- R 3 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and more preferably a trifluoromethyl group. Or it is a methyl group.
- n is preferably an integer of 2 to 100.
- the polymer (A) has a side chain having the group (2)
- one type of the group (2) may be used alone, or two or more types may be used in combination.
- the content of the silicon atom derived from the group (2) in the polymer (A) is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass. When the content of silicon atoms is within this range, the above effect can be imparted to the polymer (A) without impairing the effect of the present invention.
- the adjustment of the silicon atom content in the polymer (A) is as follows. When the polymer (A) is produced by polymerizing the raw material monomer, the raw material single amount of the monomer having the group (2) It is performed by appropriately adjusting the blending amount for the whole body.
- the polymer (A) preferably further has a side chain having an acidic group.
- the introduction of the side chain having an acidic group in the polymer (A) is performed for the purpose of improving developability.
- the developer used for the development photosensitive composition is generally an alkaline developer, and the solubility of the polymer (A) in the developer is improved by introducing an acidic group.
- the polymer (A) contained in the unexposed part of the coating film is removed by the developer.
- the acidic group which a polymer (A) has in a side chain may be 1 type, or may be 2 or more types.
- a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, etc. are mentioned.
- the introduction of acidic groups to the side chain of the polymer (A) may be performed by introducing the end group R 13 of the polyoxyalkylene group (11).
- the polymer (A) used for this invention when manufacturing a polymer (A) by superposition
- the blending amount is appropriately adjusted so that the obtained polymer (A) has the following preferable acid value.
- the polymer (A) preferably has an acid value of 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g.
- the acid value is the mass [mg] of potassium hydroxide necessary to neutralize 1 g of the sample, and the unit is described as mgKOH / g in this specification.
- the polymer (A) preferably further has a side chain having a functional group capable of undergoing a crosslinking reaction with a functional group included in the matrix constituting the partition wall by heat or light, such as an epoxy group, a mercapto group, or a hydroxyl group.
- a functional group capable of undergoing a crosslinking reaction with a functional group included in the matrix constituting the partition wall by heat or light
- these functional groups introduced into the polymer (A) can be used alone or in combination of two or more.
- the introduction of these functional groups into the side chain of the polymer (A) may be carried out by introducing it into the terminal group R 13 of the polyoxyalkylene group (11).
- the introduction of a hydroxyl group can also be performed by using R 13 as a hydrogen atom.
- the photosensitive composition of the present invention contains a photocuring initiator (B) and a binder resin (C) in addition to the polymer (A). This binder resin (C) is cured by the action of the photocuring initiator (B) when exposed.
- This binder resin (C) is cured by the action of the photocuring initiator (B) when exposed.
- cured by pattern exposure is removed with a developing solution.
- a combination of a binder resin (C) having an acidic group and an alkaline developer is usually used.
- the partition matrix has these functional groups of the polymer (A) by post-baking treatment after exposure and development.
- the polymer (A) is sufficiently fixed to the partition wall by thermally crosslinking with the acidic group derived from the binder resin (C).
- the polymer (A) particularly at a portion where the polymer (A) on the upper surface of the partition wall is present at a high density. The two are heat-crosslinked to become more polymerized and are sufficiently fixed to the partition walls.
- the polymer (A) has a mercapto group, it is sufficiently fixed to the partition wall by crosslinking with the ethylenically unsaturated double bond group derived from the binder resin (C) by post-baking treatment in the same manner as described above. The As a result, it is possible to prevent the polymer (A) from flowing out into or eluting from the partition wall, which is a concern when the ink is subsequently injected into the partition opening by inkjet.
- the introduction of the side chain having a functional group crosslinkable with the functional group of the partition matrix into the polymer (A) is performed when the polymer (A) is produced by polymerizing raw material monomers as described later.
- the blending amount of the monomer having a functional group and a functional group crosslinkable in the partition matrix with respect to the whole raw material monomer can be added to the polymer (A) without impairing the effect of the present invention. Is appropriately adjusted so that the blending amount can provide the effect of suppressing the outflow / elution of the polymer (A).
- the polymer (A) used in the present invention has a structure having a side chain having the group (1) and a side chain having a polyoxyalkylene group such as the group (11).
- a side chain having an acidic group a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light, etc. Examples thereof include a method of forming directly by a polymerization reaction or a method of forming by chemical conversion after the polymerization reaction.
- the polymer (A) has a side chain having the essential group (1), a side chain having a polyoxyalkylene group such as the group (11), and a side chain optionally having the above groups by polymerization reaction.
- a monomer having the group (1), a monomer having a side chain having a polyoxyalkylene group such as the group (11), and a monomer having the group (2) if necessary Body, monomer having an acidic group, monomer having a functional group crosslinkable with the functional group of the partition matrix, and / or other monomer may be copolymerized under appropriate conditions. .
- copolymerization examples include alternating copolymerization, block copolymerization, random copolymerization and the like, and the copolymerization can be carried out by a conventionally known method.
- the polymer (A) Is preferably a random copolymer obtained by copolymerization by random copolymerization.
- a monomer which has the said group (1) used for manufacture of a polymer (A) it is preferable that it is a compound represented by following General formula (3). These may be used individually by 1 type, or may use 2 or more types together.
- CH 2 CR 4 —COO—Y—CFXR f (3)
- R 4 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, an etheric oxygen atom or a C 1-20 fluoro atom.
- Y is a single bond or a divalent organic group having no fluorine atom having 1 to 6 carbon atoms
- —CFXR f is a group corresponding to the group (1), ie, X is A hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or a fluorine atom.
- a preferred embodiment of —CFXR f in the compound (3) is the same as that described for the group (1).
- Y which is a divalent organic group having no fluorine atom having 1 to 6 carbon atoms, represents —R 5 —, —R 5 —NR 6.
- R 5 is an alkylene group having 1 to 6 carbon atoms
- R 6 is a hydrogen atom or R 7 is a single bond or an alkylene group having 1 to 4 carbon atoms, provided that when R 6 is a methyl group, R 5 bonded to NR 6 has 1 to 5 carbon atoms. Etc.).
- R 5 -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 )-and the like.
- R 7 -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) — and the like.
- Y in the compound (3) is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
- R 4 a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a benzyl group and the like are preferable, and a hydrogen atom, a fluorine atom, a chlorine atom, A methyl group or a trifluoromethyl group is more preferable.
- R 4 is particularly preferably a hydrogen atom or a methyl group. That is, the compound (3) is particularly preferably (meth) acrylate.
- the compound represented by the general formula (3) is particularly preferably (meth) acrylate in which —CFXR f is a perfluoroalkyl group having 4 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms.
- Specific examples include 2- (perfluorohexyl) ethyl (meth) acrylate and 2- (perfluorobutyl) ethyl (meth) acrylate.
- a monomer which has the said group (11) used for manufacture of a polymer (A) it is preferable that it is a compound represented by the following general formula (12) or (13). These may be used individually by 1 type, or may use 2 or more types together.
- CH 2 CR 14 —COO— (W—O) q — (R 11 O) m (R 12 O) j R 13 (12)
- CH 2 CR 14 —O— (W—O) q — (R 11 O) m (R 12 O) j R 13 (13)
- R 14 is substituted with a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms.
- Q is 0 or 1.
- — (R 11 O) m (R 12 O) j R 13 is a group corresponding to the group (11).)
- — (R 11 O) m (R 12 O) j R 13 in the compounds (12) and (13) is the same as that described for the group (11).
- — (W—O) q — represents a single bond when q is 0.
- — (W—O) q — is an organic group having an oxygen atom on the R 11 side.
- W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, such as an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 or 6 carbon atoms, or a cycloalkylene having 5 or 6 carbon atoms.
- a cycloalkylene group-containing alkylene group having 6 to 10 carbon atoms in total and having an alkylene group having 1 to 2 carbon atoms on both sides or one side of the group is preferable.
- W is the same alkylene group as R 11 (and when q is not 0, it is also the same alkylene group as R 12 ), q is regarded as 0.
- R 14 in the compounds (12) and (13) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
- — (W—O) — represents a straight chain structure other than R 11 O and R 12 O, a branched structure, a ring structure, a partially ring
- An oxygen atom-terminated hydrocarbon group having 1 to 10 carbon atoms is preferred. More preferred is an oxygen atom-terminated hydrocarbon group having 3 to 8 carbon atoms.
- Specific examples of the oxygen atom-terminated hydrocarbon group include CH 2 C 6 H 10 CH 2 O (wherein C 6 H 10 is a cyclohexylene group), CH 2 O, CH (CH 3 ).
- W in the compounds (12) and (13) is an oxyalkylene group having 3 or 4 carbon atoms (provided that when j is not 0, the same oxyalkylene as R 12 O, for ease of availability) Are preferred).
- a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, a benzyl group, and the like are preferable, and a hydrogen atom, a chlorine atom, or a methyl group is more preferable. preferable.
- BLEMMER PME-400 (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, and the value of k is It is about 9.
- NK ester M-230G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, k The value of is about 23).
- New Frontier NF biisomer PEM6E (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CH 2 ⁇ C (CH 3 ) COO (CH 2 CH 2 O) k H: where k is about 6).
- Light ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH 2 ⁇ CHCOO (CH 2 CH 2 O) k CH 3 : where k is about 9).
- BLEMMER AE-400 (trade name, manufactured by NOF Corporation, CH 2 ⁇ CHCOO (CH 2 CH 2 O) k H: where k is about 10).
- BLEMMER 70PEP-350B (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (C 2 H 4 O) m (C 3 H 6 O) j H: where m is about 5, j is About 2).
- BLEMMER 55PET-800 (trade name, manufactured by NOF Corporation, CH 2 ⁇ C (CH 3 ) COO (C 2 H 4 O) m (C 4 H 8 O) j H: wherein m is about 10, j is About 5).
- the monomer having the group (2) used as necessary for the production of the polymer (A) is preferably a compound represented by the following general formula (4). These may be used alone or in combination of two or more.
- R 8 is a hydrogen atom or a methyl group
- Z is a single bond or a divalent organic group having 1 to 6 carbon atoms. It also has a siloxane bond bonded to Z.
- the group is a group corresponding to the group (2), that is, R 1 and R 2 are each independently a hydrogen atom, an alkyl group optionally substituted with a fluorine atom, a cycloalkyl group, or An aryl group
- R 3 is a hydrogen atom or an organic group having 1 to 10 carbon atoms
- n is an integer of 1 to 200.
- R 1 , R 2 , R 3 and n in the compound (4) are the same as those described for the group (2).
- the compound (4) has a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —CH 2 —, —CH 2 CH 2 -, -CH (CH 3 )-, -CH 2 CH 2 CH 2- , -C (CH 3 ) 2- , -CH (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -,- CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 ) — and the like can be mentioned.
- —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, and —CH 2 CH 2 CH 2 CH 2 — are preferable.
- the monomer having an acidic group used as necessary for the production of the polymer (A) is not particularly limited as long as it has an acidic group.
- a monomer having a carboxyl group, a phenolic hydroxyl group may be used.
- a monomer having a sulfonic acid group may be used alone or in combination of two or more.
- Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
- Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and one or more hydrogen atoms of these benzene rings, such as a methyl group, an ethyl group, and an n-butyl group. And an alkyl group, a methoxy group, an ethoxy group, an n-butoxy group or the like, a halogen atom, a haloalkyl group having one or more halogen atoms, a nitro group, a cyano group, a compound substituted with an amide group, etc. .
- Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, 2-methacrylic acid 2-sulfoethyl, Examples include 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropane sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, and the like.
- crosslinkable functional group Monomer having a functional group that can be cross-linked by heat or light with the functional group of the partition matrix used as necessary for the production of the polymer (A).
- crosslinkable functional group it will not be specifically limited. Specific examples include a monomer having an epoxy group and a monomer having a hydroxyl group. These may be used alone or in combination of two or more. In addition, it is preferable that the monomer which has a crosslinkable functional group does not have group (1) and group (2) substantially.
- Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
- Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl ( (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acrylate Amide, N, N-bis (hydroxymethyl) (meth) acrylamide.
- thiocarboxylic acid ester can be introduce
- the thiocarboxylic acid ester compound is, for example, a compound in which the carboxyl group of thioacetic acid, thiopropionic acid, thiobutyric acid, or thiobenzoic acid is substituted with a —COSH group.
- Monomers other than those that can be optionally used for the production of the polymer (A) include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters. , (Meth) acrylic acid esters, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes and the like, and considering the heat resistance of the partition wall, (meth) acrylic acid esters, or ( Meth) acrylamides are preferred. Note that these compounds may have a functional group such as a carbonyl group or an alkoxy group.
- monomers used for polymerization are appropriately selected from the monomers described above and copolymerized at an appropriate ratio.
- the preferable compounding ratio of the various monomers used when manufacturing a polymer (A) is as follows.
- the ratio of the monomer mass having the group (1) to the total mass of the monomer to be copolymerized is such that the fluorine atom content in the polymer (A) is in the above preferred range, specifically 20 to 50% by mass, The proportion is more preferably 25 to 42% by mass, particularly preferably 25 to 35% by mass. Although it depends on the type of the monomer having the group (1) as such a ratio, specifically, it is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, It is particularly preferably 40 to 60% by mass. If this ratio is too low, sufficient fluorine atom content cannot be secured, and sufficient development resistance tends to be not obtained, and in the vicinity of the upper surface of the partition formed using the photosensitive composition of the present invention.
- a polymer (A) becomes difficult to transfer, and as a result, the liquid repellency of the upper surface of a partition may become inadequate.
- this ratio is too high, the fluorine atom content exceeds the preferred range, the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surfaces of the partition walls may be insufficient. . Furthermore, the adhesion between the partition walls and the substrate may be reduced.
- the resulting polymer (A) when a monomer containing a fluorine atom is used as a raw material monomer in addition to the monomer having the group (1), the resulting polymer (A) What is necessary is just to adjust suitably the ratio of each raw material monomer so that fluorine atom content may become the said preferable range.
- the ratio of the monomer mass having the group (11) to the total mass of the monomer to be copolymerized is such that the content of the group (11) in the polymer (A) is 5 to 60% by mass. It is preferable to do.
- the ratio is more preferably 10 to 55% by mass, and particularly preferably 15 to 50% by mass.
- the content of the group (11) in the polymer (A) is generally within the above preferred range, and liquid repellency is maintained even when a jet rinsing step using high-pressure water after the development step is performed. be able to. Furthermore, the generation of a residual film can be prevented.
- the ratio of the monomer mass having the group (2) to the total mass of the monomer to be copolymerized is: It is preferable that the silicon (A) content in the polymer (A) is in the above preferred range, specifically 0.1 to 25% by mass, more preferably 0.5 to 20% by mass. Such a ratio depends on the type of the monomer having the group (2), but specifically, it is preferably 0.5 to 30% by mass, more preferably 2 to 20% by mass.
- the silicon atom content in the polymer (A) is generally within the above preferable range, and the ink fall resistance and UV ozone resistance are improved. Good properties and the like.
- the ratio of the mass of the monomer having an acidic group to the total mass of the monomer to be copolymerized is determined by the polymer ( It is preferable that the acid value of A) be in the above-mentioned preferable range, specifically 100 mgKOH / g or less, more preferably 10 to 50 mgKOH / g. Such a ratio depends on the type of monomer having an acidic group, but is specifically preferably 2 to 20% by mass, more preferably 4 to 12% by mass.
- the proportion of the monomer having an acidic group in all the monomers to be copolymerized is within this range, the development of the unexposed portion can be carried out satisfactorily without impairing the effects of the present invention, and the parent of the opening can be performed. Although liquidity can be improved, it is favorable.
- the ratio of the monomer mass having the crosslinkable functional group to the total mass of the monomer to be copolymerized Is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass.
- the ratio of the monomer having a crosslinkable functional group in all the monomers to be copolymerized is within this range, the polymer (A) can be immobilized on the partition wall without impairing the effects of the present invention. In addition, developability is improved.
- the ratio of the mass of the other monomers to the total mass of the monomers to be copolymerized is 70% by mass or less. It is preferable that the content is 50% by mass or less. When the ratio of this mass exceeds 70 mass%, alkali developability may fall.
- the polymer (A) used in the present invention has, as essential components, a side chain having the above group (1) and a side chain having a polyoxyalkylene group such as the above group (11).
- a monomer having a polyoxyalkylene group such as a monomer having a group (2), a monomer having an acidic group, a monomer having a thermally crosslinkable functional group, and / or It can synthesize
- a chain transfer agent as needed.
- the adjustment of the mass average molecular weight of the polymer (A) can be performed by adjusting the conditions such as the polymerization temperature and time, the amount of the polymerization initiator, the addition amount of the chain transfer agent, and the like.
- the polymer (A) thus produced is random copolymerization, but the block copolymer is prepared using a usual method such as changing the introduction timing of the raw material monomer into the copolymerization reaction system depending on the type of monomer. It is also possible to produce a polymer.
- Examples of the solvent used for the polymerization of the polymer (A) include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsorbs such as methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol Methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate Esters such as glycerol triacetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether.
- polymerization initiator examples include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent. These polymerization initiators may be used alone or in combination of two or more.
- organic peroxide examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide and the like.
- inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like.
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2 -Amidinopropane) dihydrochloride and the like.
- chain transfer agents examples include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol; chloroform, carbon tetrachloride, tetraodor Alkyl halides such as carbon halides, and the thiocarboxylic acid ester compounds mentioned in the introduction of the mercapto group into the polymer (A).
- mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol
- chloroform carbon tetrachloride
- the side chain having the above various groups in the polymer (A) used in the present invention in particular, the side chain having an acidic group or the side chain having a thermally crosslinkable functional group is also formed by chemical conversion after the polymerization reaction.
- a copolymer having a side chain having the group (1) and a side chain having a hydroxyl group is produced by the above polymerization, and a polybasic acid anhydride (such as maleic anhydride) is reacted with the hydroxyl group of the copolymer.
- a polymer (A) having a side chain having a carboxyl group as an acidic group can be produced.
- the polymer (A) is preferably contained at a ratio of 0.07 to 1% by mass with respect to the total solid content of the composition. More preferably, it is contained in a proportion of 0.5% by mass. If the content is too small, the liquid repellency of the upper surface of the partition formed using the photosensitive composition of the present invention may be insufficient. If the content is too large, the adhesion between the partition and the substrate may be insufficient. May decrease.
- action to a partition other than the said polymer (A).
- a component has a side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and is represented by the general formula (1).
- the polymer (A) ′ is a polymer essentially having a side chain having the group (2) instead of the side chain having the group (1) in the polymer (A).
- polymer (A) ' in addition to the side chain which has group (1), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) ' Can have the same configuration as that except that it does not have a side chain having the group (1).
- the silicon atom content in the polymer (A) ′ is preferably 0.1 to 25% by mass, and more preferably 0.5 to 20% by mass.
- the photosensitive composition of the present invention can be imparted with an effect of enhancing the liquid repellency of the partition wall surface obtained by using the photosensitive composition of the present invention without impairing the effects of the present invention. It becomes possible.
- the polymer (A) ′ has a side chain having the group (11), preferably the content of the group (11) with respect to the polymer (A) ′ is 5 to 60% by weight. Have in proportions.
- the polymer (A) ′ can optionally have a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light with a functional group that the partition matrix has, such as Also for the polymerization reaction for forming a structure having a side chain, the monomer having the group (1) is not used as a raw material monomer, but the monomer having the group (2) is used as an essential raw material monomer. Except for the above, it can be the same as the polymer (A).
- the polymer (A) ′ when the polymer (A) ′ is used, it is contained in a proportion of 0.5 to 30% by mass with respect to the total solid content of the composition. It is preferably contained in a proportion of 2 to 20% by mass. By using in this content, it becomes possible to give the photosensitive composition of the present invention the effect of enhancing the liquid repellency of the partition wall surface obtained by using the photosensitive composition of the present invention without impairing the effects of the present invention. Further, when the polymer (A) ′ is used, even if the polymer (A) having no side chain having the group (2) is used as the polymer (A) used in combination therewith, the same as described above. The effect can be demonstrated.
- Photocuring initiator (B) (Photopolymerization initiator (B1))
- a photopolymerization initiator (B1) that generates radicals upon irradiation with light is used as the photocuring initiator (B).
- the photopolymerization initiator (B1) is not particularly limited as long as it is a compound that generates radicals upon irradiation with light.
- ⁇ -diketones such as benzyl, diacetyl, methylphenylglyoxylate, and 9,10-phenanthrenequinone
- acyloins such as benzoin
- acylo such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether
- Inethers thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4 Thioxanthones such as sul
- the photopolymerization initiator (B1) used in the present invention is preferably a compound represented by the following general formula (5).
- R 21 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group.
- R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms that is substituted or substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a 7 to 20 carbon atom that is substituted or unsubstituted with an alkyl group a benzoyl group, a phenoxycarbonyl group alkoxycarbonyl group or an alkyl group substituted or unsubstituted 7 to 20 carbon atoms having a carbon number of 2 ⁇ 12, R 23 is an alkyl group having 1 to 12 carbon atoms There, R 24, R 25, R 26 and R 27 each independently represent a hydrogen atom, an alkyl group having 1 to 12
- R 21 is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted with an alkyl group, such as a methyl group
- an alkyl group such as a methyl group
- Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group.
- an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
- R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
- R 22 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.
- an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
- examples of the alkyl group having 1 to 12 carbon atoms represented by R 23 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.
- an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
- R 24 , R 26 and R 27 are preferably hydrogen atoms.
- R 25 is a benzoyl group having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a carbon number having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group.
- a benzylcarbonyl group is preferable, and a 2-methylbenzoyl group, a benzylcarbonyl group, or a 1,3,5-trimethylbenzylcarbonyl group is particularly preferable.
- the compound represented by the general formula (5) (O-acyloxime compound) is not particularly limited, but in the general formula (5), R 21 is a phenyl group, R 22 is an octyl group, and R 23 is an ethyl group.
- R 24 , R 26 and R 27 are hydrogen atoms, R 25 is a benzoyl group;
- R 21 is a methyl group,
- R 22 is a butyl group, heptyl group or octyl group,
- R 23 is an ethyl group,
- R 24 , R 26 and R 27 are hydrogen atoms and
- R 25 is a benzoyl group;
- R 21 is a phenyl group, R 22 is an octyl group, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and
- R 25 is compound 2-methylbenzoyl group;
- R 21 is a methyl group,
- R 22 is a methyl group or an octyl group,
- R 23 is ethyl,
- R 24, R 26 and R 27 are hydrogen atoms,
- R 5 is a 2-methylbenzoyl group compound;
- R 21 and R 22 is
- a commercially available product can be used as the photopolymerization initiator (B1).
- Examples of commercially available products include OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime): a compound in which, in the above general formula (5), R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group) Is mentioned.
- the content of the photopolymerization initiator (B1) in the radical curable photosensitive composition according to the present invention is preferably 1 to 15% by mass with respect to the total solid content of the composition, and 2 to 7% by mass. Is more preferable. When the content is 1 to 15% by mass, the curability is good and a pattern or line width close to the mask pattern can be formed by exposure and development.
- Binder resin (C) (Photosensitive resin (C1))
- the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond that is polymerized by the radical generated by the photopolymerization initiator (B1). Resin (C1) is used. Since the photosensitive resin (C1) has an ethylenic double bond involved in the photopolymerization in one molecule and further has an acidic group, the photosensitive resin (C1) is an uncured photosensitive composition using an alkaline developer. Unexposed portions can be selectively removed, and as a result, barrier ribs can be formed. In addition, it is preferable that photosensitive resin (C1) does not have group (1) and group (2) substantially.
- an acidic group which the photosensitive resin (C1) has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, You may use 2 or more types together.
- the photosensitive resin (C1) has, the double bond which addition polymerization groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, is mentioned, Two or more kinds may be used in combination.
- addition polymerization groups such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group.
- Two or more kinds may be used in combination.
- some or all of the hydrogen atoms of these addition polymerizable groups may be substituted with a hydrocarbon group, preferably a methyl group.
- the photosensitive resin (C1) is not particularly limited. Specifically, the resin (C1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin having ethylenic properties. Examples thereof include a resin (C1-2) into which a double bond and an acidic group are introduced. These may be used alone or in combination of two or more.
- Resin (C1-1) is, for example, a side chain having a reactive group obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, or an epoxy group with a monomer having an acidic group. And a copolymer having an acidic group-containing side chain, a functional group capable of bonding to the reactive group, and a compound having an ethylenic double bond dissolved in a solvent and reacted. it can.
- the monomer having a phosphate group as an acidic group is not particularly limited, and examples thereof include 2- (meth) acryloyloxyethane phosphoric acid.
- Resin (C1-2) can be synthesized, for example, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond and then reacting with a polybasic carboxylic acid or its anhydride. Can do. Specifically, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, the carboxyl group and the epoxy group of the epoxy resin react to introduce an ethylenic double bond. Next, a carboxyl group can be introduce
- the epoxy resin is not particularly limited, but is 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 naphthalene skeleton, Examples include an epoxy resin having a biphenyl skeleton represented by the formula (6), an epoxy resin represented by the following general formula (7), an epoxy resin represented by the following general formula (8), and the like.
- each hydrogen atom of the benzene ring is independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a substituent. It may be substituted with a phenyl group which may have
- R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10) .
- each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. 0 to 10)
- the epoxy resin represented by General formula (6), General formula (7), or General formula (8) and the compound which has a carboxyl group and an ethylenic double bond react, it is polybasic carboxylic acid.
- the anhydride is reacted, it is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride as the polybasic carboxylic acid anhydride.
- the molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride and the tetracarboxylic dianhydride.
- a commercially available product can be used as the resin (C1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin.
- Examples of such commercially available products are KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H.
- a resin obtained by introducing an acidic group and an ethylenic double bond into an epoxy resin represented by formula (7), or an acid group and an ethylenic double bond introduced into an epoxy resin represented by formula (8) Resin is preferred.
- the resin more black colorant can be blended in the composition, and the light shielding property and optical density can be increased.
- the coating film peeling at the time of image development is suppressed and a high resolution pattern can be obtained.
- the linearity of the line is good and preferable.
- the appearance after the post-baking step is maintained, and a smooth coating surface is easily obtained, which is preferable.
- the photosensitive resin (C1) used in the present invention preferably has a mass average molecular weight of 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , more preferably 2.0 ⁇ 10 3 to 15 ⁇ 10 3 .
- mass average molecular weight is less than 1.5 ⁇ 10 3 , curing during exposure may be insufficient, and when it exceeds 30 ⁇ 10 3 , developability may be deteriorated.
- the number of ethylenic double bonds that the photosensitive resin (C1) has is preferably 3 or more, more preferably 6 or more in one molecule on average.
- the number of ethylenic double bonds is 3 or more, the difference in alkali solubility between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller exposure amount.
- the photosensitive resin (C1) preferably has an acid value of 10 to 300 mgKOH / g, more preferably 30 to 150 mgKOH / g. When it is 10 to 300 mgKOH / g, the developability of the photosensitive composition is good.
- the content of the photosensitive resin (C1) in the radical curable photosensitive composition according to the present invention is preferably 5 to 80% by mass with respect to the total solid content of the composition, and is 10 to 60% by mass. Is more preferable. When the content is 5 to 80% by mass, the developability of the photosensitive composition is good.
- the radical curable photosensitive composition according to the present invention comprises the polymer (A), a photopolymerization initiator (B1) as a photocuring initiator (B), and a binder resin (C).
- the photosensitive resin (C1) having an acidic group and an ethylenic double bond as an optional component is described below for the purpose of improving various functions and the like as long as the effects of the present invention are not impaired. It is possible to contain components.
- the radical curable photosensitive composition according to the present invention preferably contains a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
- a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing.
- the crosslinking agent (D) having two or more ethylenic double bonds is not particularly limited, but a compound having 2 to 10 (meth) acryloyloxy groups is preferable. Specifically, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate And urethane acrylate.
- a commercially available product can be used as the crosslinking agent (D) having two or more ethylenic double bonds.
- examples of such commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) , Ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., bis ⁇ 4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicar
- urethane acrylate examples include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20.
- Etc. A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the coating film and suppressing thermal sagging.
- A-9300-1CL is preferable from the viewpoint of imparting flexibility to the coating film.
- Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
- the content of the crosslinking agent (D) in the radical curable photosensitive composition according to the present invention is preferably 1 to 50% by mass with respect to the total solid content of the composition, and preferably 5 to 30% by mass. More preferred. When the content is 1 to 50% by mass, the developability of the photosensitive composition is improved.
- Black colorant (E) The radical curable photosensitive composition according to the present invention has a black colorant (E) according to the required optical density of the partition wall when the cured product is used in applications requiring light shielding properties such as a black matrix. It is preferable to contain.
- the black colorant (E) is not particularly limited, and examples thereof include carbon black, aniline black, anthraquinone black pigment, metal oxide such as titanium black, metal particles such as silver tin alloy, and perylene black pigment. Specifically, C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
- the black colorant (E) may be a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments. Among these, carbon black is preferable in consideration of the light shielding property. Carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust the color tone of the black colorant (E), carbon black can be used in combination with a blue pigment or a purple pigment.
- the carbon black used as the black colorant (E) preferably has a specific surface area of 50 to 200 m 2 / g by the BET method. If this specific surface area is too small, the shape of the partition wall may be deteriorated. If the specific surface area is too large, the dispersion aid described later will be excessively adsorbed on the black colorant (E), resulting in a large amount of dispersion aid. It may be necessary to add an agent.
- the carbon black used as the black colorant (E) has an oil absorption of dibutyl phthalate of 120 cc / 100 g or less, and a smaller amount is more preferable.
- the carbon black used as the black colorant (E) preferably has an average primary particle diameter of 20 to 50 nm. If this average primary particle size is too small, it becomes difficult to disperse at a high concentration, it may be difficult to obtain a photosensitive composition with good stability over time, and if the average primary particle size is too large, It may cause deterioration of the shape of the partition wall.
- the carbon black preferably has an average secondary particle size of 80 to 200 nm. The particle size of carbon black can be measured using a transmission electron microscope.
- the black colorant (E) in the case where the black colorant (E) is blended in order to impart light-shielding properties such as a black matrix to the cured film.
- the content depends on the required light shielding properties and optical density, but is preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and more preferably 25 to 40% by mass based on the total solid content of the composition. % Is particularly preferred. If this content is too small, the optical density of the partition may be insufficient in the case of a black matrix or the like. If the content is too high, the curability of the photosensitive composition will be reduced and the appearance of the partition will be reduced. Liquid repellency may be reduced.
- the radical curable photosensitive composition according to the present invention contains a dispersible material such as the black colorant (E), it is preferable to contain a polymer dispersant in order to improve the dispersibility.
- the polymer dispersant is not particularly limited, and is urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acrylic type, polyether type, vinyl chloride type, vinyl chloride vinyl acetate type. Examples thereof include a polymer system, a polyamide system, and a polycarbonate system. Among these, urethane type or polyester type is preferable.
- the polymer dispersant may have a polyoxyethylene group and / or a polyoxypropylene group.
- the polymer dispersant When the polymer dispersant is used for dispersing the black colorant (E), it is preferable to use a polymer dispersant having a basic group in consideration of the affinity for the black colorant (E). Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
- Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all above). Trade names, manufactured by BYK-Chemie), Solspers 5000, Solspers 17000 (all of which are trade names, manufactured by Zeneca).
- the addition amount of the polymer dispersant is preferably 5 to 30% by mass and more preferably 10 to 25% by mass with respect to the dispersible material such as the black colorant (E). If the amount added is too small, the effect of improving dispersibility may be insufficient, and if the amount added is too large, the developability of the photosensitive composition may be lowered.
- the radical curable photosensitive composition according to the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as a dispersion aid.
- the dispersion aid is considered to have a function of improving dispersion stability by adsorbing to a dispersible material such as a black colorant (E) and a polymer dispersant.
- the radical curable photosensitive composition according to the present invention may contain fine particles as necessary. Thereby, it can suppress that the shape of a partition changes at the time of the post-baking mentioned later.
- the fine particles are not particularly limited, inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO); organic fine particles such as polyethylene and polymethyl methacrylate (PMMA) Is mentioned.
- the fine particles are preferably inorganic fine particles in view of heat resistance, and silica or zirconia is preferred in consideration of availability and dispersion stability.
- the photosensitive composition contains a black colorant (E) and a polymer dispersant in order to improve the dispersibility thereof, the fine particles can be obtained by considering the adsorptive capacity of the polymer dispersant. It is preferably negatively charged.
- the fine particles do not absorb light irradiated at the time of exposure, i-line (365 nm), h-line (405 nm), which is the main emission wavelength of an ultra-high pressure mercury lamp, It is particularly preferable not to absorb g-line (436 nm).
- the particle diameter of the fine particles is preferably 1 ⁇ m or less, more preferably 200 nm or less, since the surface smoothness of the partition wall is improved.
- the content of fine particles in the radical curable photosensitive composition according to the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the total solid content of the composition. If the content is too small, the shape of the partition wall may change during post-baking, and if the content is too large, the dispersion stability of the photosensitive composition may decrease.
- the radical curable photosensitive composition according to the present invention may contain a silane coupling agent as required. Thereby, the adhesiveness of a partition and a board
- the silane coupling agent is not particularly limited. Specifically, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyl Examples include trimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, polyoxyalkylene having a triethoxysilyl group, and imidazolesilane. Good.
- the radical curable photosensitive composition according to the present invention may contain a thermosetting agent, if necessary. Thereby, the heat resistance of a partition and water permeability resistance can be improved. Further, when the polymer (A) has a thermally crosslinkable functional group, the polymer (A) and the thermosetting agent are chemically bonded, thereby obtaining an effect of fixing the polymer (A) to the partition wall. It is done.
- thermosetting agent Amino resin (melamine compounds, such as hexamethoxymethylol melamine), a compound which has two or more epoxy groups, a compound which has two or more hydrazino groups, a polycarbodiimide compound, an oxazoline group
- Amino resin melamine compounds, such as hexamethoxymethylol melamine
- a compound which has two or more epoxy groups a compound which has two or more hydrazino groups
- a polycarbodiimide compound an oxazoline group
- a compound having two or more, a compound having two or more aziridine groups, a polyvalent metal, a compound having two or more mercapto groups, a polyisocyanate compound and the like may be mentioned, and two or more may be used in combination.
- amino resins, compounds having two or more epoxy groups, or compounds having two or more oxazoline groups are preferable.
- the radical curable photosensitive composition according to the present invention may contain a phosphate compound as necessary. This is preferable because adhesion to the substrate can be improved.
- the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
- the radical curable photosensitive composition according to the present invention includes a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, as necessary, in addition to various components other than those described above.
- An ultraviolet absorber or the like may be included.
- the radical curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
- the photosensitive composition of the present invention is an acid curable type
- the photosensitive composition comprises a polymer (A) and a photoacid generator (B) as a photocuring initiator (B).
- B2) and an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group as the binder resin (C), and a compound having two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group Contains a crosslinkable resin (C22).
- an acid is generated from the photoacid generator (B2) in the light irradiation portion during exposure in photolithography or the like, and an alkali-soluble resin having a carboxyl group and / or a phenolic hydroxyl group ( C21) and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group undergo a crosslinking reaction to form a cured coating film.
- the polymer (A) contained in the acid-curable photosensitive composition according to the present invention is a characteristic component in the photosensitive composition of the present invention, and includes the above-described radical curable photosensitive composition including preferred embodiments thereof.
- the polymer (A) described in the article can be applied to the acid-curable photosensitive composition.
- the content of the polymer (A) in the photosensitive composition can also be the same as described above.
- the polymer (A) ′ described above as a component capable of imparting a liquid repellency to the partition walls can be used in the same manner as in the case of the radical curable photosensitive composition.
- Photocuring initiator (B) (photoacid generator (B2))
- a photoacid generator (B2) that is a compound that generates an acid by light is used as the photocuring initiator (B).
- the photoacid generator (B2) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.
- diaryliodonium salt examples include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-t-butylphenyl) iodonium, and the like.
- the anion moiety of the diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate, (R f ) k PF (6-k) ⁇ (where k is an integer of 1 to 6) and the like.
- the diaryliodonium salt consists of a combination of one of the cation moieties and one of the anion moieties.
- An example is bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate.
- the cation moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, and the like.
- Specific examples of the anion moiety of the triarylsulfonium salt include specific examples of the anion moiety of the diaryl iodonium salt.
- a triarylsulfonium salt consists of a combination of one of the cation moieties and one of the anion moieties. Examples thereof include triphenylsulfonium trifluoromethanesulfonate.
- triazine compounds include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (2-furyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-furyl) ethenyl-bis (trichloromethyl)- Examples include 1,3,5-triazine and 2- (3,4-dimethoxyphenyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine.
- sulfonyl compound examples include bis (phenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.
- sulfonic acid esters include 2-nitrobenzyl p-toluenesulfonate, ⁇ - (p-toluenesulfonyloxyimino) -phenylacetonitrile, and the like.
- the content of the photoacid generator (B2) in the acid curable photosensitive composition according to the present invention is preferably 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the total solid content of the composition. More preferred. Within this range, the developability of the photosensitive composition will be good.
- Binder resin (C) (alkali-soluble resin (C21) / crosslinkable resin (C22))
- the binder resin (C) includes a carboxyl group and / or a phenolic hydroxyl group that undergoes cross-linking polymerization by the action of the acid generated by the photoacid generator (B2).
- Alkali-soluble resin (C21) The alkali-soluble resin (C21) has a carboxyl group and / or a phenolic hydroxyl group.
- a crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group, and which has two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group; It can be crosslinked to form a cured film.
- the alkali-soluble resin (C21) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive composition.
- These resins preferably have substantially no groups (1) and (2).
- a resin (C21-1) obtained by polymerizing a monomer having a carboxyl group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as an essential component is obtained by polymerizing the carboxyl group and ethylene. It can be obtained by copolymerizing a monomer having an ionic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond, if necessary, with another monomer.
- the proportion of monomer units based on other monomers is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. Within this range, the alkali solubility and developability of the photosensitive composition are good.
- the monomer having a carboxyl group and an ethylenic double bond used for preparing the alkali-soluble resin (C21-1) includes acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid. Examples include acids, fumaric acid, cinnamic acid, or salts thereof.
- Examples of the monomer having a phenolic hydroxyl group and an ethylenic double bond include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like, in which one or more hydrogen atoms of these benzene rings are methyl, ethyl, Alkyl groups such as n-butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms, haloalkyl groups in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms, nitro groups, cyano groups, amide groups And the like.
- the other monomer the same monomer as the other monomer used for the production of the polymer (A) can be used.
- phenol resin examples include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone and phenols which are at least one selected from these alkyl-substituted or halogen-substituted aromatic compounds as aldehydes such as formaldehyde, acetaldehyde and benzaldehyde.
- aldehydes such as formaldehyde, acetaldehyde and benzaldehyde.
- a phenol / formaldehyde resin, a cresol / formaldehyde resin, or a phenol / cresol / formaldehyde cocondensation resin can be used.
- the acid value of the alkali-soluble resin (C21) is preferably 10 to 600 mgKOH / g, more preferably 50 to 300 mgKOH / g. Within this range, the developability of the photosensitive composition will be good.
- the number average molecular weight of the alkali-soluble resin (C21) is preferably 200 to 20000, more preferably 2000 to 15000. Within this range, the alkali solubility and developability of the photosensitive composition will be good.
- the mass average molecular weight is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , and more preferably 2.0 ⁇ 10 3 to 15 ⁇ 10 3 . When the mass average molecular weight is less than 1.5 ⁇ 10 3 , curing during exposure may be insufficient, and when it exceeds 30 ⁇ 10 3 , developability may be deteriorated.
- the content of the alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group is 10 to 90% by mass with respect to the total solid content of the composition. Preferably, 30 to 80% by mass is more preferable. Within this range, the developability of the photosensitive composition of the present invention is good.
- the crosslinkable resin (C22) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group to form a cured coating film. Moreover, when the said polymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge
- the crosslinkable resin (C22) is preferably a compound substantially free of the group (1) and the group (2).
- the crosslinkable resin (C22) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These may be used alone or in combination of two or more.
- Amino resins include compounds in which a part or all of amino groups such as melamine compounds, guanamine compounds, urea compounds, etc. are hydroxymethylated, or part or all of the hydroxyl groups of the hydroxymethylated compounds are methanol, ethanol , A compound etherified with n-butyl alcohol, 2-methyl-1-propanol, and the like, for example, hexamethoxymethylmelamine and the like.
- Epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol / novolak type epoxy resins, cresol / novolac type epoxy resins, trisphenol methane type epoxy resins, brominated epoxy resins and other glycidyl ethers, 3, Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, glycidyl such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate Esters, tetraglycidyldiaminodiphenylmethane, glycidylamines such as triglycidylparaaminophenol, and complex such as triglycidyl isocyanurate Such expression epoxy resin.
- oxazoline compound examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl Mention may be made of copolymers of polymerizable monomers such as -4-methyl-2-oxazoline.
- the content of the crosslinkable resin (C22), which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group is the total solid content of the composition.
- the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. Within this range, the developability of the photosensitive composition will be good.
- the acid curable photosensitive composition according to the present invention includes the polymer (A), a photoacid generator (B2) as a photocuring initiator (B), and a binder resin (C). And an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group, and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group.
- various optional components can be contained for the purpose of improving various functions and the like within a range not impairing the effects of the present invention.
- optional components include all components other than the crosslinking agent (D) having two or more ethylenic double bonds among the optional components described in the radical curable photosensitive composition.
- the photosensitive composition it can be used for an acid-curable photosensitive composition.
- the acid-curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
- a diluted solution obtained by diluting the photosensitive composition with a solvent is used. It is preferable to form a coating film of the photosensitive composition by volatilizing and removing the solvent after using it to form a coating film (wet film).
- the solvent for diluting the photosensitive composition is not particularly limited. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2- Cellsorbs such as butoxyethanol and 2-propoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol; methyl acetate; Ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether
- the diluted solution obtained by diluting the photosensitive composition with a solvent is preferably prepared so that the concentration of the photosensitive composition, that is, the solid content concentration is 5 to 40% by mass, and is 10 to 25% by mass. It is more preferable to prepare.
- the partition wall of the present invention is a partition wall formed by partitioning the substrate into a plurality of pixel forming sections by using the cured film of the photosensitive composition of the present invention. It can be applied to a black matrix of an organic EL element.
- a diluted solution of the photosensitive composition of the present invention is applied to a substrate.
- the substrate is not particularly limited, and various glass plates; SiC substrate, inorganic substrate such as silicon; inorganic oxide substrate such as ITO; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate And thermoplastic resin sheets such as polysulfone, polyimide, and poly (meth) acrylic resin; and cured sheets of thermosetting resin such as epoxy resin and unsaturated polyester.
- the substrate is preferably a heat resistant resin such as a glass plate and polyimide.
- the substrate is preferably transparent.
- the substrate is a substrate in which an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
- an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
- the coating method is not particularly limited, and examples thereof include spin coating, spraying, slit coating, roll coating, spin coating, and bar coating.
- the coating film formed on the substrate is dried. Thereby, since a solvent volatilizes, the coating film of the photosensitive composition without stickiness is obtained. It does not specifically limit as a drying method, Vacuum drying and heat drying are mentioned. In order to efficiently dry the coating film without causing uneven appearance, it is preferable to use vacuum drying and heat drying in combination.
- the drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, but the vacuum drying is preferably 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and the heat drying is 50 to 120. It is preferable that the temperature is 10 to 2000 seconds at ° C.
- the coating film is exposed through a mask having a predetermined pattern.
- the light irradiated at the time of exposure is not particularly limited, and visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser, etc.
- Excimer laser, X-ray, electron beam and the like can be mentioned.
- Light having a wavelength of 100 to 600 nm is preferable, light having a wavelength of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.
- a well-known super high pressure mercury lamp etc. can be used as a light source.
- Exposure is usually 5 ⁇ 1000mJ / cm 2 at i-line standard, preferably 10 ⁇ 400mJ / cm 2, more preferably 20 ⁇ 200mJ / cm 2, particularly preferably 50 ⁇ 100mJ / cm 2.
- the exposure amount is less than 5 mJ / cm 2 , the coating film may be insufficiently cured and the developability may be deteriorated.
- it exceeds 1000 mJ / cm 2 high resolution may not be obtained.
- the developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts.
- the development time that is, the time for contact with the developer is preferably 5 to 180 seconds.
- the developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a shower method.
- Jet rinse process Furthermore, it is preferable to perform jet rinsing.
- Jet rinsing is a process in which water is compressed or water and air are compressed and sprayed onto a substrate on which a partition wall is formed.
- the pressure is preferably 2 to 20 MPa.
- post-exposure may be performed on the developed partition wall.
- the exposure may be performed from either the surface on which the partition is formed or the surface on which the partition is not formed, or may be performed from both surfaces.
- the light irradiated during exposure is preferably ultraviolet light.
- the light source a known ultra-high pressure mercury lamp, high-pressure mercury lamp, or the like can be used. These light sources generally emit light having a wavelength of 600 nm or less that contributes to hardening of the partition walls, and emit less light having a wavelength of 200 nm or less that causes oxidative decomposition of the partition walls. Furthermore, it is preferable that the quartz tube glass used for the light source has a function of an optical filter that cuts light having a wavelength of 200 nm or less.
- Exposure is usually at 50 mJ / cm 2 or more, preferably 200 mJ / cm 2 or more, more preferably 1000 mJ / cm 2 or more, 2000 mJ / cm 2 or more is particularly preferable.
- a low-pressure mercury lamp may be used as the light source.
- the exposure amount is preferably 500 mJ / cm 2 or less, and 300 mJ / cm 2 or less. Is more preferable.
- the heating condition is preferably 150 to 250 ° C. for 5 to 90 minutes, and the heating temperature is more preferably 180 ° C. or higher. If the heating temperature is too low, chemical resistance may be insufficient, and when ink is applied to the partition walls, the partition walls may swell or the ink may ooze. On the other hand, if the heating temperature is too high, the partition walls may be thermally decomposed.
- a hot plate, an oven or the like can be used as the heating device.
- the partition wall of the present invention is formed by curing the photosensitive composition of the present invention through the photolithography process as described above.
- the black matrix which exhibits black can be comprised by mix
- a black matrix will be formed by forming a partition using a photosensitive composition.
- the partition wall of the present invention preferably has a width (average value) of 100 ⁇ m or less, more preferably 20 ⁇ m or less.
- the distance between adjacent partition walls, that is, the width (average value) of the openings is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less.
- the height (average value) of the partition walls is preferably 0.05 to 50 ⁇ m, more preferably 0.2 to 10 ⁇ m.
- the liquid repellency (ink repellency) of the partition walls made of a cured film of the photosensitive composition includes water repellency and oil repellency, and water and PGMEA (propylene glycol monomethyl ether acetate: as a solvent for the ink, respectively) It can be evaluated by the contact angle of a commonly used organic solvent).
- the upper surface of the partition wall of the present invention preferably has a water contact angle of 90 ° to 150 °, more preferably 95 ° to 120 °. Further, the upper surface of the partition wall preferably has a PGMEA contact angle of 35 ° to 55 °, more preferably 40 ° to 50 °.
- the color filter of the present invention is a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, and the partition is formed of the partition of the present invention.
- the pixel is formed by an inkjet method.
- the partition walls are preferably a black matrix having an optical density of about 2 to 7.
- the color filter of the present invention is manufactured by forming a partition, for example, a black matrix on a substrate, and then forming a pixel by applying ink to the opening of the partition using an inkjet method. can do.
- the ink jet method is not particularly limited, but is a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which intermittent ink is ejected using a piezoelectric element, and ink is heated and intermittently utilizing its foaming.
- the method of injecting automatically is mentioned.
- the arrangement of the pixels is not particularly limited, and examples thereof include known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.
- the ink mainly contains a coloring component, a binder resin component, and a solvent, and may be either water-based ink or oil-based ink.
- a coloring component pigments and / or dyes excellent in heat resistance, light resistance and the like are preferable.
- the binder resin component a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
- the water-based ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and / or a water-dispersible resin as a binder resin component.
- the oil-based ink contains an organic solvent as a solvent, and a resin soluble in the organic solvent as a binder resin component.
- a pixel after applying an ink to a partition, for example, an opening of a black matrix, using an inkjet method, a pixel can be formed by performing drying, heat curing, ultraviolet curing, or the like as necessary.
- a protective film can be formed as necessary. Thereby, the surface smoothness of the color filter can be improved, and the eluent from the partition walls and pixels can be blocked from reaching the liquid crystal layer adjacent to the protective film.
- a method for removing the liquid repellency on the upper surface of the partition wall is not particularly limited, and examples thereof include plasma ashing treatment and optical ashing treatment.
- a photo spacer may be formed on a partition wall, for example, a black matrix, if necessary.
- Organic EL Element is an organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, and the partition is formed of the partition of the present invention.
- the pixel is formed by an inkjet method.
- the organic EL device of the present invention can be produced as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched into a desired pattern as necessary.
- a partition for example, a black matrix is formed on the substrate, and then a hole transport material is used as an ink in the opening of the partition (black matrix) using an ink jet method.
- the solution of the above and the solution of the light emitting material are sequentially applied and dried to form a hole transport layer and a light emitting layer.
- an organic EL element is obtained by forming an electrode, such as aluminum, using a vapor deposition method or the like to form a pixel.
- V-65 V-65 (Wako Pure Chemical Industries, 2,2'-azobis (2,4-dimethylvaleronitrile))
- Chain transfer agent n-DM: n-dodecyl mercaptan (solvent)
- MEK 2-butanone
- Photosensitive composition component photocuring initiator (B): photopolymerization initiator (B1)
- OXE02 OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (general formula (5) Wherein R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group)
- EX1010 EX-1010 (manufactured by Nagase ChemteX Corporation, a resin solution in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the general formula (7), solid content: 70% by mass, mass average molecular weight: 3,020)
- ZCR15 photocur
- the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and the 0.5 mass% tetrahydrofuran solution of the measurement sample is measured. 40 ⁇ L was injected.
- ⁇ Fluorine atom content The fluorine atom content in the polymer was calculated from the charged value of the polymerization reaction.
- the acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.
- Example 1 Polymer (A-1) (0.03 part) obtained in the above synthesis example, CB (31.6 parts) as a dispersion of black colorant (E), OXE02 as photopolymerization initiator (B1) (0.76 parts), EX1010 (6.3 parts) as a dispersion of the photosensitive resin (C1), DPHA (1.9 parts) as a crosslinking agent (D), and PGMEA (34.4 parts) as a solvent ) And cyclohexanone (25.0 parts) were mixed to obtain a diluted solution of the photosensitive composition.
- the content of the polymer (A-1) in the total solid content of the diluted liquid of the photosensitive composition was 0.20% by mass.
- a diluted solution of the photosensitive composition is applied on a glass substrate, and then dried on a hot plate at 100 ° C. for 2 minutes to form a coating film of the photosensitive composition having a thickness of 2.0 ⁇ m. did.
- the coating film was irradiated with light having an exposure amount of 100 mJ / cm 2 on the basis of i-line (365 nm) through a mask to be exposed.
- the mask has a lattice pattern with a light shielding portion of 150 ⁇ m ⁇ 400 ⁇ m and a light transmitting portion of 20 ⁇ m, and the volume of the opening formed is 120 pL.
- the area of the pattern was 10 cm 2.
- the developer used was a 10-fold diluted aqueous solution of semi-clean DL-A4 (trade name, manufactured by Yokohama Yushi Kogyo Co., Ltd.).
- a nozzle whose irradiation angle to the substrate was narrowed to 8 degrees or less was used as a nozzle, and a developing solution was discharged onto the substrate under a pressure of 0.15 MPa to generate bubbles and spin development was performed. Thereafter, the unexposed portion was washed away with water and dried.
- the glass substrate sample (1) of Example 1 in which the partition walls were formed was obtained by heating (post-baking) the glass plate in an oven at 220 ° C. for 30 minutes.
- Examples 2 to 5 Photosensitivity containing each of the polymers (A-2) to (A-5) obtained in the above synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2.
- Glass substrate samples (1) of Examples 2 to 5 in which partition walls made of a cured film of the composition were formed, and Examples 2 to 5 of which a cured product of the coating film of the photosensitive composition was formed The glass substrate sample (2) and the glass substrate sample (3) which performed jet rinse further were obtained.
- the liquid repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate sample (2). Moreover, the liquid repellency tolerance by jet rinse was evaluated by measuring the contact angle of PGMEA of the surface of the coating-film hardened
- the contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid come into contact, and is defined as an angle on the side including the liquid. For this reason, the larger the contact angle, the better the liquid repellency of the cured film.
- ⁇ State of residual film generation> In the glass substrate sample (1), the number of development defects was visually measured to evaluate the state of residual film generation. The number of development defects per area was determined to be less than 100, ⁇ for 100 to less than 200, and x for 200 or more.
- the mass average molecular weight (Mw (A)) is in the range of 2.6 ⁇ 10 4 ⁇ Mw (A) ⁇ 20 ⁇ 10 4
- polyoxyalkylene Polymers (A-1) to (A-5) corresponding to the group-containing polymer (A) (the content of polyoxyalkylene groups in the polymer is preferably 5 to 60% by mass in the present invention)
- the liquid repellency was good. This is because the polymer (A) was not peeled off from the surface layer even when the barrier ribs obtained using the photosensitive compositions of Examples 1 to 5 were subjected to high-pressure water washing called jet rinsing. Is maintained.
- the ink wets into the openings between the partition walls. It expanded and there were no white spots. This indicates that in the coating films obtained from the photosensitive compositions of Examples 1 to 5, the developability was good and the polymer (A) component did not move from the partition wall surface to the opening between the partition walls. Is.
- the weight average molecular weight of the polymer (A) was 40,000 or more.
- the ink wets and spreads in the opening between the partition walls, and there is no white spot. It was.
- a polymer (R-1) having a mass-average molecular weight Mw (A) outside the range of the polymer (A) according to the present invention specifically a mass-average molecular weight Mw of less than 2.6 ⁇ 10 4 is obtained.
- the liquid repellency after jet rinsing was remarkably lowered. Further, when about 20 pL of ink was applied to the opening between the partitions having a volume of 120 pL, that is, when the amount of ink applied was small relative to the volume of the opening, there was a portion where the ink did not spread out in the opening.
- the photosensitive composition of the present invention is an ink repellent component that does not have an ethylenic double bond, but has good ink repellency at the upper part of the partition wall, resistance to developer not corroded by the developer, residual film remaining without development It is a photosensitive composition containing an ink repellent component capable of imparting the property of suppressing the generation of ink and the good wetting and spreading property of the ink to the opening between the partition walls to the obtained partition wall.
- Such a photosensitive composition of the present invention is suitably used for forming barrier ribs, for example, for manufacturing color filters using an inkjet recording technique and for manufacturing organic EL display elements.
- a material for forming a permanent film such as a partition for partitioning each TFT of an organic TFT (Thin Film Transistor) array, a partition for an ITO electrode of a liquid crystal display element, a partition for a circuit wiring board.
Abstract
Description
また、撥インク成分として上記求められる性能を十分に備えたエチレン性二重結合を有する含フッ素樹脂においては、エチレン性二重結合を有する基を含フッ素樹脂に導入するために工程数が増える等製造面で不利な点があった。 However, in the conventional ink repellent component, when a fluorine-containing resin having an ethylenic double bond is used, the required performance of the obtained partition wall, that is, good ink repellency at the top of the partition wall, and erosion to the developer Performance such as resistance to the developer not developed, good wetting and spreading of the ink to the opening between the partition walls, etc. are sufficiently obtained, but when using a fluorine-containing resin having no ethylenic double bond, these performances The present condition is that the partition which fully satisfy | fills all is not obtained.
In addition, in the fluorine-containing resin having an ethylenic double bond sufficiently provided with the above-described performance as an ink repellent component, the number of steps is increased because a group having an ethylenic double bond is introduced into the fluorine-containing resin. There were disadvantages in manufacturing.
[1]下記一般式(1)で表される基を有する側鎖およびポリオキシアルキレン基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物であって、
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。)
前記重合体(A)の質量平均分子量(Mw(A))が、2.6×104<Mw(A)≦20×104であることを特徴とする感光性組成物。 The present invention provides a photosensitive composition, partition walls, a color filter, and an organic EL device having the following configuration.
[1] a polymer (A) having a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group and having no side chain having an ethylenic double bond; A photosensitive composition comprising a photocuring initiator (B) and a binder resin (C),
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
The polymer (A) has a mass average molecular weight (Mw (A)) of 2.6 × 10 4 <Mw (A) ≦ 20 × 10 4 .
[3]前記重合体(A)が、酸性基を有する[1]または[2]に記載の感光性組成物。
[4]前記重合体(A)におけるフッ素原子含有割合が、20~50質量%である[1]~[3]のいずれかに記載の感光性組成物。
[5]前記感光性組成物の全固形分における前記重合体(A)の割合が、0.07~1質量%である[1]~[4]のいずれかに記載の感光性組成物。 [2] The photosensitive composition according to [1], wherein the content ratio of the polyoxyalkylene group in the polymer (A) is 5 to 60% by mass.
[3] The photosensitive composition according to [1] or [2], wherein the polymer (A) has an acidic group.
[4] The photosensitive composition according to any one of [1] to [3], wherein the polymer (A) has a fluorine atom content of 20 to 50% by mass.
[5] The photosensitive composition according to any one of [1] to [4], wherein the ratio of the polymer (A) in the total solid content of the photosensitive composition is 0.07 to 1% by mass.
[7]前記重合体(A)が、さらに下記一般式(2)で表される基を有する側鎖を有する[1]~[6]のいずれかに記載の感光性組成物。 [6] The photosensitive composition according to any one of [1] to [5], wherein the polymer (A) further has at least one selected from the group consisting of an epoxy group, a mercapto group, and a hydroxyl group.
[7] The photosensitive composition according to any one of [1] to [6], wherein the polymer (A) further has a side chain having a group represented by the following general formula (2).
[9]前記光硬化開始剤(B)が光重合開始剤であり、前記バインダー樹脂(C)が酸性基とエチレン性二重結合とを有する感光性樹脂である[1]~[8]のいずれかに記載の感光性組成物。 [8] A side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and having a group represented by the general formula (1) and an ethylenic group It is a polymer (A) ′ having no side chain having a double bond, and its mass average molecular weight (Mw (A) ′) is 2.6 × 10 4 <Mw (A) ′ ≦ 20 × 10. 4. The photosensitive composition according to any one of [1] to [7], further comprising a polymer (A) ′ that is 4 .
[9] The photocuring initiator (B) is a photopolymerization initiator, and the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond. The photosensitive composition in any one.
[11]さらに、黒色着色剤(E)を含む[1]~[10]のいずれかに記載の感光性組成物。
[12]基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、[1]~[11]のいずれかに記載の感光性組成物の塗膜硬化物からなることを特徴とする隔壁。 [10] The photosensitive composition according to [9], further comprising a crosslinking agent (D) having two or more ethylenic double bonds.
[11] The photosensitive composition according to any one of [1] to [10], further comprising a black colorant (E).
[12] A partition formed in a manner that partitions the substrate into a plurality of sections for pixel formation, and is made of a cured film of the photosensitive composition according to any one of [1] to [11] Septum characterized by.
[14]基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が[12]に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする有機EL素子。 [13] A color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method A color filter characterized by being made.
[14] An organic EL element having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed by the partition described in [12], and the pixel is formed by an inkjet method. An organic EL element formed.
また、本明細書において、ポリオキシアルキレン基とは、-(RO)p-で表わされる2価の基(Rはアルキレン基、pは2以上の整数を表す)である。ポリオキシアルキレン基の一方の端は末端基と結合し、もう一方の端は重合体の主鎖側に結合する結合手である。 In the present specification, the term “photocuring initiator” is used as a general term for compounds that generate active species by light irradiation to initiate the curing reaction of the binder resin (C).
In this specification, the polyoxyalkylene group is a divalent group represented by — (RO) p — (R represents an alkylene group, and p represents an integer of 2 or more). One end of the polyoxyalkylene group is bonded to the terminal group, and the other end is a bond bonded to the main chain side of the polymer.
なお、本明細書において、特に説明のない限り、%は、質量%を表す。また、(メタ)アクリロイル基は、アクリロイル基とメタクリロイル基の両者を意味する総称として使用する。(メタ)アクリレートは、アクリレートとメタクリレートの両者を意味する総称として使用する。(メタ)アクリル酸は、アクリル酸とメタクリル酸の両者を意味する総称として使用する。(メタ)アクリルアミドは、アクリルアミドとメタクリルアミドの両者を意味する総称として使用する。(メタ)アリルは、アリルとメタリルの両者を意味する総称として使用する。一般式(1)で表される基を、基(1)ともいう。他の基も同様である。 Although the form for implementing this invention is demonstrated below, this invention is not limited to the following embodiment.
In the present specification, unless otherwise specified,% represents mass%. Further, the (meth) acryloyl group is used as a general term meaning both an acryloyl group and a methacryloyl group. (Meth) acrylate is used as a generic term for both acrylate and methacrylate. (Meth) acrylic acid is used as a generic term for both acrylic acid and methacrylic acid. (Meth) acrylamide is used as a general term for both acrylamide and methacrylamide. (Meth) allyl is used as a generic term for both allyl and methallyl. The group represented by the general formula (1) is also referred to as a group (1). The same applies to other groups.
本発明の感光性組成物は、下記一般式(1)で表される基を有する側鎖およびポリオキシアルキレン基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない、質量平均分子量(Mw(A))が、2.6×104<Mw(A)≦20×104である重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物である。
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。) <1> Photosensitive composition The photosensitive composition of the present invention has a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group, and an ethylenic double bond. A polymer (A) having a weight average molecular weight (Mw (A)) of 2.6 × 10 4 <Mw (A) ≦ 20 × 10 4 and a photocuring initiator (B And a binder resin (C).
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
ネガ型感光性組成物は、硬化の種類により、例えば、ラジカル硬化型、酸硬化型等の幾つかのタイプに分類され、その硬化の種類により、用いる光硬化開始剤(B)およびバインダー樹脂(C)の組合せが選択される。本発明の感光性組成物は、ネガ型感光性組成物であれば、いずれの硬化のタイプにも適用可能であるが、特にラジカル硬化型の感光性組成物に好適である。以下、本発明の感光性組成物の実施の形態について、ラジカル硬化型感光性組成物および酸硬化型感光性組成物を例として説明する。 The photosensitive composition of the present invention is a photosensitive composition comprising the polymer (A), a photocuring initiator (B), and a binder resin (C), and is a binder in a light irradiation portion upon exposure in photolithography or the like. It is a negative photosensitive composition in which the resin (C) is cured by the action of the photocuring initiator (B). In photolithography or the like, a portion that is not irradiated with light (an unexposed portion) is selectively removed during alkali development performed after exposure, and as a result, a partition wall made of a cured product of the photosensitive composition is formed. It is formed.
The negative photosensitive composition is classified into several types such as a radical curable type and an acid curable type depending on the type of curing, and depending on the type of curing, the photocuring initiator (B) and the binder resin ( A combination of C) is selected. The photosensitive composition of the present invention can be applied to any curing type as long as it is a negative photosensitive composition, but is particularly suitable for a radical curable photosensitive composition. Hereinafter, an embodiment of the photosensitive composition of the present invention will be described using a radical curable photosensitive composition and an acid curable photosensitive composition as examples.
本発明の感光性組成物がラジカル硬化型の場合、感光性組成物は、重合体(A)、光硬化開始剤(B)としての光重合開始剤(B1)、およびバインダー樹脂(C)としての酸性基およびエチレン性二重結合とを有する感光性樹脂(C1)を含有する。このようなラジカル硬化型感光性組成物は、フォトリソグラフィ等における露光に際して光照射部分では光重合開始剤(B1)の作用により感光性樹脂(C1)がラジカル重合し硬化が促進され塗膜硬化物を形成する。
本発明に係るラジカル硬化型感光性組成物が含有する各成分について以下に説明する。 (1) Radical curable photosensitive composition When the photosensitive composition of the present invention is a radical curable type, the photosensitive composition contains a polymer (A) and a photopolymerization initiator (B) as a photocuring initiator (B). B1) and a photosensitive resin (C1) having an acidic group and an ethylenic double bond as the binder resin (C). Such a radical curable photosensitive composition is a coating film cured product in which the photosensitive resin (C1) is radically polymerized by the action of the photopolymerization initiator (B1) in the light-irradiated portion during exposure in photolithography or the like, and curing is accelerated. Form.
Each component which the radical curable photosensitive composition concerning this invention contains is demonstrated below.
重合体(A)は、上記一般式(1)で表される基を有する側鎖を有し、ポリオキシアルキレン基を有しかつエチレン性二重結合を有する側鎖を有しない含フッ素重合体であり、その質量平均分子量(Mw(A))は、2.6×104<Mw(A)≦20×104である。 (1-1) Polymer (A)
The polymer (A) has a side chain having the group represented by the general formula (1), has a polyoxyalkylene group, and does not have a side chain having an ethylenic double bond. The mass average molecular weight (Mw (A)) is 2.6 × 10 4 <Mw (A) ≦ 20 × 10 4 .
ポリオキシアルキレン基と、他の成分、例えばバインダー樹脂(C)との相互作用、いわゆるアンカー効果により、重合体(A)は、塗膜表面から脱離しにくくなる効果が考えられる。特に、現像工程の後の高圧水を使用したジェットリンス工程を行う場合、重合体(A)は表層から脱離しやすい。しかしながら、重合体(A)は、ポリオキシアルキレン基を有する側鎖を有するため、前記アンカー効果により、塗膜表面に重合体(A)が残りやすく、塗膜は撥液性を発現しやすい傾向がある。このため、インクジェット法を用いて、隔壁で囲まれた開口部にインクを塗布する際に、隣接する開口部間における混色の発生や開口部における白抜けの発生を抑制することができる。また、重合体(A)は、ポリオキシアルキレン基を有する側鎖を有することで、以下に説明する残膜の発生を抑制することができる。 Furthermore, since the polymer (A) has a side chain having a polyoxyalkylene group, the liquid repellency can be maintained even when a jet rinsing step using high-pressure water after the development step is performed. The reason why the phenomenon is observed is not necessarily clear, but is considered as follows.
Due to the interaction between the polyoxyalkylene group and other components such as the binder resin (C), the so-called anchor effect, the polymer (A) is considered to be less likely to be detached from the coating film surface. In particular, when the jet rinsing step using high-pressure water after the development step is performed, the polymer (A) is easily detached from the surface layer. However, since the polymer (A) has a side chain having a polyoxyalkylene group, due to the anchor effect, the polymer (A) tends to remain on the surface of the coating film, and the coating film tends to exhibit liquid repellency. There is. For this reason, when ink is applied to the opening surrounded by the partition wall using the inkjet method, it is possible to suppress the occurrence of color mixing between adjacent openings and the occurrence of white spots in the openings. Moreover, a polymer (A) can suppress generation | occurrence | production of the residual film demonstrated below by having a side chain which has a polyoxyalkylene group.
ポリアルキレン鎖が残膜の発生を抑制する機構は定かではないが、現像液中の気泡が一旦、塗膜に付着したとしても、ポリアルキレン鎖が表面に存在することによって、容易に気泡が除去されるか、少なくとも同一箇所に気泡が留まりにくいことが考えられる。 That is, the phenomenon that the remaining film is generated is considered as follows. Since an alkaline developer used for producing barrier ribs or the like by photolithography or the like generally contains a surfactant, bubbles are easily generated in the development process. Moreover, when this bubble adheres to the liquid-repellent surface, it is difficult to remove. Therefore, there is a tendency that the ink repellent component contained in the photosensitive composition remains in the form of a film due to the bubbles adhering to the portion that should be dissolved and removed by the alkaline developer. The polymer (A) having a side chain having a polyoxyalkylene group can suppress the generation of the remaining film thus generated.
The mechanism by which polyalkylene chains suppress the formation of residual film is not clear, but even if bubbles in the developer once adhere to the coating, the bubbles are easily removed by the presence of polyalkylene chains on the surface. It is conceivable that bubbles are difficult to stay at least at the same location.
重合体(A)の質量平均分子量が2.6×104以下であると、隔壁間開口部の親液性が不十分であり、インクジェット法を用いてインクを塗布したときに開口部にインクが十分に濡れ拡がらない。また、質量平均分子量が20×104を超えると、アルカリ溶解性、現像性が不十分となる。
質量平均分子量(Mw(A))が3.0×104超12×104以下の範囲であると、さらにアルカリの種類や濃度、ジェットリンスの条件に因らず、撥液性が高く保たれやすく、製造マージンが広くなり好ましい。また、重合体(A)の製造のしやすさからも好ましい。 The mass average molecular weight (Mw (A)) of the polymer (A) used in the present invention is 2.6 × 10 4 <Mw (A) ≦ 20 × 10 4 . More preferably, 3.0 × 10 4 <Mw (A) ≦ 12 × 10 4 , still more preferably 3.5 × 10 4 ≦ Mw (A) ≦ 12 × 10 4 , and particularly preferably, 4.0 × 10 is a 4 ≦ Mw (a) ≦ 10 × 10 4.
When the mass average molecular weight of the polymer (A) is 2.6 × 10 4 or less, the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. Does not spread out sufficiently. On the other hand, when the mass average molecular weight exceeds 20 × 10 4 , alkali solubility and developability become insufficient.
When the mass average molecular weight (Mw (A)) is in the range of more than 3.0 × 10 4 and less than 12 × 10 4 , the liquid repellency is kept high regardless of the type and concentration of alkali and jet rinse conditions. It is preferable because it is easy to sag and has a wide manufacturing margin. Moreover, it is preferable also from the ease of manufacture of a polymer (A).
なお、本明細書において、質量平均分子量(Mw)および数平均分子量(Mn)とは、ゲルパーミエーションクロマトグラフィー法により、ポリスチレンを標準物質として測定した値をいう。 The number average molecular weight (Mn (A)) of the polymer (A) is preferably 1.0 × 10 4 ≦ Mn (A) ≦ 15.0 × 10 4 , and 1.5 × 10 4 ≦ It is more preferable that Mn (A) ≦ 12.0 × 10 4 , and it is particularly preferable that 2.0 × 10 4 ≦ Mn (A) ≦ 10.0 × 10 4 . When the number average molecular weight of the polymer (A) is less than 1.0 × 10 4 , the lyophilicity of the opening between the partition walls is insufficient, and the ink is applied to the opening when the ink is applied using an ink jet method. May not be sufficiently wet and spread, and if the number average molecular weight exceeds 15.0 × 10 4 , alkali solubility and developability may be insufficient.
In addition, in this specification, a mass average molecular weight (Mw) and a number average molecular weight (Mn) mean the value which measured polystyrene as a standard substance by the gel permeation chromatography method.
基(1)におけるRfとしては、上記エーテル性酸素原子を有していてもよい炭素数が1~20のフルオロアルキル基が好ましい。また、Xは、フッ素原子であることが特に好ましい。 The polymer (A) used for this invention has group (1) containing the fluorine atom shown by the said General formula (1) in a side chain. In the group (1), when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f may have a halogen atom excluding a fluorine atom. Good. As such a halogen atom, a chlorine atom is preferable. Further, the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable. Further, when R f is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or at the end of the fluoroalkyl group. May be.
R f in the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have the etheric oxygen atom. X is particularly preferably a fluorine atom.
Rfがエーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基の場合、Rfとしては、エーテル性酸素原子を有しないパーフルオロアルキル基とエーテル性酸素原子を有するパーフルオロアルキル基が好ましく、エーテル性酸素原子を有しないパーフルオロアルキル基がより好ましい。その炭素数は1~11が好ましく、3~5が特に好ましい。 In the above group (1), when R f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, R f is particularly limited as long as it has such a configuration. Not. As R f , specifically, —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 , —CF (CF 3 ) O (CF 2 ) 5 CF 3 , —CF 2 O (CF 2 CF 2 O) p CF 3 (p is 1 ), —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) q C 6 F 13 (q is an integer of 1 to 4), —CF (CF 3 ) O (CF 2 CF (CF 3 ) O) r C 3 F 7 (r is an integer of 1 to 5).
If R f is carbon atoms, which may have an etheric oxygen atom is 1 to 20 fluoroalkyl group, the R f, a perfluoroalkyl group and an etheric oxygen atom having no etheric oxygen atom A perfluoroalkyl group having an etheric oxygen atom is more preferable. The number of carbon atoms is preferably 1 to 11 and particularly preferably 3 to 5.
本発明で用いる重合体(A)におけるポリオキシアルキレン基の含有量は、5~60質量%が好ましい。より好ましくは、10~55質量%であり、特に好ましくは、15~50質量%である。重合体(A)におけるポリオキシアルキレン基の含有量が5質量%未満であると、現像工程の後に高圧水を使用したジェットリンス工程を行った場合、撥液性が著しく低下することがある。さらに、最終的に得られる隔壁や隔壁開口部に多くの残膜が存在する状態となるおそれがある。また、ポリオキシアルキレン基の含有量が60質量%を超えると、撥液性が低下することがある。 In addition, the polymer (A) used in the present invention has a side chain having a polyoxyalkylene group. This polyoxyalkylene group is a polyoxyalkylene group having a repeating unit of an oxyalkylene group having 2 to 4 carbon atoms.
The content of the polyoxyalkylene group in the polymer (A) used in the present invention is preferably 5 to 60% by mass. More preferably, it is 10 to 55% by mass, and particularly preferably 15 to 50% by mass. When the content of the polyoxyalkylene group in the polymer (A) is less than 5% by mass, the liquid repellency may be significantly lowered when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, there is a possibility that a large amount of residual film exists in the partition walls and partition opening portions finally obtained. Moreover, when the content of the polyoxyalkylene group exceeds 60% by mass, the liquid repellency may be lowered.
-(R11O)m(R12O)jR13 …(11)
(式(11)中、R11はエチレン基を、R12は炭素数3または4のアルキレン基を、R13は、水素原子、または、置換基を有してもよい炭素数1~10のアルキル基を、mは4~100、jは0~100の整数をそれぞれ表し、m+jは4~100である。 The polyoxyalkylene group used in the present invention is specifically a group represented by the following general formula (11) (hereinafter sometimes referred to as group (11)).
-(R 11 O) m (R 12 O) j R 13 (11)
(In the formula (11), R 11 represents an ethylene group, R 12 represents an alkylene group having 3 or 4 carbon atoms, R 13 represents a hydrogen atom or an optionally substituted substituent having 1 to 10 carbon atoms. In the alkyl group, m represents an integer of 4 to 100, j represents an integer of 0 to 100, and m + j is 4 to 100.
基(11)中、mは4~100、jは0~100の整数をそれぞれ表すが、それぞれ50以下であることが好ましく、30以下であることがより好ましい。また、ポリオキシアルキレン基中のR11の数の割合であるm/(m+j)は、50~100%であることが好ましく、80~100%であることがより好ましく、実質上100%であることが特に好ましい。
また、m+jは、4~100であり、好ましくは6~50、より好ましくは8~30である。m+jが3以下であると、現像工程の後に高圧水を使用したジェットリンス工程を行った場合、撥液性が低下する傾向がある。さらに、残膜が多く発生する傾向がある。m+jが101以上であると、ポストベイク時に開口部に重合体(A)がマイグレートし、隔壁間開口部の親液性が不十分になり、インクジェット法を用いてインクを塗布したとき、開口部にインクが十分に濡れ拡がらないおそれがある。なお、上記一般式(11)において、(R11O)m(R12O)jは、基(11)が、m個の(R11O)単位とj個の(R12O)単位を有することを表すものであって、(R11O)単位と(R12O)単位の結合の順番については特に制限されるものではない。つまり、基(11)において、m個の(R11O)単位とj個の(R12O)単位は、例えば、交互に、またはランダムに、もしくはブロックで結合していてもよい。 In the group (11), R 11 represents an ethylene group (—CH 2 CH 2 —), and R 12 represents an alkylene group having 3 or 4 carbon atoms. The structure of the alkylene group having 3 or 4 carbon atoms may be a linear structure or a branched structure. R 12 is a propylene group (—CH 2 CH (CH 3 ) —), a trimethylene group (—CH 2 CH 2 CH 2 —), an ethylethylene group (—CH 2 CH (CH 2 CH 3 ) —), 1, Examples include 2-dimethylethylene group (—CH (CH 3 ) CH (CH 3 ) —), tetramethylene group (— (CH 2 ) 4 —), and propylene group or tetramethylene group is preferable.
In the group (11), m represents an integer of 4 to 100, and j represents an integer of 0 to 100, respectively, preferably 50 or less, more preferably 30 or less. Further, m / (m + j), which is the ratio of the number of R 11 in the polyoxyalkylene group, is preferably 50 to 100%, more preferably 80 to 100%, and substantially 100%. It is particularly preferred.
M + j is 4 to 100, preferably 6 to 50, and more preferably 8 to 30. When m + j is 3 or less, the liquid repellency tends to decrease when a jet rinsing process using high-pressure water is performed after the development process. Furthermore, there is a tendency that a large amount of residual film is generated. When m + j is 101 or more, the polymer (A) migrates to the opening during post-baking, and the lyophilicity of the opening between the partition walls becomes insufficient. When the ink is applied using the inkjet method, the opening Ink may not be sufficiently wet and spread. In the general formula (11), (R 11 O) m (R 12 O) j is a group (11) having m (R 11 O) units and j (R 12 O) units. The order of bonding between the (R 11 O) unit and the (R 12 O) unit is not particularly limited. That is, in the group (11), m (R 11 O) units and j (R 12 O) units may be bonded alternately, randomly, or in blocks.
また、重合体(A)を含有する感光性組成物を用いて形成される隔壁の撥液性を考慮すると、R1およびR2は、それぞれ独立に、水素原子、メチル基、トリフルオロメチル基またはフェニル基であることが好ましく、全シロキサン単位のR1およびR2がメチル基であることが特に好ましい。
また、R3が、炭素数1以上10以下の有機基である場合、R3は窒素原子、酸素原子、フッ素原子等を有していてもよい。本発明において、R3は、水素原子、炭素数が1~5のアルキル基、またはフッ素原子で置換された炭素数1~5のアルキル基であることが好ましく、より好ましくは、トリフルオロメチル基またはメチル基である。さらに、基(2)においてnは、2~100の整数であることが好ましい。 In the group (2), R 1 and R 2 may be the same or different for each structural unit. When R 1 and R 2 are alkyl groups, the preferred carbon number is 1 to 10, and the more preferred carbon number is 1 to 6. These may have a linear structure or a branched structure. When R 1 and R 2 are cycloalkyl groups, the preferred carbon number is 3 to 10, and the more preferred carbon number is 5 or 6. When R 1 and R 2 are aryl groups, the preferred carbon number is 6-15, and the more preferred carbon number is 6-10. Some or all of the hydrogen atoms of R 1 and R 2 may be substituted with fluorine atoms.
In consideration of the liquid repellency of the partition formed using the photosensitive composition containing the polymer (A), R 1 and R 2 are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group. or it is preferably phenyl group, and particularly preferably R 1 and R 2 of the total siloxane units are methyl groups.
In addition, when R 3 is an organic group having 1 to 10 carbon atoms, R 3 may have a nitrogen atom, an oxygen atom, a fluorine atom, or the like. In the present invention, R 3 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and more preferably a trifluoromethyl group. Or it is a methyl group. Further, in the group (2), n is preferably an integer of 2 to 100.
本発明に用いる重合体(A)について、上記基(1)を有する側鎖および上記基(11)等のポリオキシアルキレン基を有する側鎖を有する構成とし、さらに任意に、上記基(2)を有する側鎖、酸性基を有する側鎖、隔壁マトリックスが有する官能基と熱または光により架橋可能な官能基を有する側鎖等を有する構成とするためには、これらの基を有する側鎖を重合反応によって直接形成する、または、重合反応後の化学変換によって形成する方法が挙げられる。 (Production of polymer (A))
The polymer (A) used in the present invention has a structure having a side chain having the group (1) and a side chain having a polyoxyalkylene group such as the group (11). In order to form a side chain having an acidic group, a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light, etc. Examples thereof include a method of forming directly by a polymerization reaction or a method of forming by chemical conversion after the polymerization reaction.
なお、共重合の種類としては、交互共重合、ブロック共重合、ランダム共重合等が挙げられ、それぞれ従来公知の方法で共重合を実行することができるが、本発明において、重合体(A)はランダム共重合により共重合して得られるランダム共重合体であることが好ましい。 The polymer (A) has a side chain having the essential group (1), a side chain having a polyoxyalkylene group such as the group (11), and a side chain optionally having the above groups by polymerization reaction. For direct formation, a monomer having the group (1), a monomer having a side chain having a polyoxyalkylene group such as the group (11), and a monomer having the group (2) if necessary Body, monomer having an acidic group, monomer having a functional group crosslinkable with the functional group of the partition matrix, and / or other monomer may be copolymerized under appropriate conditions. .
Examples of copolymerization include alternating copolymerization, block copolymerization, random copolymerization and the like, and the copolymerization can be carried out by a conventionally known method. In the present invention, the polymer (A) Is preferably a random copolymer obtained by copolymerization by random copolymerization.
CH2=CR4-COO-Y-CFXRf …(3) As a monomer which has the said group (1) used for manufacture of a polymer (A), it is preferable that it is a compound represented by following General formula (3). These may be used individually by 1 type, or may use 2 or more types together.
CH 2 = CR 4 —COO—Y—CFXR f (3)
これらのうちでも、化合物(3)におけるYとしては、入手の容易さから、炭素数が2~4のアルキレン基が好ましい。 Among the groups represented by Y in the above formula (3), Y, which is a divalent organic group having no fluorine atom having 1 to 6 carbon atoms, represents —R 5 —, —R 5 —NR 6. —SO 2 —, —R 5 —NR 6 —CO—, —CH 2 CH (OH) —R 7 — (R 5 is an alkylene group having 1 to 6 carbon atoms, and R 6 is a hydrogen atom or R 7 is a single bond or an alkylene group having 1 to 4 carbon atoms, provided that when R 6 is a methyl group, R 5 bonded to NR 6 has 1 to 5 carbon atoms. Etc.). Specific examples R 5, -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 )-and the like. Specific examples R 7, -CH 2 -, - CH 2 CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3 ) —, —CH 2 CH 2 CH 2 CH 2 —, —CH (CH 2 CH 2 CH 3 ) — and the like.
Among these, Y in the compound (3) is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
CH2=CR14-COO-(W-O)q-(R11O)m(R12O)jR13 …(12)
CH2=CR14-O-(W-O)q-(R11O)m(R12O)jR13 …(13)
(式(12)および(13)中、R14は、水素原子、塩素原子、臭素原子、ヨウ素原子、シアノ基、炭素数1~20のアルキル基、炭素数7~20のアリール基で置換されたアルキル基、炭素数6~20のアリール基、または炭素数3~20のシクロアルキル基、である。Wは、炭素数が1~10のフッ素原子を有さない2価の有機基である。qは0または1である。-(R11O)m(R12O)jR13は上記基(11)に相当する基である。) As a monomer which has the said group (11) used for manufacture of a polymer (A), it is preferable that it is a compound represented by the following general formula (12) or (13). These may be used individually by 1 type, or may use 2 or more types together.
CH 2 = CR 14 —COO— (W—O) q — (R 11 O) m (R 12 O) j R 13 (12)
CH 2 = CR 14 —O— (W—O) q — (R 11 O) m (R 12 O) j R 13 (13)
(In the formulas (12) and (13), R 14 is substituted with a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms. An alkyl group, an aryl group having 6 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and W is a divalent organic group having 1 to 10 carbon atoms and no fluorine atom. Q is 0 or 1. — (R 11 O) m (R 12 O) j R 13 is a group corresponding to the group (11).)
化合物(12)および(13)における-(W-O)q-は、qが0の場合は単結合を表す。qが1の場合、-(W-O)q-はR11側に酸素原子を有する有機基である。qが1の場合、Wは炭素数2~10の2価の炭化水素基が好ましく、炭素数2~6のアルキレン基、炭素数5または6のシクロアルキレン基、炭素数5または6のシクロアルキレン基の両側または片側に炭素数1~2のアルキレン基を有する合計炭素数6~10のシクロアルキレン基含有アルキレン基であることが好ましい。ただし、WがR11と同一のアルキレン基である場合は(さらに、qが0でない場合にはR12と同一のアルキレン基である場合も)、qが0とみなす。
また、上記化合物(12)および(13)におけるR14としては、水素原子、フッ素原子、塩素原子、メチル基、またはトリフルオロメチル基が好ましく、水素原子またはメチル基が特に好ましい。 The preferred embodiment of — (R 11 O) m (R 12 O) j R 13 in the compounds (12) and (13) is the same as that described for the group (11).
In the compounds (12) and (13), — (W—O) q — represents a single bond when q is 0. When q is 1, — (W—O) q — is an organic group having an oxygen atom on the R 11 side. When q is 1, W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, such as an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 or 6 carbon atoms, or a cycloalkylene having 5 or 6 carbon atoms. A cycloalkylene group-containing alkylene group having 6 to 10 carbon atoms in total and having an alkylene group having 1 to 2 carbon atoms on both sides or one side of the group is preferable. However, when W is the same alkylene group as R 11 (and when q is not 0, it is also the same alkylene group as R 12 ), q is regarded as 0.
Further, R 14 in the compounds (12) and (13) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
(一般式(12)で表される化合物))
CH2=CHOCH2C6H10CH2O(CH2CH2O)mR13
CH2=CHO(CH2)4O(CH2CH2O)mR13 As a compound represented by the said General formula (12) and General formula (13), the compound shown below etc. are mentioned as a preferable compound.
(Compound represented by formula (12)))
CH 2 = CHOCH 2 C 6 H 10 CH 2 O (CH 2 CH 2 O) m R 13
CH 2 = CHO (CH 2) 4 O (CH 2 CH 2 O) m R 13
CH2=CHCOO(CH2CH2O)mR13、
CH2=C(CH3)COO(CH2CH2O)mR13、
CH2=CHCOO(CH2CH2O)m(C3H6O)jR13、
CH2=C(CH3)COO(CH2CH2O)m(C3H6O)jR13、
CH2=CHCOO(CH2CH2O)m(C4H8O)jR13、
(上記式中、m、jは前記と同じ。C6H10はシクロヘキシレン基、C3H6はプロピレン基、C4H8はテトラメチレン基である。式中のR13は、炭素数1~10の直鎖、非置換のアルキル基、例えば、メチル基、水素原子等である。) (Compound represented by the general formula (13))
CH 2 = CHCOO (CH 2 CH 2 O) m R 13,
CH 2 = C (CH 3) COO (CH 2 CH 2 O) m R 13,
CH 2 = CHCOO (CH 2 CH 2 O) m (C 3 H 6 O) j R 13,
CH 2 = C (CH 3) COO (CH 2 CH 2 O) m (C 3 H 6 O) j R 13,
CH 2 = CHCOO (CH 2 CH 2 O) m (C 4 H 8 O) j R 13,
(In the above formula, m and j are the same as above. C 6 H 10 is a cyclohexylene group, C 3 H 6 is a propylene group, and C 4 H 8 is a tetramethylene group. In the formula, R 13 is the number of carbon atoms. 1 to 10 linear or unsubstituted alkyl groups such as a methyl group and a hydrogen atom)
ブレンマーPME-400(商品名、日本油脂社製、CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は約9である。以下、各市販品の分子式におけるk、m、jは全て分子間の平均値を示す。)。
NKエステルM-230G:(商品名、新中村化学社製、CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は約23である。)。
ニューフロンティアNFバイソマーPEM6E(商品名、第一工業製薬社製、CH2=C(CH3)COO(CH2CH2O)kH:式中、kは約6である。)。
ライトエステル130A(商品名、共栄社化学社製、CH2=CHCOO(CH2CH2O)kCH3:式中、kは約9である。)。
ブレンマーAE-400(商品名、日本油脂社製、CH2=CHCOO(CH2CH2O)kH:式中、kは約10である。)。
ブレンマーPP-800(商品名、日本油脂社製、CH2=C(CH3)COO(C3H6O)kH:式中、kは約13である。)、
ブレンマーAP-800(商品名、日本油脂社製、CH2=CHCOO(C3H6O)kH:式中、kは約13である。)。
ブレンマー70PEP-350B(商品名、日本油脂社製、CH2=C(CH3)COO(C2H4O)m(C3H6O)jH:式中、mは約5、jは約2である。)。
ブレンマー55PET-800(商品名、日本油脂社製、CH2=C(CH3)COO(C2H4O)m(C4H8O)jH:式中、mは約10、jは約5である。)。 In the preparation of the polymer (A), commercially available products can be used as the compounds (12) and (13) used for the purpose of introducing the group (11) into the side chain. Examples of such commercially available products include the following.
BLEMMER PME-400 (trade name, manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, and the value of k is It is about 9. Hereinafter, k, m, and j in the molecular formula of each commercially available product are all average values between molecules.)
NK ester M-230G: (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, k The value of is about 23).
New Frontier NF biisomer PEM6E (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) k H: where k is about 6).
Light ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH 2 ═CHCOO (CH 2 CH 2 O) k CH 3 : where k is about 9).
BLEMMER AE-400 (trade name, manufactured by NOF Corporation, CH 2 ═CHCOO (CH 2 CH 2 O) k H: where k is about 10).
BLEMMER PP-800 (trade name, manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (C 3 H 6 O) k H: wherein k is about 13),
Blemmer AP-800 (trade name, manufactured by NOF Corporation, CH 2 = CHCOO (C 3 H 6 O) k H: where k is about 13).
BLEMMER 70PEP-350B (trade name, manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (C 2 H 4 O) m (C 3 H 6 O) j H: where m is about 5, j is About 2).
BLEMMER 55PET-800 (trade name, manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (C 2 H 4 O) m (C 4 H 8 O) j H: wherein m is about 10, j is About 5).
上記Zが示す基のうちでも、化合物(4)が有するZとしては、炭素数が1~6の2価の炭化水素基が好ましく、具体的には、-CH2-、-CH2CH2-、-CH(CH3)-、-CH2CH2CH2-、-C(CH3)2-、-CH(CH2CH3)-、-CH2CH2CH2CH2-、-CH(CH2CH2CH3)-、-CH2(CH2)3CH2-、-CH(CH2CH(CH3)2)-等が挙げられる。特に、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-が好ましい。 Preferred embodiments of R 1 , R 2 , R 3 and n in the compound (4) are the same as those described for the group (2).
Of the groups represented by Z, the compound (4) has a divalent hydrocarbon group having 1 to 6 carbon atoms, specifically, —CH 2 —, —CH 2 CH 2 -, -CH (CH 3 )-, -CH 2 CH 2 CH 2- , -C (CH 3 ) 2- , -CH (CH 2 CH 3 )-, -CH 2 CH 2 CH 2 CH 2 -,- CH (CH 2 CH 2 CH 3 ) —, —CH 2 (CH 2 ) 3 CH 2 —, —CH (CH 2 CH (CH 3 ) 2 ) — and the like can be mentioned. In particular, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, and —CH 2 CH 2 CH 2 CH 2 — are preferable.
なお、重合体(A)の製造に際して、原料単量体として、基(1)を有する単量体以外にフッ素原子を含有する単量体を用いる場合には、得られる重合体(A)におけるフッ素原子含有量が上記好ましい範囲となるように、各原料単量体の割合を適宜調整すればよい。 The ratio of the monomer mass having the group (1) to the total mass of the monomer to be copolymerized is such that the fluorine atom content in the polymer (A) is in the above preferred range, specifically 20 to 50% by mass, The proportion is more preferably 25 to 42% by mass, particularly preferably 25 to 35% by mass. Although it depends on the type of the monomer having the group (1) as such a ratio, specifically, it is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, It is particularly preferably 40 to 60% by mass. If this ratio is too low, sufficient fluorine atom content cannot be secured, and sufficient development resistance tends to be not obtained, and in the vicinity of the upper surface of the partition formed using the photosensitive composition of the present invention. A polymer (A) becomes difficult to transfer, and as a result, the liquid repellency of the upper surface of a partition may become inadequate. On the other hand, if this ratio is too high, the fluorine atom content exceeds the preferred range, the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surfaces of the partition walls may be insufficient. . Furthermore, the adhesion between the partition walls and the substrate may be reduced.
In the production of the polymer (A), when a monomer containing a fluorine atom is used as a raw material monomer in addition to the monomer having the group (1), the resulting polymer (A) What is necessary is just to adjust suitably the ratio of each raw material monomer so that fluorine atom content may become the said preferable range.
このようにして製造される重合体(A)はランダム共重合であるが、共重合反応系へ原料単量体の導入時期を単量体の種類により変える等の通常の方法を用いてブロック共重合体を製造することも可能である。 The polymer (A) used in the present invention has, as essential components, a side chain having the above group (1) and a side chain having a polyoxyalkylene group such as the above group (11). A copolymer having a side chain having a group (2), a side chain having an acidic group, a side chain having a thermally crosslinkable functional group, and the like, the monomer having the group (1) and the group (11) A monomer having a polyoxyalkylene group such as a monomer having a group (2), a monomer having an acidic group, a monomer having a thermally crosslinkable functional group, and / or It can synthesize | combine by melt | dissolving another monomer in a solvent, heating, adding a polymerization initiator, and making it copolymerize. In addition, when making it copolymerize, it is preferable to add a chain transfer agent as needed. Moreover, you may add a monomer, a polymerization initiator, a solvent, and a chain transfer agent continuously. Here, the adjustment of the mass average molecular weight of the polymer (A) can be performed by adjusting the conditions such as the polymerization temperature and time, the amount of the polymerization initiator, the addition amount of the chain transfer agent, and the like.
The polymer (A) thus produced is random copolymerization, but the block copolymer is prepared using a usual method such as changing the introduction timing of the raw material monomer into the copolymerization reaction system depending on the type of monomer. It is also possible to produce a polymer.
重合体(A)’は、言い換えれば、重合体(A)において基(1)を有する側鎖に替えて基(2)を有する側鎖を必須に有する重合体である。また、上記重合体(A)において、基(1)を有する側鎖に加えて、基(2)を有する側鎖を有する重合体(A)について構成を記載したが、重合体(A)’は、基(1)を有する側鎖を有しないことを除いて、その構成と同様の構成とすることができる。 Moreover, in the radical curable photosensitive composition which concerns on this invention, it is possible to contain the component which can provide a liquid-repellent effect | action to a partition other than the said polymer (A). Specifically, such a component has a side chain having a group represented by the general formula (2) and a side chain having a polyoxyalkylene group, and is represented by the general formula (1). Polymer (A) ′ having neither a side chain having a group nor a side chain having an ethylenic double bond, and the mass average molecular weight (Mw (A) ′) is 2.6 × 10 4 <Mw (A) A polymer (A) ′ in which ≦ 20 × 10 4 is mentioned.
In other words, the polymer (A) ′ is a polymer essentially having a side chain having the group (2) instead of the side chain having the group (1) in the polymer (A). Moreover, in the said polymer (A), in addition to the side chain which has group (1), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) ' Can have the same configuration as that except that it does not have a side chain having the group (1).
重合体(A)’は、重合体(A)と同様、基(11)を有する側鎖を、好ましくは重合体(A)’に対する基(11)の含有量として5~60重量%となるような割合で、有する。さらに重合体(A)’は任意に、酸性基を有する側鎖、隔壁マトリックスが有する官能基と熱または光により架橋可能な官能基を有する側鎖等を有することが可能であり、このような側鎖を有する構成とするための重合反応についても、基(1)を有する単量体を原料単量体として用いず、必須の原料単量体として基(2)を有する単量体を用いる以外は、上記重合体(A)と同様とすることができる。 Specifically, the silicon atom content in the polymer (A) ′ is preferably 0.1 to 25% by mass, and more preferably 0.5 to 20% by mass. When the silicon atom content is within this range, the photosensitive composition of the present invention can be imparted with an effect of enhancing the liquid repellency of the partition wall surface obtained by using the photosensitive composition of the present invention without impairing the effects of the present invention. It becomes possible.
As in the polymer (A), the polymer (A) ′ has a side chain having the group (11), preferably the content of the group (11) with respect to the polymer (A) ′ is 5 to 60% by weight. Have in proportions. Furthermore, the polymer (A) ′ can optionally have a side chain having an acidic group, a side chain having a functional group that can be cross-linked by heat or light with a functional group that the partition matrix has, such as Also for the polymerization reaction for forming a structure having a side chain, the monomer having the group (1) is not used as a raw material monomer, but the monomer having the group (2) is used as an essential raw material monomer. Except for the above, it can be the same as the polymer (A).
本発明の感光性組成物がラジカル硬化型の場合、光硬化開始剤(B)としては、光の照射によりラジカルを発生する光重合開始剤(B1)が用いられる。 (1-2) Photocuring initiator (B) (Photopolymerization initiator (B1))
When the photosensitive composition of the present invention is a radical curable type, a photopolymerization initiator (B1) that generates radicals upon irradiation with light is used as the photocuring initiator (B).
本発明の感光性組成物がラジカル硬化型の場合、バインダー樹脂(C)としては、上記光重合開始剤(B1)が発生したラジカルにより重合する、酸性基およびエチレン性二重結合を有する感光性樹脂(C1)が用いられる。
感光性樹脂(C1)は、1分子内に上記光重合に関与するエチレン性二重結合を有し、さらに酸性基を有するため、アルカリ現像液を用いて、硬化されていない感光性組成物の未露光部を選択的に除去することができ、その結果、隔壁を形成することができる。なお、感光性樹脂(C1)は、基(1)および基(2)を実質的に有しないことが好ましい。 (1-3) Binder resin (C) (Photosensitive resin (C1))
When the photosensitive composition of the present invention is a radical curable type, the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond that is polymerized by the radical generated by the photopolymerization initiator (B1). Resin (C1) is used.
Since the photosensitive resin (C1) has an ethylenic double bond involved in the photopolymerization in one molecule and further has an acidic group, the photosensitive resin (C1) is an uncured photosensitive composition using an alkaline developer. Unexposed portions can be selectively removed, and as a result, barrier ribs can be formed. In addition, it is preferable that photosensitive resin (C1) does not have group (1) and group (2) substantially.
エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂(C1-2)としては、式(6)で表されるビフェニル骨格を有するエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、式(7)で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂または式(8)で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂が好ましい。当該樹脂を使用することにより、黒色着色剤を組成物中により多く配合でき、遮光性、光学濃度を高くすることが可能となる。また、現像時の塗膜剥離が抑制されて、高解像度のパターンを得ることができる。一方で、ラインの直線性が良好であり好ましい。さらに、ポストベーク工程後の外観が維持され、平滑な塗膜表面が得られやすく、好ましい。 A commercially available product can be used as the resin (C1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin. Examples of such commercially available products are KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H. , TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H (above And Nippon Kayaku Co., Ltd.) and EX1010 (manufactured by Nagase ChemteX Corporation).
As a resin (C1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin, an acidic group and an ethylenic double bond are introduced into an epoxy resin having a biphenyl skeleton represented by the formula (6) Resin, a resin obtained by introducing an acidic group and an ethylenic double bond into an epoxy resin represented by formula (7), or an acid group and an ethylenic double bond introduced into an epoxy resin represented by formula (8) Resin is preferred. By using the resin, more black colorant can be blended in the composition, and the light shielding property and optical density can be increased. Moreover, the coating film peeling at the time of image development is suppressed and a high resolution pattern can be obtained. On the other hand, the linearity of the line is good and preferable. Furthermore, the appearance after the post-baking step is maintained, and a smooth coating surface is easily obtained, which is preferable.
本発明に係るラジカル硬化型感光性組成物は、上記重合体(A)、光硬化開始剤(B)としての光重合開始剤(B1)、およびバインダー樹脂(C)としての酸性基およびエチレン性二重結合とを有する感光性樹脂(C1)を必須成分として含有するが、本発明の効果を損なわない範囲において、各種機能の向上等を目的として以下に説明する任意成分を含有することが可能である。
(エチレン性二重結合を2個以上有する架橋剤(D))
本発明に係るラジカル硬化型感光性組成物は、ラジカル硬化を促進する任意成分として、エチレン性二重結合を2個以上有する架橋剤(D)を含むことが好ましい。これにより、露光時における上記感光性樹脂(C1)の硬化性が向上し、隔壁を形成する際の露光量を低減することができる。なお、上記架橋剤(D)は、酸性基を実質的に有しないことが好ましい。 (1-3) Optional Components The radical curable photosensitive composition according to the present invention comprises the polymer (A), a photopolymerization initiator (B1) as a photocuring initiator (B), and a binder resin (C). As an essential component, the photosensitive resin (C1) having an acidic group and an ethylenic double bond as an optional component is described below for the purpose of improving various functions and the like as long as the effects of the present invention are not impaired. It is possible to contain components.
(Crosslinking agent (D) having two or more ethylenic double bonds)
The radical curable photosensitive composition according to the present invention preferably contains a crosslinking agent (D) having two or more ethylenic double bonds as an optional component for promoting radical curing. Thereby, the sclerosis | hardenability of the said photosensitive resin (C1) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced. In addition, it is preferable that the said crosslinking agent (D) does not have an acidic group substantially.
ウレタンアクリレートとしては、日本化薬社製のKAYARAD UXシリーズが挙げられ、具体的商品名としては、UX-3204、UX-6101、UX-0937、DPHA-40H、UX-5000、UX-5002D-P20などが挙げられる。
A-9300、BANI-MおよびBANI-Xは塗膜に硬さを付与し、熱垂れを抑制する観点から好ましい。A-9300-1CLは塗膜に柔軟性を付与する観点から好ましい。ウレタンアクリレートは、適度な現像時間が実現可能となり、現像性が良好になるので好ましい。 In the present invention, a commercially available product can be used as the crosslinking agent (D) having two or more ethylenic double bonds. Examples of such commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) , Ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane), BANI-X (trade name, Maruzen Petrochemical) N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene- , 3-dicarboximide)), and the like.
Examples of urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. Etc.
A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the coating film and suppressing thermal sagging. A-9300-1CL is preferable from the viewpoint of imparting flexibility to the coating film. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
本発明に係るラジカル硬化型感光性組成物は、この硬化物がブラックマトリックスのように遮光性を求められる用途に用いられる場合には、求められる隔壁の光学濃度に応じて黒色着色剤(E)を含有することが好ましい。 (Black colorant (E))
The radical curable photosensitive composition according to the present invention has a black colorant (E) according to the required optical density of the partition wall when the cured product is used in applications requiring light shielding properties such as a black matrix. It is preferable to contain.
本発明に係るラジカル硬化型感光性組成物が、上記黒色着色剤(E)等の分散性材料を含有する場合、その分散性を向上させるために、高分子分散剤を含有することが好ましい。高分子分散剤としては、特に限定されず、ウレタン系、ポリイミド系、アルキッド系、エポキシ系、ポリエステル系、メラミン系、フェノール系、アクリル系、ポリエーテル系、塩化ビニル系、塩化ビニル酢酸ビニル系共重合体系、ポリアミド系、ポリカーボネート系等が挙げられる。その中でも、ウレタン系、またはポリエステル系が好ましい。また、高分子分散剤は、ポリオキシエチレン基および/またはポリオキシプロピレン基を有していてもよい。 (Polymer dispersant / dispersion aid)
When the radical curable photosensitive composition according to the present invention contains a dispersible material such as the black colorant (E), it is preferable to contain a polymer dispersant in order to improve the dispersibility. The polymer dispersant is not particularly limited, and is urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acrylic type, polyether type, vinyl chloride type, vinyl chloride vinyl acetate type. Examples thereof include a polymer system, a polyamide system, and a polycarbonate system. Among these, urethane type or polyester type is preferable. The polymer dispersant may have a polyoxyethylene group and / or a polyoxypropylene group.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、微粒子を含んでいてもよい。これにより、後述するポストベイク時に隔壁の形状が変化することを抑制することができる。 (Fine particles)
The radical curable photosensitive composition according to the present invention may contain fine particles as necessary. Thereby, it can suppress that the shape of a partition changes at the time of the post-baking mentioned later.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、シランカップリング剤を含んでいてもよい。これにより、隔壁と基板との密着性を向上させることができる。 (Silane coupling agent)
The radical curable photosensitive composition according to the present invention may contain a silane coupling agent as required. Thereby, the adhesiveness of a partition and a board | substrate can be improved.
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、熱硬化剤を含んでいてもよい。これにより、隔壁の耐熱性、耐透水性を向上させることができる。また、上記重合体(A)が熱架橋性官能基を有する場合には、重合体(A)と熱硬化剤が化学結合し、それにより重合体(A)を隔壁に固定化する効果も得られる。 (Thermosetting agent)
The radical curable photosensitive composition according to the present invention may contain a thermosetting agent, if necessary. Thereby, the heat resistance of a partition and water permeability resistance can be improved. Further, when the polymer (A) has a thermally crosslinkable functional group, the polymer (A) and the thermosetting agent are chemically bonded, thereby obtaining an effect of fixing the polymer (A) to the partition wall. It is done.
(リン酸化合物)
本発明に係るラジカル硬化型感光性組成物は、必要に応じて、リン酸化合物を含んでいてもよい。これにより、基板との密着性を向上させることができるので好ましい。リン酸化合物しては、モノ(メタ)アクリロイルオキシエチルフォスフェート、ジ(メタ)アクリロイルオキシエチルフォスフェート、トリス(メタ)アクリロイルオキシエチルフォスフェートなどが挙げられる。 Although it does not specifically limit as a thermosetting agent, Amino resin (melamine compounds, such as hexamethoxymethylol melamine), a compound which has two or more epoxy groups, a compound which has two or more hydrazino groups, a polycarbodiimide compound, an oxazoline group A compound having two or more, a compound having two or more aziridine groups, a polyvalent metal, a compound having two or more mercapto groups, a polyisocyanate compound and the like may be mentioned, and two or more may be used in combination. Among these, considering the chemical resistance of the partition walls, amino resins, compounds having two or more epoxy groups, or compounds having two or more oxazoline groups are preferable.
(Phosphate compound)
The radical curable photosensitive composition according to the present invention may contain a phosphate compound as necessary. This is preferable because adhesion to the substrate can be improved. Examples of the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
また、本発明に係るラジカル硬化型感光性組成物は、上記以外の各種成分に加えて必要に応じて、硬化促進剤、増粘剤、可塑剤、消泡剤、レベリング剤、ハジキ防止剤、紫外線吸収剤等を含んでいてもよい。
本発明に係るラジカル硬化型感光性組成物は、上記説明した各種必須成分と、必要に応じて添加される任意成分を、上記配合量に合わせて、通常の方法で均一に混合することにより調製することができる。 (Other optional ingredients)
Moreover, the radical curable photosensitive composition according to the present invention includes a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, as necessary, in addition to various components other than those described above. An ultraviolet absorber or the like may be included.
The radical curable photosensitive composition according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. can do.
本発明の感光性組成物が酸硬化型の場合、感光性組成物は、重合体(A)、光硬化開始剤(B)としての光酸発生剤(B2)、およびバインダー樹脂(C)としてのカルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)を含有する。このような酸硬化型の感光性組成物は、フォトリソグラフィ等における露光に際して光照射部分では光酸発生剤(B2)から酸が発生し、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)とが架橋反応することにより塗膜硬化物を形成する。 (2) Acid curable photosensitive composition When the photosensitive composition of the present invention is an acid curable type, the photosensitive composition comprises a polymer (A) and a photoacid generator (B) as a photocuring initiator (B). B2) and an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group as the binder resin (C), and a compound having two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group Contains a crosslinkable resin (C22). In such an acid-curable photosensitive composition, an acid is generated from the photoacid generator (B2) in the light irradiation portion during exposure in photolithography or the like, and an alkali-soluble resin having a carboxyl group and / or a phenolic hydroxyl group ( C21) and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group undergo a crosslinking reaction to form a cured coating film.
(2-1)重合体(A)
本発明に係る酸硬化型感光性組成物が含有する重合体(A)は、本発明の感光性組成物における特徴的な成分であり、その好ましい態様も含めて、上記ラジカル硬化型感光性組成物において説明した重合体(A)が、酸硬化型感光性組成物において適用可能である。
また、重合体(A)の感光性組成物における含有量も上記同様とすることができる。さらに、上記重合体(A)以外に隔壁に撥液作用を付与できる成分として上で説明した重合体(A)’をラジカル硬化型感光性組成物の場合と同様に用いることが可能である。 Each component contained in the acid-curable photosensitive composition according to the present invention will be described below.
(2-1) Polymer (A)
The polymer (A) contained in the acid-curable photosensitive composition according to the present invention is a characteristic component in the photosensitive composition of the present invention, and includes the above-described radical curable photosensitive composition including preferred embodiments thereof. The polymer (A) described in the article can be applied to the acid-curable photosensitive composition.
The content of the polymer (A) in the photosensitive composition can also be the same as described above. Furthermore, in addition to the polymer (A), the polymer (A) ′ described above as a component capable of imparting a liquid repellency to the partition walls can be used in the same manner as in the case of the radical curable photosensitive composition.
本発明の感光性組成物が酸硬化型の場合、光硬化開始剤(B)としては、光により酸を発生する化合物である光酸発生剤(B2)が用いられる。光酸発生剤(B2)としては、例えば、ジアリールヨードニウム塩、トリアリールスルホニウム塩、トリアジン系化合物、スルホニル化合物、スルホン酸エステル類等が挙げられる。 (2-2) Photocuring initiator (B) (photoacid generator (B2))
When the photosensitive composition of the present invention is an acid curable type, a photoacid generator (B2) that is a compound that generates an acid by light is used as the photocuring initiator (B). Examples of the photoacid generator (B2) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.
本発明の感光性組成物が酸硬化型の場合、バインダー樹脂(C)としては、上記光酸発生剤(B2)が発生した酸の作用により架橋重合する、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)の組合せが挙げられる。 (2-2) Binder resin (C) (alkali-soluble resin (C21) / crosslinkable resin (C22))
When the photosensitive composition of the present invention is an acid curable type, the binder resin (C) includes a carboxyl group and / or a phenolic hydroxyl group that undergoes cross-linking polymerization by the action of the acid generated by the photoacid generator (B2). And a combination of the alkali-soluble resin (C21) having a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group.
アルカリ可溶性樹脂(C21)は、カルボキシル基および/またはフェノール性水酸基を有する。カルボキシル基および/またはフェノール性水酸基を有することによりアルカリ性溶液に可溶であり、また、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)と架橋し塗膜硬化物を形成し得る。アルカリ可溶性樹脂(C21)は、感光性組成物のフォトリソグラフィ等において使用する現像液を構成するアルカリ性溶液に対して可溶の樹脂であれば何等制限なく使用することが可能であり、例えば、カルボキシル基とエチレン性二重結合を有する単量体および/またはフェノール性水酸基とエチレン性二重結合を有する単量体を必須として重合させて得られる樹脂(C21-1)、フェノール樹脂等が挙げられる。これらの樹脂は、基(1)および基(2)を実質的に有しないことが好ましい。 (Alkali-soluble resin (C21))
The alkali-soluble resin (C21) has a carboxyl group and / or a phenolic hydroxyl group. A crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group, and which has two or more groups capable of reacting with the carboxyl group and / or the phenolic hydroxyl group; It can be crosslinked to form a cured film. The alkali-soluble resin (C21) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive composition. And a resin (C21-1) obtained by polymerizing a monomer having a group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as essential, and a phenol resin. . These resins preferably have substantially no groups (1) and (2).
架橋性樹脂(C22)は、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である。カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有することにより、カルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と架橋し塗膜硬化物を形成し得る。また、上記重合体(A)がカルボキシル基および/または水酸基を有する場合には重合体(A)とも架橋し塗膜硬化物を形成し得る。架橋性樹脂(C22)は、基(1)および基(2)を実質的に有しない化合物であることが好ましい。 (Crosslinkable resin (C22))
The crosslinkable resin (C22) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group to form a cured coating film. Moreover, when the said polymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge | crosslink with a polymer (A) and a coating-film cured | curing material can be formed. The crosslinkable resin (C22) is preferably a compound substantially free of the group (1) and the group (2).
本発明に係る酸硬化型感光性組成物は、上記重合体(A)、光硬化開始剤(B)としての光酸発生剤(B2)、およびバインダー樹脂(C)としてのカルボキシル基および/またはフェノール性水酸基を有するアルカリ可溶性樹脂(C21)と、カルボキシル基および/またはフェノール性水酸基と反応し得る基を2個以上有する化合物である架橋性樹脂(C22)を含有するが、本発明の効果を損なわない範囲において、各種機能の向上等を目的として各種任意成分を含有することが可能である。
このような任意成分としては、上記ラジカル硬化型感光性組成物で説明した任意成分のうちの、エチレン性二重結合を2個以上有する架橋剤(D)以外の全ての成分を、ラジカル硬化型感光性組成物の場合と同様に、酸硬化型感光性組成物に用いることが可能である。 (2-3) Optional Components The acid curable photosensitive composition according to the present invention includes the polymer (A), a photoacid generator (B2) as a photocuring initiator (B), and a binder resin (C). And an alkali-soluble resin (C21) having a carboxyl group and / or a phenolic hydroxyl group, and a crosslinkable resin (C22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. However, various optional components can be contained for the purpose of improving various functions and the like within a range not impairing the effects of the present invention.
Examples of such optional components include all components other than the crosslinking agent (D) having two or more ethylenic double bonds among the optional components described in the radical curable photosensitive composition. As in the case of the photosensitive composition, it can be used for an acid-curable photosensitive composition.
上記説明したラジカル硬化型感光性組成物や酸硬化型感光性組成物等の本発明の感光性組成物を用いて隔壁を形成する際には、感光性組成物を溶媒で希釈した希釈液を用いて塗膜(湿潤膜)を形成した後に、溶媒を揮発除去し、感光性組成物の塗膜を形成することが好ましい。 [Dilution solvent]
When forming a partition using the photosensitive composition of the present invention such as the above-described radical curable photosensitive composition or acid curable photosensitive composition, a diluted solution obtained by diluting the photosensitive composition with a solvent is used. It is preferable to form a coating film of the photosensitive composition by volatilizing and removing the solvent after using it to form a coating film (wet film).
本発明の隔壁は、上記本発明の感光性組成物の塗膜硬化物により、基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、カラーフィルタや有機EL素子のブラックマトリックス等に適用することができる。 <2> Partition Wall The partition wall of the present invention is a partition wall formed by partitioning the substrate into a plurality of pixel forming sections by using the cured film of the photosensitive composition of the present invention. It can be applied to a black matrix of an organic EL element.
まず、本発明の感光性組成物の希釈液を基板に塗布する。基板としては、特に限定されず、各種ガラス板;SiC基板、シリコン等の無機基板;ITO等の無機酸化物基板;ポリエステル(ポリエチレンテレフタレート等)、ポリオレフィン(ポリエチレン、ポリプロピレン等)、ポリカーボネート、ポリメチルメタクリレート、ポリスルホン、ポリイミド、ポリ(メタ)アクリル樹脂等の熱可塑性樹脂シート;エポキシ樹脂、不飽和ポリエステル等の熱硬化性樹脂の硬化シート等が挙げられる。耐熱性を考慮すると、基板としては、ガラス板とポリイミド等の耐熱性樹脂が好ましい。また、基板の隔壁が形成されていない側の面からの露光が可能であることから、基板は、透明であることが好ましい。さらに、基板は、ガラス基板等の透明基板上に、有機膜またはTFT(Thin Film Transistor:薄膜トランジスタ)、ITO、SiO2等の無機酸化物膜が形成された基板またはパターニングされた基板、シリコンナイトライドやポリイミドなどの絶縁膜を形成させた基板、これらの基板が積層されている積層基板であってもよい。 (Coating process)
First, a diluted solution of the photosensitive composition of the present invention is applied to a substrate. The substrate is not particularly limited, and various glass plates; SiC substrate, inorganic substrate such as silicon; inorganic oxide substrate such as ITO; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate And thermoplastic resin sheets such as polysulfone, polyimide, and poly (meth) acrylic resin; and cured sheets of thermosetting resin such as epoxy resin and unsaturated polyester. Considering heat resistance, the substrate is preferably a heat resistant resin such as a glass plate and polyimide. Moreover, since the exposure from the surface where the partition wall of the substrate is not formed is possible, the substrate is preferably transparent. Furthermore, the substrate is a substrate in which an inorganic film such as an organic film or TFT (Thin Film Transistor), ITO, SiO 2 is formed on a transparent substrate such as a glass substrate, or a patterned substrate, silicon nitride Or a substrate on which an insulating film such as polyimide is formed, or a laminated substrate in which these substrates are laminated.
次に、基板に形成された塗膜を乾燥する。これにより、溶媒が揮発するため、粘着性のない感光性組成物の塗膜が得られる。乾燥方法としては、特に限定されず、真空乾燥、加熱乾燥が挙げられる。塗膜の外観のムラを発生させず、効率よく乾燥させるために、真空乾燥と加熱乾燥を併用することが好ましい。乾燥条件は、感光性組成物に含まれる成分の種類、組成等により異なるが、真空乾燥は、10~500Pa(絶対圧)で10~300秒間であることが好ましく、加熱乾燥は、50~120℃で10~2000秒間であることが好ましい。 (Drying process)
Next, the coating film formed on the substrate is dried. Thereby, since a solvent volatilizes, the coating film of the photosensitive composition without stickiness is obtained. It does not specifically limit as a drying method, Vacuum drying and heat drying are mentioned. In order to efficiently dry the coating film without causing uneven appearance, it is preferable to use vacuum drying and heat drying in combination. The drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, but the vacuum drying is preferably 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and the heat drying is 50 to 120. It is preferable that the temperature is 10 to 2000 seconds at ° C.
次に、所定パターンのマスクを介して、塗膜を露光する。露光時に照射される光としては、特に限定されず、可視光、紫外線、遠紫外線、KrFエキシマレーザー、ArFエキシマレーザー、F2エキシマレーザー、Kr2エキシマレーザー、KrArエキシマレーザー、Ar2エキシマレーザー等のエキシマレーザー、X線、電子線等が挙げられる。波長が100~600nmの光が好ましく、波長が300~500nmの光がより好ましく、i線(365nm)、h線(405nm)、g線(436nm)が特に好ましい。なお、光源としては、公知の超高圧水銀灯等を用いることができる。 (Exposure process)
Next, the coating film is exposed through a mask having a predetermined pattern. The light irradiated at the time of exposure is not particularly limited, and visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser, etc. Excimer laser, X-ray, electron beam and the like can be mentioned. Light having a wavelength of 100 to 600 nm is preferable, light having a wavelength of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable. In addition, a well-known super high pressure mercury lamp etc. can be used as a light source.
次に、現像液を用いて、塗膜の未露光部を除去し、現像する。現像液としては、特に限定されないが、無機アルカリ類、アミン類、アルカノールアミン類、第4級アンモニウム塩等のアルカリの水溶液が挙げられる。現像時間、すなわち、現像液に接触させる時間は、5~180秒間であることが好ましい。現像方法としては、特に限定されないが、液盛り法、ディッピング法、シャワー法等が挙げられる。 (Development process)
Next, using a developing solution, the unexposed part of the coating film is removed and developed. The developer is not particularly limited, and examples thereof include aqueous alkali solutions such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts. The development time, that is, the time for contact with the developer is preferably 5 to 180 seconds. The developing method is not particularly limited, and examples thereof include a liquid filling method, a dipping method, and a shower method.
さらに、ジェットリンスを行うことが好ましい。ジェットリンスとは、隔壁が形成された基板に対し、水を圧縮、または水および空気を圧縮し、噴霧する工程である。圧力は2~20MPaであることが好ましい。ジェットリンスを行うことによって、現像工程にて溶け残った残渣や、現像中に溶解した感光性組成物の成分の一部が、基板に再付着したものを除去することが可能である。
なお、ジェットリンス後に、圧縮空気や圧縮窒素で風乾させることにより、基板上の水分を除去することができる。 (Jet rinse process)
Furthermore, it is preferable to perform jet rinsing. Jet rinsing is a process in which water is compressed or water and air are compressed and sprayed onto a substrate on which a partition wall is formed. The pressure is preferably 2 to 20 MPa. By carrying out the jet rinsing, it is possible to remove the residue that remains undissolved in the development process and the part of the components of the photosensitive composition dissolved during the development that are reattached to the substrate.
Note that water on the substrate can be removed by air drying with compressed air or compressed nitrogen after jet rinsing.
次に、現像された隔壁に対してポスト露光を行ってもよい。このとき、隔壁が形成されている側の面および隔壁が形成されていない側の面のいずれから露光してもよいし、両面から露光してもよい。露光時に照射される光は、紫外線であることが好ましい。 (Post exposure process)
Next, post-exposure may be performed on the developed partition wall. At this time, the exposure may be performed from either the surface on which the partition is formed or the surface on which the partition is not formed, or may be performed from both surfaces. The light irradiated during exposure is preferably ultraviolet light.
現像後(ポスト露光を行う際は、ポスト露光後)に、隔壁を加熱することが好ましい。加熱条件は、150~250℃で5~90分間であることが好ましく、加熱温度は、180℃以上がより好ましい。加熱温度が低すぎると、耐薬品性が不十分となることがあり、隔壁にインクを塗布した場合に、隔壁が膨潤したり、インクが滲んだりすることがある。
一方、加熱温度が高すぎると、隔壁が熱分解することがある。 (Post-baking process)
It is preferable to heat the partition after development (when post-exposure is performed, after post-exposure). The heating condition is preferably 150 to 250 ° C. for 5 to 90 minutes, and the heating temperature is more preferably 180 ° C. or higher. If the heating temperature is too low, chemical resistance may be insufficient, and when ink is applied to the partition walls, the partition walls may swell or the ink may ooze.
On the other hand, if the heating temperature is too high, the partition walls may be thermally decomposed.
本発明のカラーフィルタは、基板上に複数の画素と隣接する画素間に位置する隔壁とを有するカラーフィルタであって、前記隔壁が上記本発明の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする。なお、本発明のカラーフィルタにおいて、隔壁は光学濃度が2~7程度のブラックマトリックスであることが好ましい。
本発明のカラーフィルタは、前述のように、基板上に、隔壁、例えば、ブラックマトリックスを形成した後、インクジェット法を用いて、隔壁の開口部にインクを塗布して画素を形成することにより製造することができる。 <3> Color filter The color filter of the present invention is a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, and the partition is formed of the partition of the present invention. The pixel is formed by an inkjet method. In the color filter of the present invention, the partition walls are preferably a black matrix having an optical density of about 2 to 7.
As described above, the color filter of the present invention is manufactured by forming a partition, for example, a black matrix on a substrate, and then forming a pixel by applying ink to the opening of the partition using an inkjet method. can do.
本発明の有機EL素子は、基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が上記本発明の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする。
本発明の有機EL素子は、以下のようにして、製造することができる。まず、スパッタ法等を用いて、ガラス基板等の透明基板にITO等の透明電極を形成し、必要に応じて、透明電極を所望のパターンにエッチングする。次に、カラーフィルタの場合と同様にして、基板上に、隔壁、例えば、ブラックマトリックスを形成した後、インクジェット法を用いて、隔壁(ブラックマトリックス)の開口部に、インクとして、正孔輸送材料の溶液および発光材料の溶液を順次塗布、乾燥して、正孔輸送層および発光層を形成する。さらに、蒸着法等を用いて、アルミニウム等の電極を形成して画素を形成することにより、有機EL素子が得られる。 <4> Organic EL Element The organic EL element of the present invention is an organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, and the partition is formed of the partition of the present invention. The pixel is formed by an inkjet method.
The organic EL device of the present invention can be produced as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched into a desired pattern as necessary. Next, in the same manner as in the case of the color filter, a partition, for example, a black matrix is formed on the substrate, and then a hole transport material is used as an ink in the opening of the partition (black matrix) using an ink jet method. The solution of the above and the solution of the light emitting material are sequentially applied and dried to form a hole transport layer and a light emitting layer. Furthermore, an organic EL element is obtained by forming an electrode, such as aluminum, using a vapor deposition method or the like to form a pixel.
以下の各例において用いた化合物の略号を以下に示す。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, a part means a mass part.
The abbreviations of the compounds used in the following examples are shown below.
(単量体)
C6FMA:CH2=C(CH3)COOCH2CH2(CF2)6F
X-24-8201:ジメチルシリコーン鎖含有メタクリレートX-24-8201(信越化学工業社製)(一般式(4)において、R8がメチル基、Zがトリメチレン基、R1、R2、R3がそれぞれメチル基、nが分子間の平均値として24である化合物)
MAA:メタクリル酸
2-HEMA:2-ヒドロキシエチルメタクリレート
PME400:ブレンマーPME-400(日本油脂社製、CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は約9である。)
PME1000:ブレンマーPME-1000(日本油脂社製、CH2=C(CH3)COO(CH2CH2O)kCH3:式中のkは分子間の平均値を示し、kの値は約23である。)
GMA:グリシジルメタクリレート
MMA:メタクリル酸メチル [1] Compound (monomer) used for production of polymer (A) and polymer (R)
C6FMA: CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2) 6 F
X-24-8201: Dimethyl silicone chain-containing methacrylate X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.) (in the general formula (4), R 8 is a methyl group, Z is a trimethylene group, R 1 , R 2 , R 3 Are compounds in which each is a methyl group and n is 24 as an average value between molecules)
MAA: methacrylic acid 2-HEMA: 2-hydroxyethyl methacrylate PME400: BLEMMER PME-400 (manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula is (The average value between molecules is shown, and the value of k is about 9.)
PME1000: Blemmer PME-1000 (manufactured by NOF Corporation, CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, and the value of k is about 23.)
GMA: Glycidyl methacrylate MMA: Methyl methacrylate
V-65:V-65(和光純薬社製、2,2'-アゾビス(2,4-ジメチルバレロニトリル))
(連鎖移動剤)
n-DM:n-ドデシルメルカプタン
(溶媒)
MEK:2-ブタノン (Polymerization initiator)
V-65: V-65 (Wako Pure Chemical Industries, 2,2'-azobis (2,4-dimethylvaleronitrile))
(Chain transfer agent)
n-DM: n-dodecyl mercaptan (solvent)
MEK: 2-butanone
(光硬化開始剤(B):光重合開始剤(B1))
OXE02:OXE02(チバスペシャルティケミカルズ社製、エタノン 1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾイル-3-イル]-1-(O-アセチルオキシム)(一般式(5)において、R21およびR22がメチル基、R23がエチル基、R24、R26およびR27が水素原子、R25が2-メチルベンゾイル基である化合物)
(バインダー樹脂(C):感光性樹脂(C1))
EX1010:EX-1010(ナガセケムテックス社製、一般式(7)で表されるエポキシ樹脂にエチレン性二重結合と酸性基とを導入した樹脂の溶液、固形分70質量%、質量平均分子量:3,020)
ZCR1569H:ZCR-1569H(日本化薬社製、一般式(6)で表されるビフェニル骨格を有するエポキシ樹脂にエチレン性二重結合と酸性基とを導入した樹脂の溶液;固形分70質量%、質量平均分子量:4,710) [2] Photosensitive composition component (photocuring initiator (B): photopolymerization initiator (B1))
OXE02: OXE02 (manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (general formula (5) Wherein R 21 and R 22 are methyl groups, R 23 is an ethyl group, R 24 , R 26 and R 27 are hydrogen atoms, and R 25 is a 2-methylbenzoyl group)
(Binder resin (C): photosensitive resin (C1))
EX1010: EX-1010 (manufactured by Nagase ChemteX Corporation, a resin solution in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the general formula (7), solid content: 70% by mass, mass average molecular weight: 3,020)
ZCR1569H: ZCR-1569H (manufactured by Nippon Kayaku Co., Ltd., a solution of a resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the general formula (6); solid content: 70% by mass; (Mass average molecular weight: 4,710)
DPHA:KAYARAD DPHA(日本化薬社製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物)
A9300:NKエステル A-9300(新中村化学工業社製、エトキシ化イソシアヌル酸トリアクリレート)
(溶媒)
PGMEA:プロピレングリコールモノメチルエーテルアセテート
(黒色着色剤(E)、微粒子)
CB:カーボンブラック分散液(平均二次粒径120nm、分散媒:PGMEA、カーボンブラック20質量%、アミン価が18mgKOH/gのポリウレタン系高分子分散剤5質量%)
シリカ:シリカ分散液(平均粒径20nm、分散媒PGMEA、固形分30質量%) (Crosslinking agent (D))
DPHA: KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
A9300: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)
(solvent)
PGMEA: Propylene glycol monomethyl ether acetate (black colorant (E), fine particles)
CB: carbon black dispersion (average secondary particle size 120 nm, dispersion medium: PGMEA, carbon black 20% by mass, polyurethane polymer dispersant 5% by mass with amine value of 18 mgKOH / g)
Silica: Silica dispersion (average particle size 20 nm, dispersion medium PGMEA, solid content 30% by mass)
撹拌機を備えた内容積1Lのオートクレーブに、MEK(420.0g)、C6FMA(90.0g)、MAA(9.0g)、PME1000(81.0g)、および重合開始剤V-65(0.5g)を仕込み、窒素雰囲気下で撹拌しながら、50℃で24時間重合させ、粗共重合体を合成した。得られた粗共重合体の溶液にヘキサンを加えて再沈精製した後、真空乾燥し、重合体(A)に相当する重合体(A-1)(162.4g)を得た。
重合体(A-1)は、数平均分子量が37,800、質量平均分子量が58,730であった。 [Synthesis Example 1 of Polymer (A)]
To an autoclave with an internal volume of 1 L equipped with a stirrer, MEK (420.0 g), C6FMA (90.0 g), MAA (9.0 g), PME1000 (81.0 g), and polymerization initiator V-65 (0. 5 g) was charged and polymerized at 50 ° C. for 24 hours with stirring under a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the obtained crude copolymer solution for purification by reprecipitation, followed by vacuum drying to obtain polymer (A-1) (162.4 g) corresponding to polymer (A).
The polymer (A-1) had a number average molecular weight of 37,800 and a weight average molecular weight of 58,730.
上記重合体(A-1)の合成において、原料の配合を表1のように変更した他は同様の反応により、重合体(A)に相当する重合体(A-2)~(A-4)を得た。 [Synthesis Examples 2 to 4 of Polymer (A)]
In the synthesis of the polymer (A-1), polymers (A-2) to (A-4) corresponding to the polymer (A) were obtained by the same reaction except that the composition of the raw materials was changed as shown in Table 1. )
上記重合体(A-1)の合成において、原料の配合を表1のように変更した他は同様の反応により、本発明における重合体(A)に適合しない重合体(R-1)、(R-2)を得た。 [Comparative Synthesis Examples 1 and 2]: Synthesis of Comparative Example Polymer (R) Not Suitable for Polymer (A) Produced the polymers (R-1) and (R-2) which were not compatible with the polymer (A) in the present invention by the same reaction.
数平均分子量(Mn)および質量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー法により、ポリスチレンを標準物質として測定した。ゲルパーミエーションクロマトグラフィーとしては、HPLC-8220GPC(東ソー社製)を使用した。カラムとしては、shodex LF-604を3本接続したものを使用した。検出器としては、RI検出器を使用した。標準物質としては、EasiCal PS1(Polymer Laboratories社製)を使用した。さらに、数平均分子量および質量平均分子量を測定する際は、カラムを37℃で保持し、溶離液としてはテトラヒドロフランを用い、流速を0.2mL/分とし、測定サンプルの0.5質量%テトラヒドロフラン溶液40μLを注入した。 <Molecular weight>
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance. As the gel permeation chromatography, HPLC-8220GPC (manufactured by Tosoh Corporation) was used. As the column, a column in which three shodex LF-604 were connected was used. An RI detector was used as the detector. As a standard substance, EasiCal PS1 (manufactured by Polymer Laboratories) was used. Further, when measuring the number average molecular weight and the mass average molecular weight, the column is maintained at 37 ° C., tetrahydrofuran is used as the eluent, the flow rate is 0.2 mL / min, and the 0.5 mass% tetrahydrofuran solution of the measurement sample is measured. 40 μL was injected.
重合体中のフッ素原子の含有量は、重合反応の仕込み値から算出した。
<ポリオキシアルキレン基の含有割合>
重合体中のポリオキシアルキレン基の含有割合は、重合反応の仕込み値から算出した。
<ケイ素原子含有量>
重合体中のケイ素原子の含有量は、重合反応の仕込み値から算出した。 <Fluorine atom content>
The fluorine atom content in the polymer was calculated from the charged value of the polymerization reaction.
<Content of polyoxyalkylene group>
The content ratio of the polyoxyalkylene group in the polymer was calculated from the charged value of the polymerization reaction.
<Silicon atom content>
The content of silicon atoms in the polymer was calculated from the charged value of the polymerization reaction.
酸価は、原料である単量体の配合割合から算出した理論値である。 <Acid value>
The acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.
上記で得られた各重合体を、0.1%のNaCO3水溶液(pH11、温度23℃)に添加し、撹拌条件:50rpmで溶解した重合体の割合(質量%)を求め、重合体のアルカリ水溶液に対する溶解性の指標とした。 <Developer solubility>
Each polymer obtained above was added to a 0.1% aqueous NaCO 3 solution (pH 11, temperature 23 ° C.), and the stirring condition: the ratio (mass%) of the polymer dissolved at 50 rpm was determined. It was used as an index of solubility in an alkaline aqueous solution.
上記合成例で得られた重合体(A-1)(0.03部)、黒色着色剤(E)の分散液としてのCB(31.6部)、光重合開始剤(B1)としてのOXE02(0.76部)、感光性樹脂(C1)の分散液としてのEX1010(6.3部)、架橋剤(D)としてのDPHA(1.9部)および溶媒としてのPGMEA(34.4部)、シクロヘキサノン(25.0部)を混合して、感光性組成物の希釈液を得た。感光性組成物の希釈液の全固形分中の重合体(A-1)の含有量は、0.20質量%であった。 [Example 1]
Polymer (A-1) (0.03 part) obtained in the above synthesis example, CB (31.6 parts) as a dispersion of black colorant (E), OXE02 as photopolymerization initiator (B1) (0.76 parts), EX1010 (6.3 parts) as a dispersion of the photosensitive resin (C1), DPHA (1.9 parts) as a crosslinking agent (D), and PGMEA (34.4 parts) as a solvent ) And cyclohexanone (25.0 parts) were mixed to obtain a diluted solution of the photosensitive composition. The content of the polymer (A-1) in the total solid content of the diluted liquid of the photosensitive composition was 0.20% by mass.
各成分の配合を表2に示すように変更した以外は、実施例1と同様にして、上記合成例で得られた重合体(A-2)~(A-5)をそれぞれ含有する感光性組成物の塗膜硬化物からなる隔壁が形成された実施例2~5のガラス基板サンプル(1)、および、該感光性組成物の塗膜の硬化物が形成された実施例2~5のガラス基板サンプル(2)およびジェットリンスをさらに行ったガラス基板サンプル(3)を得た。 [Examples 2 to 5]
Photosensitivity containing each of the polymers (A-2) to (A-5) obtained in the above synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2. Glass substrate samples (1) of Examples 2 to 5 in which partition walls made of a cured film of the composition were formed, and Examples 2 to 5 of which a cured product of the coating film of the photosensitive composition was formed The glass substrate sample (2) and the glass substrate sample (3) which performed jet rinse further were obtained.
各成分の配合を表2に示すように変更した以外は、実施例1と同様にして、上記比較合成例で得られた重合体(R-1)、(R-2)をそれぞれ含有する感光性組成物の塗膜硬化物からなる隔壁が形成された比較例1、2のガラス基板サンプル(1)、および、該感光性組成物の塗膜の硬化物が形成された比較例1、2のガラス基板サンプル(2)およびジェットリンスをさらに行ったガラス基板サンプル(3)を得た。 [Comparative Examples 1 and 2]
Photosensitive materials each containing the polymers (R-1) and (R-2) obtained in the above comparative synthesis examples in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2. Glass substrate sample (1) of Comparative Examples 1 and 2 in which a partition wall made of a cured film of the photosensitive composition was formed, and Comparative Examples 1 and 2 in which a cured product of the coating film of the photosensitive composition was formed A glass substrate sample (2) and a glass substrate sample (3) subjected to jet rinsing were obtained.
以下に説明する方法で、上記各実施例および比較例で作製したガラス基板サンプル(2)およびガラス基板サンプル(3)を用いて撥液性を評価した。また上記各実施例および比較例で作製したガラス基板サンプル(1)を用いて、隔壁間開口部内のインクの濡れ拡がり性、残膜発生の状態を評価した。評価結果を、感光性組成物の全固形成分における各成分の含有質量%とともに表3に示す。
表中、◎は最良、○は良、△は可、×は不可を示す。本発明は、全ての評価が◎または○であるものが良い。 [Evaluation method and evaluation results]
With the method described below, the liquid repellency was evaluated using the glass substrate sample (2) and the glass substrate sample (3) prepared in each of the above Examples and Comparative Examples. In addition, using the glass substrate samples (1) prepared in each of the above Examples and Comparative Examples, the ink wettability and the state of residual film generation in the opening between the partition walls were evaluated. An evaluation result is shown in Table 3 with the content mass% of each component in the total solid component of the photosensitive composition.
In the table, ◎ indicates the best, ○ indicates good, Δ indicates acceptable, and × indicates impossibility. In the present invention, all evaluations are good or good.
ガラス基板サンプル(2)の塗膜硬化物の表面のPGMEAの接触角を測定することにより、撥液性を評価した。また、ガラス基板サンプル(3)の塗膜硬化物の表面のPGMEAの接触角を測定することにより、ジェットリンスによる撥液性耐性を評価した。
接触角とは、固体と液体が接触する点における液体表面に対する接線と固体表面がなす角であり、液体を含む側の角度で定義する。このため、接触角が大きい程、塗膜硬化物の撥液性が優れることを意味する。PGMEAの接触角が40°以上50°以下のものを○、35°以上40°未満のものを△、35°未満のものを×として、判定した。 <Liquid repellency>
The liquid repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate sample (2). Moreover, the liquid repellency tolerance by jet rinse was evaluated by measuring the contact angle of PGMEA of the surface of the coating-film hardened | cured material of a glass substrate sample (3).
The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid come into contact, and is defined as an angle on the side including the liquid. For this reason, the larger the contact angle, the better the liquid repellency of the cured film. The case where the contact angle of PGMEA was 40 ° or more and 50 ° or less was evaluated as ◯, the case where it was 35 ° or more and less than 40 ° was evaluated as Δ, and the case where it was less than 35 ° was evaluated as ×.
ガラス基板サンプル(1)において、現像欠陥数を目視により計測することにより残膜発生の状態を評価した。面積あたりの現像欠陥数が100個未満のものを○、100個以上200個未満のものを△、200個以上のものを×として、判定した。 <State of residual film generation>
In the glass substrate sample (1), the number of development defects was visually measured to evaluate the state of residual film generation. The number of development defects per area was determined to be less than 100, ◯ for 100 to less than 200, and x for 200 or more.
液状エポキシME-562(日本ペルノックス社製)(6.25g)、硬化剤HV-562(日本ペルノックス社製)(6.25g)、アジピン酸ジエチル(12.5g)およびマロン酸ジエチル(25.0g)を、スターラーを用いて1時間攪拌混合し、インクを調製した。
インクジェット法を用いて、ガラス基板サンプル(1)の隔壁間開口部に上記で調製したインク約10pLまたは、約20pLを塗布し、超深度形状測定顕微鏡VK-8500(キーエンス社製)を用いて撮影した写真を観察することにより、隔壁間開口部内のインクの濡れ拡がり性を評価した。 <Wetting and spreading of ink in the opening between the partition walls>
Liquid epoxy ME-562 (Nihon Pernox) (6.25 g), curing agent HV-562 (Nihon Pernox) (6.25 g), diethyl adipate (12.5 g) and diethyl malonate (25.0 g) ) Was stirred and mixed using a stirrer for 1 hour to prepare an ink.
Using the ink jet method, about 10 pL or about 20 pL of the ink prepared above is applied to the opening between the partition walls of the glass substrate sample (1), and photographed using an ultra-deep shape measuring microscope VK-8500 (manufactured by Keyence Corporation). By observing the photograph, wetting and spreading properties of the ink in the opening between the partition walls were evaluated.
更に、より少ない約10pLのインクを塗布した場合でも、重合体(A)の質量平均分子量が40000以上である、実施例1~4はインクが隔壁間の開口部内に濡れ拡がり、白抜けがなかった。 The polymer (A-1) corresponding to the polymer (A) even when about 20 pL of ink is applied to the opening between the partitions having a volume of 120 pL, that is, even when the amount of ink applied is small relative to the volume of the opening In the glass substrate samples (1) of Examples 1 to 5 having partition walls obtained by using the photosensitive composition of the present invention each containing ~ (A-5), the ink wets into the openings between the partition walls. It expanded and there were no white spots. This indicates that in the coating films obtained from the photosensitive compositions of Examples 1 to 5, the developability was good and the polymer (A) component did not move from the partition wall surface to the opening between the partition walls. Is.
Further, even when a smaller amount of about 10 pL of ink was applied, the weight average molecular weight of the polymer (A) was 40,000 or more. In Examples 1 to 4, the ink wets and spreads in the opening between the partition walls, and there is no white spot. It was.
ポリオキシアルキレン基を有さない重合体(R-2)を含有する感光性組成物を用いて得られた隔壁を有する比較例2のガラス基板サンプル(1)は、残膜が多数の発生していた。 On the other hand, a polymer (R-1) having a mass-average molecular weight Mw (A) outside the range of the polymer (A) according to the present invention, specifically a mass-average molecular weight Mw of less than 2.6 × 10 4 is obtained. In the glass substrate sample (3) of Comparative Example 1 having partition walls obtained using the photosensitive composition contained, the liquid repellency after jet rinsing was remarkably lowered. Further, when about 20 pL of ink was applied to the opening between the partitions having a volume of 120 pL, that is, when the amount of ink applied was small relative to the volume of the opening, there was a portion where the ink did not spread out in the opening. This indicates that the polymer (R-1) migrated into the opening during post-baking, and the lyophilicity of the opening decreased.
In the glass substrate sample (1) of Comparative Example 2 having a partition wall obtained using the photosensitive composition containing the polymer (R-2) having no polyoxyalkylene group, a large number of residual films were generated. It was.
このような本発明の感光性組成物は、例えば、インクジェット記録技術法を利用したカラーフィルタ製造用、有機EL表示素子製造用として隔壁の形成に好適に用いられる。さらには、有機TFT(Thin Film Transistor:薄膜トランジスタ)アレイの各TFTを仕切る隔壁、液晶表示素子のITO電極の隔壁、回路配線基板の隔壁等の永久膜を形成する材料として好適に用いられる。
なお、2009年12月28日に出願された日本特許出願2009-298961号の明細書、特許請求の範囲及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The photosensitive composition of the present invention is an ink repellent component that does not have an ethylenic double bond, but has good ink repellency at the upper part of the partition wall, resistance to developer not corroded by the developer, residual film remaining without development It is a photosensitive composition containing an ink repellent component capable of imparting the property of suppressing the generation of ink and the good wetting and spreading property of the ink to the opening between the partition walls to the obtained partition wall.
Such a photosensitive composition of the present invention is suitably used for forming barrier ribs, for example, for manufacturing color filters using an inkjet recording technique and for manufacturing organic EL display elements. Furthermore, it is suitably used as a material for forming a permanent film such as a partition for partitioning each TFT of an organic TFT (Thin Film Transistor) array, a partition for an ITO electrode of a liquid crystal display element, a partition for a circuit wiring board.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-298961 filed on Dec. 28, 2009 are incorporated herein as the disclosure of the specification of the present invention. It is.
Claims (14)
- 下記一般式(1)で表される基を有する側鎖およびポリオキシアルキレン基を有する側鎖を有し、かつエチレン性二重結合を有する側鎖を有しない重合体(A)と、光硬化開始剤(B)と、バインダー樹脂(C)とを含む感光性組成物であって、
-CFXRf …(1)
(式中、Xは、水素原子、フッ素原子またはトリフルオロメチル基を表し、Rfは、エーテル性酸素原子を有していてもよい炭素数が1以上20以下のフルオロアルキル基またはフッ素原子を表す。)
前記重合体(A)の質量平均分子量(Mw(A))が、2.6×104<Mw(A)≦20×104であることを特徴とする感光性組成物。 A polymer (A) having a side chain having a group represented by the following general formula (1) and a side chain having a polyoxyalkylene group and having no ethylenic double bond, and photocuring A photosensitive composition comprising an initiator (B) and a binder resin (C),
-CFXR f (1)
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an etheric oxygen atom. To express.)
The polymer (A) has a mass average molecular weight (Mw (A)) of 2.6 × 10 4 <Mw (A) ≦ 20 × 10 4 . - 前記重合体(A)におけるポリオキシアルキレン基の含有割合が5~60質量%であることを特徴とする請求項1に記載の感光性組成物。 2. The photosensitive composition according to claim 1, wherein the content ratio of the polyoxyalkylene group in the polymer (A) is 5 to 60% by mass.
- 前記重合体(A)が、酸性基を有する請求項1または2に記載の感光性組成物。 The photosensitive composition according to claim 1 or 2, wherein the polymer (A) has an acidic group.
- 前記重合体(A)におけるフッ素原子含有割合が、20~50質量%である請求項1~3のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 3, wherein a fluorine atom content ratio in the polymer (A) is 20 to 50 mass%.
- 前記感光性組成物の全固形分における前記重合体(A)の割合が、0.07~1質量%である請求項1~4のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 4, wherein the ratio of the polymer (A) in the total solid content of the photosensitive composition is 0.07 to 1% by mass.
- 前記重合体(A)が、エポキシ基、メルカプト基および水酸基からなる群から選ばれる1種以上をさらに有する請求項1~5のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 5, wherein the polymer (A) further comprises one or more selected from the group consisting of an epoxy group, a mercapto group, and a hydroxyl group.
- 前記重合体(A)が、さらに下記一般式(2)で表される基を有する側鎖を有する請求項1~6のいずれか1項に記載の感光性組成物。
- 下記一般式(2)で表される基を有する側鎖およびポリオキシアルキレン基を有する側鎖を有し、かつ前記一般式(1)で表される基を有する側鎖とエチレン性二重結合を有する側鎖のいずれも有しない重合体(A)’であって、質量平均分子量(Mw(A)’)が、2.6×104<Mw(A)’≦20×104である重合体(A)’を、さらに含有する請求項1~7のいずれか1項に記載の感光性組成物。
- 前記光硬化開始剤(B)が光重合開始剤であり、前記バインダー樹脂(C)が酸性基とエチレン性二重結合とを有する感光性樹脂である請求項1~8のいずれか1項に記載の感光性組成物。 9. The photo-initiator (B) is a photo-polymerization initiator, and the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond. The photosensitive composition as described.
- さらに、エチレン性二重結合を2個以上有する架橋剤(D)を含む請求項9に記載の感光性組成物。 Furthermore, the photosensitive composition of Claim 9 containing the crosslinking agent (D) which has 2 or more of ethylenic double bonds.
- さらに、黒色着色剤(E)を含む請求項1~10のいずれか1項に記載の感光性組成物。 The photosensitive composition according to any one of claims 1 to 10, further comprising a black colorant (E).
- 基板上を画素形成用の複数の区画に仕切るかたちに形成された隔壁であって、請求項1~11のいずれか1項に記載の感光性組成物の塗膜硬化物からなることを特徴とする隔壁。 A partition formed in the form of partitioning a substrate into a plurality of sections for pixel formation, wherein the partition is made of a cured coating film of the photosensitive composition according to any one of claims 1 to 11. Partition wall.
- 基板上に複数の画素と隣接する画素間に位置する隔壁とを有するカラーフィルタであって、前記隔壁が請求項12に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とするカラーフィルタ。 A color filter having a plurality of pixels and a partition located between adjacent pixels on a substrate, wherein the partition is formed by the partition according to claim 12, and the pixel is formed by an inkjet method The color filter characterized by being.
- 基板上に複数の画素と隣接する画素間に位置する隔壁とを有する有機EL素子であって、前記隔壁が請求項12に記載の隔壁で形成されており、前記画素がインクジェット法により形成されたものであることを特徴とする有機EL素子。 An organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, wherein the partition is formed by the partition according to claim 12, and the pixel is formed by an inkjet method. An organic EL element characterized by being a thing.
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TW201129861A (en) | 2011-09-01 |
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JPWO2011081151A1 (en) | 2013-05-13 |
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