WO2013069789A1 - ネガ型感光性樹脂組成物、隔壁、ブラックマトリックス及び光学素子 - Google Patents
ネガ型感光性樹脂組成物、隔壁、ブラックマトリックス及び光学素子 Download PDFInfo
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- WO2013069789A1 WO2013069789A1 PCT/JP2012/079177 JP2012079177W WO2013069789A1 WO 2013069789 A1 WO2013069789 A1 WO 2013069789A1 JP 2012079177 W JP2012079177 W JP 2012079177W WO 2013069789 A1 WO2013069789 A1 WO 2013069789A1
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the present invention relates to a negative photosensitive resin composition, a partition and a black matrix using the same, and an optical element having the black matrix.
- a color filter-on-array technique has been proposed in which a color filter as an optical element is formed on a TFT (Thin Film Transistor) array substrate side (see, for example, Patent Document 1). ).
- a color filter on array type color filter a black matrix for partitioning pixels is formed on an array substrate. Therefore, this type of color filter is also referred to as a black matrix on array type (hereinafter referred to as “BOA type”). It is also called a color filter.
- the color filter and the TFT array substrate are manufactured separately, and accuracy can be secured without alignment as compared with a normal color filter that requires accuracy for alignment. Therefore, the partition wall can be thinned, the aperture ratio is improved, and a liquid crystal display device that achieves both low power consumption and high luminance can be obtained.
- a BOA type color filter unlike a color filter manufactured on a common counter substrate side, in order to connect a switching element such as a TFT and a pixel electrode, it is necessary to form a through hole called a contact hole in a partition wall. There is. Further, in order to increase the area of the pixel formation portion, that is, the display portion, the partition wall is required to be thinned, and the contact hole formed in the partition wall is also required to be miniaturized.
- a high resistance and a low dielectric constant are required for the partition walls in order to ensure the insulation between the pixel electrodes other than the contact holes and the switching elements such as wirings and TFTs.
- carbon black was used as the black colorant for the partition walls.
- carbon black has a low resistance and a high dielectric constant, so the amount used cannot be increased, and it is difficult to achieve both sufficient light shielding properties and electrical characteristics. It was.
- black organic pigments mixed with red, green, blue, etc., and single black organic pigments that absorb a wide range of visible light are inferior to carbon black but contain high resistance and low dielectric constant. The amount can be increased, and both light shielding properties and electrical characteristics can be achieved.
- an organic EL (Electro-Luminescence) element that is an optical element
- a black matrix including partition walls that partition pixels is used from the viewpoint of improving contrast and preventing reflection.
- the partition wall may be required to have a high resistance and a low dielectric constant.
- Patent Document 2 describes a photosensitive resin composition for a black resist containing a light-shielding disperse pigment that has excellent pattern stability in a partition having a film thickness of 1.5 ⁇ m or more used for a BOA type color filter or the like.
- Patent Document 3 discloses a specific pigment having an acid group or an amino group in order to improve dispersibility of an organic pigment in the photosensitive resin composition for forming a pixel or the like containing an organic pigment.
- a photosensitive resin composition using a dispersant is described.
- Patent Document 4 describes a photosensitive resin composition for forming an EL element light-shielding film, which contains a photopolymerizable compound and a black pigment.
- the photosensitive resin composition described in Patent Document 2 when manufacturing a partition having sufficient light-shielding properties, high sensitivity and formation of fine contact holes are trade-offs. It is in an off relationship, and it is difficult to achieve both. Furthermore, according to the knowledge of the present inventors, the photosensitive resin composition described in Patent Document 3 has insufficient dispersibility of the organic pigment in the organic solvent, and the photosensitive resin composition contains the organic solvent. The storage stability of is insufficient. Further, according to the knowledge of the present inventors, the photosensitive resin composition described in Patent Document 4 uses carbon black as a black pigment. Since the acrylic copolymer containing no is used, the resolution of the partition line is insufficient.
- the present invention can form a partition having both a fine line pattern and a fine contact hole, and is contained in an alkaline developer used for development.
- An object of the present invention is to provide a negative photosensitive resin composition having good dispersibility of the black organic pigment and good storage stability of itself.
- Another object of the present invention is to provide a partition and a black matrix applicable to a BOA type optical element and an organic EL element obtained by curing the negative photosensitive resin composition, and an optical element having the black matrix.
- the present invention provides a negative photosensitive resin composition, a partition, a black matrix, and an optical element having the following configurations [1] to [15].
- Alkali-soluble resin (A1) having an aromatic ring in the main chain and having an acidic group and an ethylenic double bond in the molecule; and an acidic group in the molecule having no aromatic ring in the main chain
- a negative photosensitive resin composition comprising an alkali-soluble resin (A2), a black organic pigment (B), and a photopolymerization initiator (C), the solid content acid value of which is 10 to 10 Negative photosensitive resin composition characterized by being 50 mgKOH / g.
- the total content of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) in the total solid content in the negative photosensitive resin composition is 5 to 80% by mass.
- the negative photosensitive resin composition as described.
- the negative photosensitive resin as described in [1] or [2] above, wherein the content ratio of the black organic pigment (B) in the total solid content in the negative photosensitive resin composition is 20 to 65% by mass.
- Resin composition [4]
- the negative photosensitive resin as described in any one of [1] to [3] above, wherein the mass average molecular weight of any one of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) is 10,000 or more. Resin composition.
- R 1 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 a hydrogen atom in a benzene ring.
- R 1 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 a hydrogen atom in a benzene ring.
- R 2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 20 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- the content of the compound represented by the formula (1) in the total amount of the photopolymerization initiator (C) is 85 to 95% by mass, and the total solid content of the negative photosensitive resin composition
- the negative photosensitive resin composition according to any one of [6].
- the ink repellent agent (E) has a side chain having a group represented by the following formula (3) or a group represented by the following formula (4) in one molecule and an ethylenic double bond.
- -CFXR f (3) In the formula (3), X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f represents a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or fluorine.
- R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R 14 represents a hydrogen atom or the number of carbon atoms.
- An alkyl group which may contain 1 to 10 etheric oxygen atoms or nitrogen atoms, and n represents an integer of 1 to 200.
- X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f represents a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or a fluorine atom.
- [11] The negative photosensitive resin composition according to any one of [1] to [10], further including a solvent (F).
- the partition wall has a through-hole penetrating in the film thickness direction of the partition wall, the horizontal maximum hole diameter in the through-hole is 20 ⁇ m or less, and the minimum hole diameter is 1 ⁇ m or more.
- Black matrix [15] An optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, wherein the partition is made of the black matrix described in [13] or [14]. Optical element.
- a negative photosensitive resin composition containing a black organic pigment in a negative photosensitive resin composition containing a black organic pigment, it is possible to form a partition having both a fine line pattern and a fine contact hole.
- a negative photosensitive resin composition having good dispersibility of the contained black organic pigment and good storage stability of itself can be provided.
- curing this negative photosensitive resin composition, and the optical element which has this black matrix can be provided.
- the “acid value” in the present specification refers to the number of milligrams of potassium hydroxide necessary for neutralizing resin acid and the like in 1 g of a sample.
- the “solid content acid value” refers to the number of milligrams of potassium hydroxide necessary to neutralize the resin acid in 1 g of the total solid content such as resin and pigment in the sample. All are values that can be measured according to the measurement method of JIS K 0070, and the unit is mgKOH / g.
- “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, (meth) allyl ..., (meth) acrylic resin.
- the “side chain” in the present specification is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer in which a repeating unit constitutes the main chain.
- the compound represented by Formula (1) in this specification is called compound (1).
- the group represented by the formula (3) in this specification is referred to as a group (3).
- the “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue.
- a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”.
- a cured film formed so as to partition the substrate surface into a plurality of compartments is referred to as a “partition wall”. Since the negative photosensitive resin composition contains a black organic pigment, the “partition” formed so as to partition the substrate surface into a plurality of compartments is referred to as “black matrix”.
- the “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
- the “ink” in the present specification is a general term for liquid compositions having, for example, optical and electrical functions after being dried and cured, and is not limited to conventionally used coloring materials. .
- “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by the partition walls.
- the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.
- the “contact hole” refers to a through hole provided to connect an element and an electrode in the direction of the film thickness of a partition wall.
- “Fine” of a minute contact hole means a size in which the maximum horizontal hole diameter in a through hole constituting the contact hole is approximately 20 ⁇ m or less.
- the horizontal maximum hole diameter in the through hole refers to the long diameter in the cross section having the maximum area in the horizontal cross section of the through hole, and the minimum hole diameter in the cross section having the minimum area in the horizontal cross section of the through hole. The minor axis.
- the “black organic pigment” refers to a colorant composed of a single organic pigment or a plurality of organic pigments that absorb light having a wavelength in the visible light region (400 to 800 nm). The present invention will be described in detail below. In addition, unless otherwise indicated in this specification,% represents the mass%.
- the negative photosensitive resin composition of the present invention includes an alkali-soluble resin (A1) having an aromatic ring in the main chain, an acidic group and an ethylenic double bond in the molecule, and an aromatic ring in the main chain.
- the alkali-soluble resin (A) including the alkali-soluble resin (A2) having an acidic group in the molecule is not included.
- the alkali-soluble resin (A) may contain an alkali-soluble resin other than the alkali-soluble resin (A1) and the alkali-soluble resin (A2), but is composed only of the alkali-soluble resin (A1) and the alkali-soluble resin (A2). It is preferable.
- the mass average molecular weights of either alkali-soluble resin (A1) and alkali-soluble resin (A2) are 10,000 or more.
- the upper limit of the mass average molecular weight is not particularly limited, and can be the same as the upper limit described later for each alkali-soluble resin.
- the alkali-soluble resin (A1) and the alkali-soluble resin (A2) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
- the mass average molecular weights of either alkali-soluble resin (A1) and alkali-soluble resin (A2) are 10,000 or more.
- the content of the alkali-soluble resin having a mass average molecular weight of 10,000 or more in the total amount of the alkali-soluble resin is preferably 5% by mass or more.
- the content of the alkali-soluble resin (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass.
- alkali-soluble resin (A) contains alkali-soluble resin other than alkali-soluble resin (A1) and alkali-soluble resin (A2)
- the ratio is 10 mass% or less with respect to the whole quantity of alkali-soluble resin (A).
- the alkali-soluble resin (A) is composed only of the alkali-soluble resin (A1) and the alkali-soluble resin (A2), and the content ratio of each resin is that of the alkali-soluble resin (A1): alkali-soluble resin (A2).
- the mass ratio is preferably 99 to 80: 1 to 20, particularly preferably 97 to 85: 3 to 15.
- the acid value of the alkali-soluble resin (A) is preferably 10 to 350 mgKOH / g, more preferably 20 to 300 mgKOH / g, and particularly preferably 30 to 250 mgKOH / g.
- the solid content acid value in the negative photosensitive resin composition is determined by the acid value and blending amount of the alkali-soluble resin (A). When the acid value of the alkali-soluble resin (A) is within the above range, the solid content acid value in the negative photosensitive resin composition can be easily adjusted within the range of the present invention, that is, 10 to 50 mgKOH / g.
- the negative photosensitive resin composition of the present invention contains a black organic pigment (B) in order to make the partition obtained as described later have high resistance and low dielectric constant.
- both the alkali-soluble resin (A1) and the alkali-soluble resin (A2) are blended in the negative photosensitive resin composition containing the black organic pigment (B) as the alkali-soluble resin (A). This makes it possible to improve the dispersibility in the alkaline developer while maintaining the dispersion stability of the black organic pigment (B) in the negative photosensitive resin composition.
- the reason for the improvement in dispersibility is presumed as follows.
- a negative photosensitive resin composition for a black matrix uses an alkali-soluble resin (A1) having an aromatic ring in the main chain and having an acidic group and an ethylenic double bond in the molecule.
- the negative photosensitive resin composition is required to have pigment dispersibility in an alkaline developer that is recycled, but according to the knowledge of the present inventors, only the alkali-soluble resin (A1) is used as the alkali-soluble resin. When used, the dispersibility of the black organic pigment (B) in an alkaline developer may be insufficient.
- the black organic pigment (B) By using together the alkali-soluble resin (A1) and the alkali-soluble resin (A2) which does not contain an aromatic ring in the main chain and has an acidic group in the molecule, the black organic pigment (B) It was confirmed that the dispersibility in an alkali developer can be improved. Although the detailed mechanism is unknown, since the alkali-soluble resin (A2) does not contain a rigid aromatic ring in the main chain, the alkali-soluble resin (A) as a whole covers the black organic pigment (B) densely. It is assumed that the dispersibility of the black organic pigment (B) in the alkaline developer can be improved.
- the alkali-soluble resin (A1) in the present invention is a photosensitive resin having an aromatic ring in the main chain and having an acidic group and an ethylenic double bond in the molecule. Since the alkali-soluble resin (A1) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator. The cured exposed portion is not removed with an alkaline developer. Moreover, since the alkali-soluble resin (A1) has an acidic group in the molecule, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkali developer. As a result, a partition wall can be formed. In addition, it is preferable that alkali-soluble resin (A1) does not contain substantially the group (1) or group (2) which the below-mentioned ink repellent agent (E) has.
- Examples of the aromatic ring contained in the main chain of the alkali-soluble resin (A1) include divalent aromatic ring structures such as a phenylene group, a naphthylene group, and an anthracenylene group.
- the carbon atom in the aromatic ring may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
- a phenylene group is preferable, and a biphenyl group in which two phenylene groups are bonded is particularly preferable.
- the alkali-soluble resin (A1) is not particularly limited, but a resin (A1-1) having an aromatic ring in the main chain and having a side chain having an acidic group and a side chain having an ethylenic double bond, Resin (A1-2) having an acidic group and an ethylenic double bond introduced into an epoxy resin having an aromatic ring in the chain, having a side chain having an acidic group and a side chain having an ethylenic double bond And a monomer (A1-3) containing an aromatic ring in the portion constituting the main chain by polymerization.
- One type may be used alone or two or more types may be used in combination.
- Resin (A1-2) is prepared by reacting an epoxy resin having an aromatic ring in the main chain with a compound having a carboxy group and an ethylenic double bond, which will be described later, and a polyvalent carboxylic acid or an anhydride thereof. Can be synthesized by reacting. Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin having an aromatic ring in the main chain with a compound having a carboxy group and an ethylenic double bond. Next, a carboxy group can be introduced by reacting an epoxy resin containing an aromatic ring with a polyvalent carboxylic acid or an anhydride thereof in the main chain into which the ethylenic double bond has been introduced.
- the epoxy resin is not particularly limited as long as it is an epoxy resin containing an aromatic ring in the main chain.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, represented by the following formula (A1-2a)
- v is an integer of 1 to 50, preferably an integer of 2 to 10.
- the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, halogen An atom or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.
- 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 w is 0 to (It is an integer of 10.)
- the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent.
- u is an integer of 0 to 10.
- the epoxy resin represented by the formulas (A1-2a) to (A1-2c) is reacted with a compound having a carboxy group and an ethylenic double bond and then reacted with a polyvalent carboxylic acid anhydride. It is preferable to use a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride as the polyvalent carboxylic acid anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.
- (meth) acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof are preferable.
- Acrylic acid is particularly preferred.
- the resin (A1-2) a commercially available product can be used.
- commercial products all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, Nipponization) Yakuhin Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), EA-7440 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
- Examples of the resin (A1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acid group and ethylenic double bond introduced into novolac type epoxy resin, resin with acid group and ethylenic double bond introduced into cresol novolac type epoxy resin, acid group and ethylene into trisphenol methane type epoxy resin A resin into which an acidic double bond is introduced, and a resin in which an acidic group and an ethylenic double bond are introduced into the epoxy resins represented by the formulas (A1-2a) to (A1-2c) are particularly preferable.
- the number of ethylenic double bonds that the alkali-soluble resin (A1) has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more.
- the exposed portion is excellent in curability, and a fine pattern can be formed with a smaller exposure amount.
- the weight average molecular weight of the alkali-soluble resin (A1) (Mw) is more preferably 1.5 ⁇ 10 3 ⁇ 100 ⁇ 10 3 is preferably 1.5 ⁇ 10 3 ⁇ 30 ⁇ 10 3, 2 ⁇ 10 3 ⁇ 20 ⁇ 10 3 is particularly preferred.
- the number average molecular weight (Mn) is preferably 500 to 50 ⁇ 10 3, more preferably 500 to 20 ⁇ 10 3, and particularly preferably 1 ⁇ 10 3 to 10 ⁇ 10 3 .
- the acid value of the alkali-soluble resin (A1) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is in the above range, the developability of the negative photosensitive resin composition is improved.
- the alkali-soluble resin (A2) is a photosensitive resin that does not contain an aromatic ring in the main chain and has an acidic group in the molecule. By having an acidic group in the molecule, it becomes soluble in an alkaline aqueous solution, and the unexposed portion can be dissolved.
- the acidic group is not particularly limited, and examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfo group, and a phosphoric acid group, and a carboxy group is preferable. One type may be used alone or two or more types may be used in combination.
- the alkali-soluble resin (A2) may have an ethylenic double bond in the side chain as necessary in addition to the acidic group.
- the ethylenic double bond is the same as the ethylenic double bond of the alkali-soluble resin (A1).
- the alkali-soluble resin (A2) can be synthesized, for example, by the following method. Examples include a method of polymerizing a monomer having a reactive group such as an acidic group and an ethylenic double bond, a method of copolymerizing a monomer having no acidic group and a monomer having the acidic group, and the like. It is done. In addition, all the monomers to be used are monomers having a structure in which the obtained (co) polymer has no aromatic ring in the main chain. However, the obtained (co) polymer may have an aromatic ring in the side chain.
- the double bond which has addition polymerizability such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, a vinyloxyalkyl group, is mentioned, These are 1 You may use a seed
- some or all of the hydrogen atoms of the ethylenic double bond group may be substituted with an alkyl group, preferably a methyl group.
- the monomer which can comprise alkali-soluble resin (A2), and its combination are demonstrated concretely.
- a monomer having a reactive group such as an acidic group and an ethylenic double bond a compound having a carboxy group as an acidic group and an ethylenic double bond is preferable, (meth) acrylic acid, vinyl acetic acid, Crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof are preferred, and (meth) acrylic acid is particularly preferred.
- each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 20 carbon atoms.
- Styrene aromatic vinyl compounds such as ⁇ -methylstyrene optionally substituted with an alkyl group having 1 to 20 carbon atoms; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2- Unsaturated carboxylic acid esters such as hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; N-methylmaleimide, N-ethylmaleimide, N- (2-hydroxy N) such as ethyl) maleimide, N-cyclohexylmaleimide, N-pheny
- styrene, ethyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide are particularly preferable.
- (meth) acrylic acid is used as the monomer having an acidic group, and the side chain in the copolymer obtained as a monomer having no acidic group is used.
- a combination using at least one monomer having a benzene ring is preferred.
- alkali-soluble resin (A2) examples include (meth) acrylic acid / styrene, (meth) acrylic acid / long chain alkylstyrene, (meth) acrylic acid / Styrene / ethyl (meth) acrylate, (meth) acrylic acid / N-ethylmaleimide / benzyl (meth) acrylate, (meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate, (meth) acrylic acid / styrene / N-phenylmaleimide / benzyl (meth) acrylate is preferred.
- (meth) acrylic acid / styrene (meth) acrylic acid / N-ethylmaleimide / benzyl (meth) acrylate, (meth) acrylic acid / styrene / N-phenylmaleimide / Benzyl (meth) acrylate is particularly preferred.
- the molar ratio of the constituent monomers in each combination is not particularly limited, but may be adjusted so that the molecular weight and the acid value are in the following ranges. preferable. Further, when the alkali-soluble resin (A2) has a benzene ring in the side chain, the molar ratio of the monomer having a benzene ring used for copolymerization to the other monomer is determined as the monomer 1 having a benzene ring.
- the amount of other monomers is preferably about 0.05 to 4 mol, particularly preferably 0.05 to 2 mol, relative to mol.
- the mass average molecular weight of the alkali-soluble resin (A2) is preferably 5 ⁇ 10 3 to 10 ⁇ 10 4. From the viewpoint of stable dispersibility of the black organic pigment (B) in an alkali developer, 1 ⁇ 10 4 to 10 ⁇ 10 4 is particularly preferred.
- the number average molecular weight (Mn) is preferably 1 ⁇ 10 3 to 2 ⁇ 10 4 , particularly preferably 2 ⁇ 10 3 to 1 ⁇ 10 4 .
- the acid value of the alkali-soluble resin (A2) is preferably in the range of 20 to 300 mgKOH / g, and particularly preferably in the range of 30 to 250 mgKOH / g in order to maintain the pattern shape.
- the acid value of the alkali-soluble resin (A2) is in the above range, the acid value as the alkali-soluble resin (A) can be easily adjusted to the range described later, and further, the solid content of the negative photosensitive resin composition It is easy to adjust the acid value within the range of the present invention.
- the alkali-soluble resin (A2) may have an ethylenic double bond in the side chain as necessary in addition to the acidic group.
- the method for introducing an ethylenic double bond into the side chain is the same as in the case of the alkali-soluble resin (A1).
- the number of ethylenic double bonds that the alkali-soluble resin (A2) has in one molecule is the same as that of the alkali-soluble resin (A1).
- alkali-soluble resin (A2) a commercially available product can be used.
- commercial products all are trade names, UC-3080, UC-3900, UC-3920 (manufactured by Toa Gosei Co., Ltd., acrylic acid / styrene copolymer), UF-5022 (manufactured by Toa Gosei Co., Ltd., acrylic acid / long) Chain alkyl styrene copolymer), MSP-9610, MSP-9611, MSP9612, MSP9617 (manufactured by Shin-Nakamura Chemical Co., Ltd., methacrylic acid / styrene / N-phenylmaleimide / benzyl methacrylate copolymer) and the like.
- Black organic pigment (B) The negative photosensitive resin composition in the present invention contains a black organic pigment (B) as a light-shielding agent.
- the black organic pigment (B) include anthraquinone black pigments, perylene black pigments, azomethine black pigments, and the like.
- C.I. I. Examples thereof include black organic pigments (B) made of a single organic pigment that widely absorbs light having a wavelength in the visible light region such as CI Pigment Black 1, 6, 7, 12, 20, 31 and the like.
- the black organic pigment (B) two or more chromatic organic pigments such as a red pigment, a blue pigment, a green pigment, and a yellow pigment are mixed, and the resulting mixture becomes black, that is, a wavelength in the visible light region. It is also possible to use a black organic pigment (B) mixed and mixed so as to absorb a large amount of light.
- Specific examples of the chromatic organic pigment that can be used for the production of such a black organic pigment (B) include C.I. I. Pigment blue 2, 3, 9, 15: 1, 15: 3, 15: 6, 22, 25: 4, 60, 61, 66, 80, C.I. I.
- the black organic pigment (B) obtained as a mixture of these chromatic organic pigments C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. Pigment green 36, C.I.
- a combination of I. Pigment Yellow 150 is preferable from the viewpoint of dispersibility and dispersion stability.
- the blending ratio of each organic pigment is not particularly limited as long as the ratio becomes black after mixing.
- BET specific surface area of the black organic pigment (B), from the viewpoint of the shape of the black matrix is preferably 50 ⁇ 200m 2 / g, particularly preferably 50 ⁇ 150m 2 / g.
- the specific surface area is 50 m 2 / g or more, the black matrix shape is hardly deteriorated.
- the dispersion aid is not excessively adsorbed on the black organic pigment (B), and it is not necessary to add a large amount of dispersion aid in order to develop various physical properties.
- the average primary particle diameter of the black organic pigment (B) observed with a transmission electron microscope is preferably 20 to 150 nm, and particularly preferably 30 to 130 nm.
- the average primary particle size is 20 nm or more, the negative photosensitive resin composition can be dispersed at a high concentration with the negative photosensitive resin composition, and a negative photosensitive resin composition with good temporal stability can be easily obtained.
- the black matrix shape is hardly deteriorated.
- the average secondary particle diameter by observation with a transmission electron microscope is preferably from 80 to 200 nm, particularly preferably from 100 to 200 nm.
- the content ratio of the black organic pigment (B) in the total solid content in the negative photosensitive resin composition is preferably 20 to 65% by mass, more preferably 25 to 60% by mass, and particularly preferably 30 to 55% by mass.
- the content ratio is equal to or higher than the lower limit of the above range, the optical density, which is a value indicating the light blocking property of the obtained partition wall, is sufficient.
- the curability of the negative photosensitive resin composition becomes good, and a cured film having a good appearance can be obtained.
- the content ratio is less than or equal to the upper limit of the above range, the dispersibility of the black organic pigment (B) in the alkali developer after development is good, and the circulatory filter of the alkali developer flocculates and settles. Less likely to cause clogging.
- the polymer dispersant is preferably a compound having an acidic functional group or a basic functional group from the viewpoint of affinity for the black organic pigment (B).
- the acidic functional group include a carboxy group, a sulfo group, and a phosphoric acid group, and a carboxy group is preferable.
- the acid value of the polymer dispersant is preferably 10 to 100 mgKOH / g.
- the basic functional group has a primary, secondary or tertiary amino group, the dispersibility is particularly excellent.
- Polymer dispersing agents include urethane, polyimide, alkyd, epoxy, unsaturated polyester, melamine, phenol, acrylic, vinyl chloride, vinyl chloride vinyl acetate copolymer, polyamide, polycarbonate And the like. Of these, urethane-based and polyester-based compounds are particularly preferable.
- the amount of the polymer dispersant used is preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight, based on the black organic pigment (B).
- the black organic pigment (B) is usually used as a dispersion containing the black organic pigment (B), a polymer dispersant and a dispersion medium.
- the dispersion is produced, for example, by subjecting a mixture containing a black organic pigment (B), a polymer dispersant, and a dispersion medium to a wet pulverization / dispersion treatment using a known wet pulverization / dispersion device such as a paint conditioner or a bead mill. it can.
- a wet pulverization / dispersion device such as a paint conditioner or a bead mill.
- the dispersion medium to be used those similar to the solvent (F) of the negative photosensitive resin composition described later can be used.
- the amount of the dispersion medium in the dispersion is usually about 65 to 90% by mass of the total dispersion.
- a commercially available product can be used as the dispersion.
- the negative photosensitive resin composition in the present invention contains a photopolymerization initiator (C).
- C photopolymerization initiator
- the partition walls have low light transmittance, when the conventional photolithographic method is used, the photocurability at the bottom of the partition walls is poor, and if a high-sensitivity photopolymerization initiator is not used, the pattern dissolves during alkali development and is good. Difficult pattern formation becomes difficult.
- the photopolymerization initiator (C) it is preferable to use a compound represented by the following formula (1) (hereinafter also referred to as “photopolymerization initiator (C1)”).
- photopolymerization initiator (C1) By using the photopolymerization initiator (C1), the curability is good, and after forming the coating film, in the partition wall obtained through the exposure process and the development process, the line pattern and the line width have a shape close to the mask pattern at the time of exposure. A negative photosensitive resin composition that can be formed and capable of forming minute contact holes is obtained.
- the photopolymerization initiator (C1) is used as the photopolymerization initiator (C)
- sufficient ink repellency is imparted to the partition walls when the negative photosensitive resin composition contains the ink repellent agent (E). And the solubility of the black organic pigment (B) in the alkaline developer is not inhibited.
- the photopolymerization initiator (C1) is composed of an O-acyloxime compound represented by the following formula (1).
- R 1 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 a hydrogen atom in a benzene ring.
- R 2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 20 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 1 is preferably an alkyl group having 1 to 10 carbon atoms, or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- the alkyl group an alkyl group having 1 to 4 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
- a phenyl group is likewise preferred.
- R 2 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms.
- R 2 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms.
- an alkyl group having 1 to 6 carbon atoms is more preferable, and a hexyl group and a methyl group are particularly preferable.
- a commercial item can be used for a photoinitiator (C1).
- Examples of commercially available products include IRGACURE OXE01 (trade name, manufactured by BASF: a compound in which R 1 is a phenyl group and R 2 is a hexyl group in the above formula (1)).
- the content of the photopolymerization initiator (C) containing the photopolymerization initiator (C1) in the total solid content in the negative photosensitive resin composition is preferably 3.5 to 7% by mass. 6 to 6% by mass is more preferable, and 3.7 to 5.5% by mass is particularly preferable. If it exists in the said range, sclerosis
- the line pattern and line width can be formed in a shape close to the mask pattern at the time of exposure, and a minute contact hole can be formed. Further, the solubility of the black organic pigment (B) in the alkaline developer is not inhibited.
- the negative photosensitive resin composition contains the ink repellent agent (E), sufficient ink repellency can be imparted to the partition walls.
- a photoinitiator (C1) may be used for a photoinitiator (C), the said effect acquired by mix
- Examples of the photopolymerization initiator used in combination with the photopolymerization initiator (C1) include photopolymerization initiators that are more sensitive than the photopolymerization initiator (C1), particularly in that the photocurability at the lower part of the partition wall can be enhanced.
- a photopolymerization initiator more sensitive O-acyloxime compounds such as Adekaoptomer N-1919, Adeka Cruz NCI-831, NCI-930 (all manufactured by ADEKA, trade names) ), A compound represented by the following formula (2) (hereinafter also referred to as “photopolymerization initiator (C2)”), and the like.
- the photopolymerization initiator (C2) is preferable.
- R 3 represents a hydrogen atom, R 61 or OR 62 , and each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring.
- R 4 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 5 is an alkyl group having 1 to 20 carbon atoms, a hydrogen atom in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring is an alkyl group.
- An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
- R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring.
- a benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom It represents an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or an amide group having 1 to 20 carbon atoms.
- R 0 represents R 61 , OR 62 , a cyano group or a halogen atom.
- a is an integer of 0 to 3.
- R 3 represents 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 a hydrogen atom in a benzene ring.
- R 3 represents a phenyl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, or a phenoxy group having 6 to 20 carbon atoms where a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 20 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 5 represents an alkyl group having 1 to 12 carbon atoms.
- R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group.
- R 3 is preferably an alkyl group having 1 to 10 carbon atoms, or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 3 is preferably an alkyl group having 1 to 10 carbon atoms, or a phenyl group having 6 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 4 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms.
- R 4 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms.
- an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
- R 5 is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, an alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
- R 6 , R 8 and R 9 are preferably a hydrogen atom or a nitro group.
- R 7 includes a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and a carbon atom number in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- a benzylcarbonyl group of 7 to 20 or a nitro group is preferable, and a benzoyl group, 2-methylbenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2- A methyl-5-tetrahydropyranylmethoxybenzoyl group, a benzylcarbonyl group, a 1,3,5 trimethylbenzylcarbonyl group and a nitro group are particularly preferred. “A” indicating the number of R 0 is 0.
- the photopolymerization initiator (C2) include compounds (2-1) in which, in the formula (2), R 3 to R 9 are each the following groups, and a indicating the number of R 0 is 0: To (2-10).
- R 3 phenyl group
- R 4 octyl group
- R 5 ethyl group
- R 6 , R 8 , R 9 hydrogen atom
- R 7 benzoyl group
- R 3 methyl group
- R 7 benzoyl group (2-2)
- a commercial item can be used for a photoinitiator (C2).
- Examples of commercially available products include IRGACURE OXE02 (trade name, manufactured by BASF: equivalent to the above compound (2-7)).
- the content rate of the photoinitiator (C2) in the whole quantity of a photoinitiator (C) is photoinitiator (C1 ), That is, 5 to 15% by weight, preferably 5 to 10% by weight.
- the ratio of the photopolymerization initiator (C2) in the photopolymerization initiator (C) is within the above range, the above-described effect due to the photopolymerization initiator (C1) can be sufficiently obtained, and the photocurability at the lower part of the black matrix can be obtained. It is possible to increase.
- Examples of the photopolymerization initiator that can be used in combination with the photopolymerization initiator (C1) include the following photopolymerization initiators in addition to the highly sensitive O-acyloxime compound containing the photopolymerization initiator (C2). It is done.
- ⁇ -diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2-chloro Thioxanthones such as thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone Benzophenones such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone;
- the negative photosensitive resin composition in the present invention may contain a crosslinking agent (D) as an optional component for promoting radical curing.
- a crosslinking agent (D) the compound which has two or more ethylenic double bonds in 1 molecule, and does not have an acidic group is preferable.
- crosslinking agent (D) examples include 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 penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ⁇ -caprolactone modified tris- (2-acryloxyethyl) isocyanurate, ⁇ 4-
- hept-5-ene-2,3-dicarboximide 1,3-dicarboximide
- urethane acrylate 1,3-dicarboximide
- photoreactivity it is preferable to have a large number of ethylenic double bonds.
- these may be used individually by 1 type, or may use 2 or more types together.
- crosslinking agent (D) Commercial products can be used as the crosslinking agent (D).
- 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-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK Este A-9300 (trade name, Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co
- 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. are mentioned.
- the content of the crosslinking agent (D) in the total solid content in the negative photosensitive resin composition is preferably 1 to 60% by mass, particularly preferably 2 to 15% by mass. Within the above range, the alkali developability of the negative photosensitive resin composition is improved.
- the negative photosensitive resin composition in the present invention contains an ink repellent agent (E) as necessary.
- the ink repellent agent (E) is a compound that is unevenly distributed on the surface of the coating film and imparts an ink repellent function to the surface of the cured film.
- ink repellent agent (E) a group represented by the following formula (3) (hereinafter also referred to as “group (3)”) or a group represented by the following formula (4) (hereinafter, A compound having a side chain having "group (4)”) is preferred, and a compound having both a side chain having group (3) or group (4) and a side chain having an ethylenic double bond (hereinafter referred to as “group (4)”) , Also referred to as “ink repellent agent (E1)”).
- X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group
- R f represents a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, or a fluorine atom. Indicates.
- R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group
- R 14 represents a hydrogen atom or a carbon atom number of 1
- n represents an integer of 1 to 200.
- the ink repellent agent (E1) comprises a polymer having a side chain containing a group (3) and a side chain having an ethylenic double bond, a side chain containing a group (4) and a side chain having an ethylenic double bond. Or a polymer having a side chain containing a group (3), a side chain containing a group (4), and a side chain having an ethylenic double bond. It may consist of more than seeds.
- the ink repellent agent (E) is a group exhibiting ink repellency, for example, the ink repellent agent (E1) has a side chain having the group (3) or the group (4), so that the surface free energy is small, Sufficient surface migration. That is, in the negative photosensitive resin composition of the present invention containing the above various solid components and the solvent (F) described later, when forming a coating film, these are sufficiently compatible and uniform. Although formed as a composition, in the process of evaporating the solvent (F) in the drying step of the coating film of the composition, a sufficient repulsive force is brought between the ink repellent agent (E) and other solid components, The ink repellent agent (E) moves to the vicinity of the film surface to form an ink repellent agent layer.
- the partition wall made of a cured film of the composition has an ink repellent agent layer having an appropriate thickness on its surface, thereby repelling the ink. Ink properties are developed. Further, ink injected by the ink jet method does not overflow from the dots (locations that become pixels), and color mixing between adjacent pixels hardly occurs. Furthermore, if the ink repellent agent (E1) having a side chain having an ethylenic double bond is used as the ink repellent agent (E), a curing reaction of the ink repellent agent (E1) occurs during exposure, and the ink repellent agent (E1) is immobilized on the partition wall surface. Cheap.
- the partition walls obtained from the negative photosensitive resin composition containing the ink repellent agent (E), particularly the ink repellent agent (E1) have high ink repellency and ink falling onto the dots (display portion). Sex can be expressed.
- the side chain having the group (3) or the group (4) may be formed directly by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction. Further, the side chain having an ethylenic double bond can be formed by chemical conversion after the polymerization reaction.
- R f in the group (3) is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom
- the hydrogen atom in the fluoroalkyl group may be other than a fluorine atom.
- the other halogen atom is preferably a chlorine atom.
- the etheric oxygen atom may be present between the carbon-carbon bonds of the alkyl group or may be present at the terminal of the alkyl group.
- Examples of the structure of the alkyl group include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.
- the group (3) is preferably a perfluoroalkyl group or a polyfluoroalkyl group containing one hydrogen atom, and particularly preferably a perfluoroalkyl group (provided that the alkyl group includes an etheric oxygen atom). .) Thereby, the partition formed from a negative photosensitive resin composition becomes favorable in ink repellency.
- the total number of carbon atoms in the group (3) is preferably 4-6.
- the group (3) is particularly preferably a perfluoroalkyl group having 4 to 6 carbon atoms in total.
- group (3) include the following. -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 an integer of 1 to 8), -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 (CF 3
- R 10 and R 11 in the group (4) may be the same or different for each siloxane unit. Since the partition formed from the negative photosensitive resin composition exhibits excellent ink repellency, R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group. Or an aryl group, more preferably a hydrogen atom, a methyl group, or a phenyl group, and R 10 and R 11 of all siloxane units are particularly preferably a methyl group. In the group (4), R 12 , R 13 and R 14 are groups bonded to the silicon atom at the terminal of the siloxane bond, and R 12 and R 13 can be the same as R 10 and R 11.
- R 14 may contain an etheric oxygen atom (—O—) or a nitrogen atom (—NR 40 —; R 40 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
- R 14 is particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- n is preferably an integer of 1 to 200, particularly preferably an integer of 2 to 100.
- group (4) include the following. - (Si (CH 3) 2 O) n -Si (CH 3) 2 H, - (Si (CH 3) 2 O) n -Si (CH 3) 2 CH 3, - (Si (CH 3) 2 O N- Si (CH 3 ) 2 C 2 H 5 ,-(Si (CH 3 ) 2 O) n -Si (CH 3 ) 2 C 3 H 7 ,-(Si (CH 3 ) 2 O) n -Si (CH 3 ) 2 C 4 H 9 , — (Si (CH 3 ) 2 O) n —Si (CH 3 ) 2 C 5 H 10 , — (Si (CH 3 ) 2 O) n —Si (CH 3 ) 2 OH, — (Si (CH 3 ) 2 O) n —Si (CH 3 ) 2 OCH 3 , — (Si (CH 3 ) 2 O) n —Si (CH 3
- ethylenic double bond examples include double bonds having addition polymerizability such as (meth) acryloyl group, allyl group, vinyl group, vinyloxy group, vinyloxyalkyl group, and these are used alone. Also, two or more of them may be used in combination. In addition, a part or all of the hydrogen atoms of the addition polymerizable group may be substituted with an alkyl group, preferably a methyl group.
- the ink repellent agent (E) containing the ink repellent agent (E1) is preferably a polymer having a side chain having an acidic group. Some molecules of the ink repellent agent (E) that did not undergo a curing reaction in the exposure process are washed away from the partition wall surface during development because they have side chains having acidic groups, and are not fixed in the partition walls. The remaining molecules are difficult to remain. In the previous stage of the post-baking process, the number of molecules that can migrate to the dots can be further reduced, and the ink affinity of the dots can be further improved.
- the side chain having an acidic group may be formed by a polymerization reaction of a monomer having an acidic group, or may be formed by a chemical conversion after the polymerization reaction.
- the ink repellent agent (E1) having a side chain having the group (3) or the group (4) and a side chain having an ethylenic double bond which is preferably used in the present invention, is a monomer (a1) described later. And / or copolymerizing two or more monomers including the monomer (a2) and the monomer (a3) having a reactive group, and then obtaining the copolymer and the reactive group It can manufacture by making the compound (z1) which has a functional group which can couple
- the monomer (a1) is a monomer having the group (3), and the monomer (11) represented by the following formula (11) is preferable.
- CH 2 CR 21 COO-Y-CFXR f (11)
- R 21 represents a hydrogen atom, a methyl group or a trifluoromethyl group
- Y represents a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms
- R f represents an etheric group. It represents an alkyl group in which at least one hydrogen atom having 1 to 20 carbon atoms which may have an oxygen atom is substituted with a fluorine atom, or a fluorine atom.
- the preferred embodiment of —CFXR f is the same as the preferred embodiment of the group (3).
- Y is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
- Examples of the monomer (11) include the following.
- R 24 CFXR f
- R 21 represents a hydrogen atom, a methyl group, or a trifluoromethyl group
- R 22 represents an alkylene group having 1 to 6 carbon atoms
- R 23 represents a hydrogen atom or a methyl group
- R 24 represents a single atom.
- R represents a bond or an alkylene group having 1 to 4 carbon atoms
- R f has the same meaning as described above.
- R 22 are, -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 24 are, -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.
- monomer (11) examples include 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, and the like.
- Monomer (11) may use 1 type and may use 2 or more types together.
- the monomer (a2) is a monomer having the group (4), and the monomer (21) represented by the following formula (21) is preferable.
- CH 2 CR 25 COO-Z- (SiR 10 R 11 O) n -SiR 12 R 13 R 14 (21)
- R 25 represents a hydrogen atom or a methyl group
- Z represents a divalent organic group having 1 to 6 carbon atoms
- R 10 , R 11 , R 12 and R 13 are each independently ,
- R 14 is a hydrogen atom, or an etheric oxygen atom or nitrogen atom having 1 to 10 carbon atoms (—NR 41 —.
- R 41 is a hydrogen atom or An alkyl group having 1 to 5 carbon atoms.
- N represents an integer of 1 to 200.
- preferred embodiments of R 10 , R 11 , R 12 , R 13 , R 14 , and n are the same as the preferred embodiment of the group (4).
- Z is preferably a divalent alkyl group having 1 to 6 carbon atoms. Specific examples include the following. -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.
- the said monomer (21) may use 1 type and may use 2 or more types together.
- the monomer (a3) is a monomer having a reactive group, a monomer having a hydroxyl group, a monomer having an acid anhydride group, a monomer having a carboxy group, and a monomer having an epoxy group Etc.
- the reactive group include a hydroxyl group, an acid anhydride group, a carboxy group, and an epoxy group.
- a monomer (a3) does not contain group (3) and group (4) substantially.
- the monomer having a hydroxyl group examples 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 (meta) Acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.
- the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group.
- CH 2 CHOCH 2 C 6 H 10 CH 2 O (C 2 H 4 O) h H (where h is an integer of 1 to 100, the same shall apply hereinafter)
- CH 2 CHOC 4 H 8 O (C 2 H 4 O) h H
- CH 2 CHCOOC 2 H 4 O (C 2 H 4 O) h H
- CH 2 C (CH 3) COOC 2 H 4 O (C 2 H 4 O) h H
- CH 2 CHCOOC 2 H 4 O (C 2 H 4 O) i (C 3 H 6 O) g H (where i is an integer from 0 to 100, g is an integer from 1 to 100, and m + j is 1 to 100.
- a commercial item can be used as a monomer which has a hydroxyl group.
- the following are mentioned as a commercial item.
- 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: wherein k is about 6)
- 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
- the monomer having an acid anhydride group examples include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6- Examples thereof include tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, and 2-buten-1-yl succinic anhydride.
- Specific 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.
- Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
- the monomer (a3) is preferably a compound having a hydroxyl group at the terminal, more preferably (meth) acrylate having a hydroxyl group at the terminal, and particularly preferably 2-hydroxyethyl (meth) acrylate.
- the compound (z1) is selected according to the reactive group possessed by the monomer (a3).
- Examples of the combination of the reactive group and the compound (z1) include the following examples. (1) An acid anhydride having an ethylenic double bond as the compound (z1) with respect to a hydroxyl group as a reactive group, (2) A compound having an isocyanate group and an ethylenic double bond as the compound (z1) with respect to the hydroxyl group as the reactive group, (3) A compound having an acyl chloride group and an ethylenic double bond as the compound (z1) with respect to the hydroxyl group as the reactive group, (4) A compound having a hydroxyl group and an ethylenic double bond as the compound (z1) with respect to the acid anhydride group as the reactive group, (5) A compound having an epoxy group and an ethylenic double bond as the compound (z1) with respect to the carboxy group as the reactive group, (6) A compound having a carboxy group and an ethylenic
- Specific examples of the acid anhydride having an ethylenic double bond as the compound (z1) include the same compounds as those described above for the monomer having an acid anhydride group.
- Specific examples of the compound having an isocyanate group and an ethylenic double bond as the compound (z1) include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
- Specific examples of the compound having an acyl chloride group and an ethylenic double bond as the compound (z1) include (meth) acryloyl chloride.
- Specific examples of the compound having a hydroxyl group and an ethylenic double bond as the compound (z1) include the above-described monomer examples having a hydroxyl group.
- Specific examples of the compound having an epoxy group and an ethylenic double bond as the compound (z1) include the above-described monomers having an epoxy group.
- Specific examples of the compound having a carboxy group and an ethylenic double bond as the compound (z1) include the above-described monomers having a carboxy group.
- the combination (2) is preferable, and it is particularly preferable to use 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate as the compound (z1).
- the ink repellent agent (E) has side chains having two or more ethylenic double bonds per side chain, and the ink repellent agent (E) is immobilized on the partition wall surface. This is because a partition wall excellent in ink repellency can be obtained.
- the ink repellent agent (E) has a side chain having an acidic group
- the monomer (a4) having an acidic group include a monomer having a carboxy group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfo group.
- the monomer having a carboxy group include the same monomers as exemplified in the above monomer (a3).
- Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.
- one or more hydrogen atoms of these benzene rings are alkyl groups such as methyl group, ethyl group and n-butyl group, alkoxy groups such as methoxy group, ethoxy group and n-butoxy group, halogen atoms and alkyl groups. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, an amide group, or the like.
- Examples of the monomer having a sulfo group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, (meth) acrylic acid-2-sulfoethyl, (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like.
- the other monomer (a5) is preferably a compound (51) represented by the following formula (51) having a polyoxyalkylene group or a compound (52) represented by the following formula (52). . These may be used individually by 1 type, or may use 2 or more types together.
- CH 2 CR 26 —COO—W— (R 27 O) m (R 28 O) j R 29 (51)
- CH 2 CR 26 —OW— (R 27 O) m (R 28 O) j R 29 (52)
- R 26 represents 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.
- W is a divalent organic group having no single bond or a fluorine atom having 1 to 10 carbon atoms.
- R 27 and R 28 are each independently an alkylene group having 2 to 4 carbon atoms, and R 29 has 1 to 10 carbon atoms in which some of the hydrogen atoms may be substituted with substituents. It is an alkyl group.
- m is an integer from 0 to 100
- j is an integer from 0 to 100
- m + j is an integer from 4 to 100.
- R 27 and R 28 are each independently an alkylene group having 2 to 4 carbon atoms. It may be a structure. R 27 and R 28 may be the same or different. Among such R 27 and R 28 , both are independently —CH 2 CH 2 — or C 3 H 6 —, or a combination of —CH 2 CH 2 — and —C 4 H 8 —. It is preferable that both are —CH 2 CH 2 —, or a combination of —CH 2 CH 2 — and —CH 2 CH (CH 3 ) — is particularly preferable.
- m and j are each preferably an integer of 0 to 50, particularly preferably an integer of 0 to 30.
- M + j is preferably an integer of 6 to 50, particularly preferably an integer of 8 to 30.
- m + j is equal to or greater than the lower limit of the above range, ink repellency is unlikely to deteriorate when a jet rinse process using high-pressure water is performed after the development process. Furthermore, it is difficult to generate a residual film.
- m + j is less than or equal to the upper limit of the above range, the ink repellent agent (E) does not migrate to the opening during post-baking, and the ink affinity of the opening between the partition walls is sufficient. When the ink is applied, the ink is sufficiently spread in the opening.
- Formula (51) and Formula (52) show that Compound (51) and Compound (52) have m (R 27 O) units and j (R 28 O) units.
- the order of bonding of the (R 27 O) unit and the (R 28 O) unit is not particularly limited. That is, in the compound (51) and the compound (52), m (R 27 O) units and j (R 28 O) units are, for example, bonded alternately or randomly or in blocks. Also good.
- R 29 is an alkyl group having 1 to 10 carbon atoms in which some hydrogen atoms may be substituted with substituents.
- the structure of the alkyl chain may be a linear structure, a branched structure, a ring structure, a structure having a partial ring, or the like.
- Specific examples of the substituent include a carboxy group, a hydroxyl group, and an alkoxy group having 1 to 5 carbon atoms.
- R 29 in the formulas (51) and (52) is preferably a linear or unsubstituted alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group.
- (R 27 O) and (R 28 O) in formula (51) and formula (52) include —CH 2 C 6 H 10 CH 2 O— (wherein C 6 H 10 is cyclohexylene Group)), —CH 2 O—, —CH 2 CH 2 O—, —CH (CH 3 ) O—, —CH 2 CH 2 CH 2 O—, —C (CH 3 ) 2 O—, — CH (CH 2 CH 3 ) O—, —CH 2 CH 2 CH 2 CH 2 O—, —CH (CH 2 CH 2 CH 3 ) O—, —CH 2 (CH 2 ) 3 CH 2 O—, —CH (CH 2 CH (CH 3 ) 2 ) O— and the like.
- R 27 O m (R 28 O) j R 29 , (R 27 O) and (R 28 O) are both selected from the oxyalkylene groups exemplified above, and m + j is 4 to 4 A group which is an integer of 100 and R 29 is CH 3 .
- W which is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms
- R 27 O, R 28 O is represented by R 27 O, R 28 O.
- Other examples include oxyalkylene groups having 1 to 10 carbon atoms, single bonds, and the like, such as a straight chain structure, a branched structure, a ring structure, and a partial ring structure.
- Specific examples of the oxyalkylene group include CH 2 C 6 H 10 CH 2 O (where C 6 H 10 is a cyclohexylene group), CH 2 O, CH 2 CH 2 O, and CH (CH 3 ).
- W in the compounds (51) and (52) is preferably an oxyalkylene group having 2 to 4 carbon atoms from the viewpoint of availability.
- 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 preferable. More preferred.
- C 6 H 10 is a cyclohexylene group.
- C 2 H 4 , C 3 H 6 , and C 4 H 8 are either a linear structure or a branched structure.
- R 29 in the formula has the same meaning as described above, and is preferably a linear or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group or a hydrogen atom.
- a commercial item can be used as a compound (51).
- the following are mentioned as a commercial item of a compound (51).
- 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 In the following, k, m, and j in the molecular formula of each commercial product are all average values between molecules).
- BLEMMER PME-1000 (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 About 23.)
- 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 Is about 9.)
- Light ester 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd., CH 2 ⁇ CHCOO (CH 2 CH 2 O) k CH 3 : k in the formula represents an average value between molecules, and k is about 9).
- the ink repellent agent (E1) can be synthesized, for example, by the following method. First, a monomer for obtaining a desired copolymer is dissolved in a solvent and heated, and a polymerization initiator is added for copolymerization to obtain a copolymer. In the copolymerization reaction, it is preferable that a chain transfer agent is present if necessary. You may add a monomer, a polymerization initiator, a solvent, and a chain transfer agent continuously.
- 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.
- organic peroxide examples include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl- ⁇ -cumyl peroxide and the like.
- inorganic peroxide examples 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, Examples include 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like.
- a commercially available product V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) can be used as the azo polymerization initiator.
- the solvent examples include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxy Cellsolves such as ethanol 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, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobut
- chain transfer agents examples include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol; chloroform, carbon tetrachloride, tetraodor And alkyl halides such as carbon halides.
- mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol
- chloroform carbon tetrachloride
- tetraodor And alkyl halides such as carbon halides.
- an ink repellent agent (E1) which is a compound having a side chain having a group (3) or group (4) in one molecule and a side chain having an ethylenic double bond
- the above-mentioned common agent is used.
- the monomer (a1) and / or monomer (a2) and the monomer (a3) having a reactive group are copolymerized by a polymerization reaction.
- the obtained copolymer and compound (z1) are reacted.
- the solvent the solvent used in the above copolymerization reaction is used.
- Examples of the polymerization inhibitor include 2,6-di-t-butyl-p-cresol.
- a catalyst or a neutralizing agent may be added.
- a tin compound such as dibutyltin dilaurate can be used.
- a basic catalyst can be used.
- the preferable ratio of each monomer with respect to the total amount of monomers to be copolymerized is as follows.
- the proportion of monomer (a1) and / or monomer (a2) is preferably 20 to 80% by mass, particularly preferably 30 to 60% by mass.
- the proportion of the monomer (a3) is preferably 20 to 70% by mass, particularly preferably 30 to 50% by mass.
- the ink repellent agent (a4) is copolymerized with the monomers (a1) to (a3) to form an ink repellent agent ( E1) is obtained.
- the proportion of the monomer (a4) is preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass. Within this range, residual molecules that have not been immobilized in the exposure process are easily washed away from the partition walls in the development process.
- the proportion thereof is preferably 5 to 45% by mass, particularly preferably 5 to 35% by mass. Within this range, alkali solubility and developability are good.
- Monomer (a1) and / or monomer (a2): monomer (a3): monomer (a4): monomer (a5) 30 to 60% by mass: 30 to 50% by mass: 1 To 10% by mass: 9 to 35% by mass.
- the copolymer and the compound (z1) are preferably charged so that the value of the equivalent ratio of [functional group of the compound (z1)] / [reactive group of the copolymer] is 0.5 to 2. 0.8 to 1.5 is particularly preferable.
- the equivalent ratio is not less than the lower limit of the above range, the ink repellent agent (E) can be fixed to the partition walls.
- the amount is not more than the upper limit of the above range, the amount of the unreacted compound (z1) present as an impurity can be kept low, and the coating film appearance can be maintained well.
- the content of fluorine atoms in the ink repellent agent (E) is preferably 5 to 35 mass%, particularly preferably 10 to 30 mass%.
- the content is at least the lower limit of the above range, the surface tension of the partition formed from the negative photosensitive resin composition can be reduced, and a partition excellent in ink repellency can be obtained. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.
- the silicon atom content in the ink repellent agent (E) is preferably from 0.1 to 25 mass%, particularly preferably from 0.5 to 10 mass%.
- the content is equal to or higher than the lower limit of the above range, the surface tension of the partition formed from the negative photosensitive resin composition can be reduced and the ink falling property to dots (display portions) can be improved. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.
- the amount of the ethylenic double bond of the ink repellent agent (E1) is preferably 1.0 ⁇ 10 ⁇ 3 to 5.0 ⁇ 10 ⁇ 3 mol / g, and 1.5 ⁇ 10 ⁇ 3 to 3.0 ⁇ . 10 ⁇ 3 mol / g is particularly preferred. Within the above range, the fixing of the ink repellent agent (E) to the partition and the developability are good.
- the acid value thereof is preferably 100 mgKOH / g or less, particularly preferably 10 to 50 mgKOH / g. Within the above range, residual molecules that have not been immobilized in the exposure step are easily washed away from the partition walls in the development step.
- the number average molecular weight (Mn) of the ink repellent agent (E) including the ink repellent agent (E1) is preferably from 1,500 to 50,000, particularly preferably from 10,000 to 50,000.
- the mass average molecular weight (Mw) of the ink repellent agent (E) is preferably 1.2 ⁇ 10 4 to 15 ⁇ 10 4 , particularly preferably 5 ⁇ 10 4 to 15 ⁇ 10 4 .
- a fluorine-containing silane compound (hereinafter also referred to as “ink repellent agent (E2)”) may be used.
- the ink repellent agent (E2) include compounds having the aforementioned group (3) in the side chain and the main chain being an organopolysiloxane chain.
- a fluorine-containing silane compound obtained by partial hydrolytic condensation of one or more hydrolyzable silane compounds including a hydrolyzable silane compound containing a fluorine atom is preferable.
- R F a monovalent organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms
- X 1 hydrolyzable group. However, three X 1 present in the compound may be different from each other or the same.
- R H a monovalent organic group having no perfluoroalkyl group
- X 2 hydrolyzable group
- p 0, 1 or 2.
- R H and X2 may mutually differ or may be the same.
- the content of fluorine atoms in the ink repellent agent (E2) is preferably 10 to 55% by mass, more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. Within the above range, excellent ink repellency and ink repellency of UV / ozone resistance can be imparted to the partition obtained from the negative photosensitive resin composition.
- the ink repellent agent (E2) preferably has a silanol group (that is, a hydroxyl group bonded to a silicon atom).
- the number of silanol groups is preferably 0.2 to 3.5, more preferably 0.2 to 2.0, and particularly preferably 0.5 to 1.5 per silicon atom.
- the solubility of the ink repellent agent (E2) in the solvent and the compatibility with other components in the negative photosensitive resin composition are good, and workability is improved.
- it is below the upper limit of the above range evaporation of the ink repellent agent (E2) from the substrate surface can be prevented when forming the partition using the negative photosensitive resin composition.
- the number of silanol groups in the ink repellent agent (E2) is calculated from the ratio of peak areas of Si groups having silanol groups and Si groups having no silanol groups, as measured by 29 Si-NMR.
- the hydrolyzable silane compound partially hydrolyzed condensate is an oligomer (multimer) produced by hydrolyzing a polyfunctional hydrolyzable silane compound and then dehydrating and condensing it in a solvent. Of high molecular weight. A relatively low molecular weight multimer such as a dimer to tetramer of a silane compound is also a partial hydrolysis condensate in the present invention.
- the partially hydrolyzed condensate has a silanol group generated by hydrolysis of a hydrolyzable group, and may have an unreacted hydrolyzable group.
- the relatively high molecular weight partially hydrolyzed condensate mainly has silanol groups, and the relatively low molecular weight partially hydrolyzed condensates may further have hydrolyzable groups.
- the partially hydrolyzed condensate has the property of finally becoming a high molecular weight cured product that does not dissolve in the solvent as a result of further condensation or hydrolysis.
- the partial hydrolysis-condensation product may be a mixture of oligomers having different degrees of multimerization.
- the partially hydrolyzed condensate can be produced, for example, by stirring the hydrolyzable silane compound for a predetermined time under a predetermined reaction temperature condition in the presence of an acid catalyst and water.
- the degree of multimerization of the resulting partially hydrolyzed condensate can be appropriately adjusted depending on the acid concentration, reaction temperature, reaction time, and the like.
- the molar ratio indicating the ratio of the following silane compounds is the ratio of the number of silicon atoms derived from each silane compound when at least one of the following silane compounds is a partially hydrolyzed condensate. It is.
- Q 1 is a divalent organic group that connects the group (3) and the hydrolyzable silyl group (—SiX 1 3 ), and is a divalent organic group that does not contain a fluorine atom having 1 to 10 carbon atoms. is there.
- Q 1 is expressed as — (CH 2 ) i1 — (where i1 is 1 to 5) when Si is represented as the right bond and R f —CFX— is bonded to the left bond.
- the Q 1 is preferably a group represented by — (CH 2 ) i1 — (i1 is the same as above).
- i1 is preferably an integer of 2 to 4, and — (CH 2 ) 2 — in which i1 is 2 is particularly preferable.
- the above Q 1 includes — (CH 2 ) i1 —, —CH 2 O (CH 2 ) i2 —, A group represented by —SO 2 NR 1 — (CH 2 ) i3 —, — (C ⁇ O) —NR 1 — (CH 2 ) i4 — (i1 to i4 and R 1 are the same as described above) is preferable. Also in this case, — (CH 2 ) 2 — is particularly preferable.
- X 1 represents a hydrolyzable group bonded to a silicon atom.
- X 1 include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which a hydrogen atom of the amino group is substituted with an alkyl group.
- an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable, and a methoxy group, an ethoxy group, or a chlorine atom is particularly preferable.
- the group becomes a hydroxyl group (silanol group) by a hydrolysis reaction, and further, a reaction for forming a Si—O—Si bond through a condensation reaction between molecules tends to proceed smoothly.
- Specific examples of the compound (e2-1) include the following compounds. F (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 Si (OCH 2 CH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 SiCl 3 , F (CF 2) 6 CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 6 CH 2 CH 2 Si (OCH 2 CH 3) 3, F (CF 2) 6 CH 2 CH 2 SiCl 3, F ( CF 2) 8 CH 2 CH 2 Si (OCH 3) 3.
- compound (e2-1) among others, F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 Si (OCH 2 CH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 SiCl 3 , F (CF 2) 3 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3 are particularly preferred.
- compound (e2-1) may be used alone or in combination of two or more.
- the mixture of hydrolyzable silane compounds may contain a partial hydrolysis condensate of compound (e2-1). However, the compound (e2-1) alone is preferable to the partial hydrolysis-condensation product.
- R H is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- RH other than alkyl groups include alkenyl groups such as vinyl groups and allyl groups, and hydrocarbon groups having rings such as phenyl groups and cycloalkyl groups.
- X 2 is a hydrolyzable group, and is the same as X 1 in the above formula (e2-1), including preferred embodiments. p is 0, 1 or 2. However, when R is 2, two R H1 and (4-p) X 2 may be different from each other or the same.
- the compound (e2-2) is preferably a tetrafunctional compound in which p is 0 or a trifunctional compound in which p is 1.
- the ink repellent (E2) water repellency is expressed by the compound (E2-1) from the group (3) and the compound (E2-2) from the R H, oil repellency is expressed primarily by group (3)
- the ratio of the group (3) to the total of the groups (3) and RH in the ink repellent agent (E2) Is preferably high.
- the ratio of the group (3) in the ink repellent agent (E2) is increased, the oil repellency is improved, and the film forming property is excellent.
- the ink repellent agent (E2) is easily dissolved in a hydrocarbon solvent, and a coating film of a negative photosensitive resin composition is formed on the surface of the substrate.
- a relatively inexpensive solvent can be selected.
- the following compounds are preferred. Further, a partially hydrolyzed condensate of compound (e2-2) can be used in place of compound (e2-2).
- the partial hydrolysis-condensation product is preferably a relatively low molecular weight compound. Specific examples of the compound (e2-2) include the following compounds.
- Si (OCH 3 ) 4 Si (OCH 2 CH 3 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OCH 2 CH 3 ) 3 , CH 3 CH 2 Si (OCH 3 ) 3 , CH 3 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 , partial hydrolysis condensate of Si (OCH 3 ) 4 (for example, , Methyl silicate 51 (trade name) manufactured by Colcoat, Inc., and a partial hydrolysis condensate of Si (OCH 2 CH 3 ) 4 (for example, ethyl silicate 40 and ethyl silicate 48 (trade name) manufactured by Colcoat).
- Si (OCH 3 ) 4 for example, Methyl silicate 51 (trade name) manufactured by Colcoat, Inc.
- compound (e2-2) may be used alone or in combination of two or more.
- a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
- the content of the compound (e2-2) in the hydrolyzable silane compound mixture is preferably 0.1 to 9 mol of the compound (e2-2) with respect to 1 mol of the compound (e2-1). ⁇ 9 mol is particularly preferred.
- a hydrolyzable silane compound other than the compound (e2-1) and the compound (e2-2) (hereinafter also referred to as “compound (e2-3)”) or a partial hydrolysis condensate of the compound (e2-3) May be included.
- the compound (e2-3) is a bifunctional or trifunctional silane compound having a hydrolyzable group and is a compound that co-condenses with the compound (e2-1) and the compound (e2-2).
- a well-known silane compound can be used.
- the compound (e2-3) is a silane compound having a structure having a hydrocarbon group substituted with a hydrocarbon group having 7 or more carbon atoms or a reactive group in place of RH in the formula (e2-2). Preferably there is. However, when p in formula (E2-2) is 2, one of the two R H may be R H.
- a (meth) acryloyloxy group, an amino group, a hydrocarbon-substituted amino group, an epoxy group, and the like are preferable.
- a reactive group having an ethylenic double bond such as a (meth) acryloyloxy group is preferred.
- a preferred compound (e2-3) is a hydrolyzable silane compound having a reactive group having an ethylenic double bond, and a trialkoxysilane or dialkoxysilane having a (meth) acryloyloxy group-substituted alkyl group is particularly preferred.
- an ink repellent agent (E2) having an ethylenic double bond can be obtained.
- particularly preferred compound (e2-3) include the following compounds.
- CH 2 C (CH 3) COO (CH 2) 3 Si (OCH 3) 3
- CH 2 C (CH 3) COO (CH 2) 3 Si (OCH 2 CH 3) 3
- CH 2 CHCOO (CH 2) 3 Si (OCH 3) 3
- CH 2 CHCOO (CH 2) 3 Si (OCH 2 CH 3) 3
- [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 3) 2
- [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 3) 2
- [CH 2 C (CH 3 ) COO (CH 2) 3] CH 3 Si (OCH 2 CH 3) 2
- C 6 H 5) NH ( CH 2) 3 Si (OCH 3) 3.
- compound (e2-3) may be used alone or in combination of two or more.
- the compounding amount of the compound (e2-3) in the mixture of the hydrolyzable silane compound of the present invention is 5 mol or less with respect to 1 mol of the total amount of the compound (e2-1) and the compound (e2-2). It is preferably 4 mol or less.
- a monofunctional silane compound can be blended with the hydrolyzable silane compound as the hydrolyzable silane compound.
- the monofunctional silane compound functions as a molecular weight regulator when hydrolyzing and condensing the hydrolyzable silane compound mixture into a partially hydrolyzed condensate. That is, it is used for the purpose of producing a partially hydrolyzed condensate having a relatively low molecular weight or for the purpose of preventing the partially hydrolyzed condensate from becoming too high in molecular weight and becoming insoluble in a solvent. It is preferable to appropriately adjust the amount used depending on the molecular weight of the target partial hydrolysis-condensation product.
- a compound having a structure where p is 3 or hexaalkyldisiloxane in the formula (e2-2) is preferable.
- the alkyl group in these compounds preferably has 4 or less carbon atoms, and more preferably a methyl group or an ethyl group.
- the partial hydrolysis-condensation product produced using the compound (e2-1) and the compound (e2-2) has a structure having an average composition formula represented by the following formula (e4).
- the average composition formula represented by the formula (e4) is such that all hydrolyzable groups or silanol groups are completely hydrolyzed and condensed to form siloxane bonds. Is the chemical formula.
- R F , R H , Q 1 and p are the same as those described above.
- s and t are the average number of moles of each unit in a plurality of partial hydrolysis-condensation products having different degrees of polymerization.
- the units derived from the compound (e2-1) and the compound (e2-2) are arranged randomly. Guessed.
- the s / t (molar ratio) in the average composition formula (e4) when using the compound (e2-1) and the compound (e2-2) is the hydrolysis value as the average value of the entire ink repellent agent (E2).
- the content of the compound (e2-2) with respect to the compound (e2-1) in the silane compound mixture is preferably in the above-mentioned range, that is, 10/1 to 90 (molar ratio), particularly 10/5 to 90 (molar ratio). preferable.
- the formula (e4) is derived from the compound (e2-3).
- the unit has a structure of an average composition formula further co-condensed.
- Compound (e2) a partial hydrolysis-condensation product of a mixture of the following silane compounds is preferable.
- Compound (e2-1) At least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane.
- Compound (e2-2) tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane.
- Compound (e2-1) At least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane.
- Monofunctional silane compound hexamethyldisiloxane or trimethylmethoxysilane (combination 3)
- Compound (e2-1) At least one selected from 2- (perfluorohexyl) ethyltrimethoxysilane and 2- (perfluorobutyl) ethyltrimethoxysilane.
- Compound (e2-2) tetraethoxysilane or tetraethoxysilane and methyltriethoxysilane.
- the ink-repellent agent (E2) in the negative photosensitive resin composition of the present invention has excellent ink repellency even when it is exposed to ultraviolet rays / ozone by further condensing silanol groups in the process of exposure and curing. It is considered to form a partition wall showing
- the number average molecular weight (Mn) of the ink repellent agent (E2) in the negative photosensitive resin composition of the present invention is preferably 500 or more, preferably less than 1,000,000, and particularly preferably less than 10,000.
- the number average molecular weight (Mn) is not less than the lower limit of the above range, detachment from the substrate surface can be prevented when the partition is formed using the negative photosensitive resin composition.
- the number average molecular weight (Mn) is less than the upper limit of the above range, the solubility in a solvent is good and the workability is excellent.
- the number average molecular weight (Mn) of the ink repellent agent (E2) can be adjusted by selecting reaction conditions and the like.
- the ink repellent agent (E2) in the negative photosensitive resin composition of the present invention is produced by hydrolyzing and partially condensing the above-mentioned mixture of hydrolyzable silane compounds (hereinafter also referred to as “reaction process”). It can.
- hydrolysis and partial condensation are reactions in which a silanol group is generated by a hydrolysis reaction of a hydrolyzable group and a siloxane bond is generated by a dehydration condensation reaction between silanol groups.
- the reaction conditions usually used for the reaction of hydrolyzing and condensing the hydrolyzable silane compound can be applied without particular limitation. For example, water, a catalyst, an organic solvent, etc. can be used.
- the amount thereof is preferably 25 to 9,900 parts by weight, particularly preferably 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.
- the ink repellent agent (E2) can be produced by hydrolyzing and condensing a mixture containing the hydrolyzable silane compound described above.
- the reaction it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acid such as acetic acid, oxalic acid and maleic acid as a catalyst, and hydrochloric acid, sulfuric acid and nitric acid are particularly preferable.
- the amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass, based on the total amount of the mixture containing the hydrolyzable silane compound.
- a solvent may be used for the reaction.
- the solvent an organic solvent is preferable, and as the organic solvent, a solvent that can be used in the synthesis of the ink repellent agent (E1) described above can be used.
- An organic solvent may be used individually by 1 type, or may use 2 or more types together.
- the amount of the organic solvent is preferably from 25 to 9,900 parts by weight, particularly preferably from 100 to 1,900 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound mixture.
- the resulting partially hydrolyzed condensate is blended into the negative photosensitive resin composition together with the solvent used in the reaction step. Therefore, it is preferable to use a solvent that stabilizes the silanol group in the ink repellent agent (E2) as the solvent used in the reaction step.
- a solvent that stabilizes the silanol group include compounds having a hydroxyl group and a relative dielectric constant ( ⁇ ) at 25 ° C. in the range of 5 to 20.
- glycol monoalkyl ether acetate solvents having 2 to 8 carbon atoms examples include glycol monoalkyl ether acetate solvents having 2 to 8 carbon atoms, glycol monoalkyl ether solvents, glyme solvents, hydrocarbon alcohols having 2 to 4 carbon atoms, and the like. More specifically, propylene glycol monomethyl ether acetate ( ⁇ : 8.3) as a glycol-based monoalkyl ether acetate solvent, propylene glycol monomethyl ether ( ⁇ : 12.3) as a glycol-based monoalkyl ether solvent, carbonization
- the hydrogen alcohol examples include 2-propanol ( ⁇ : 19.92). Propylene glycol monomethyl ether is particularly preferred because of its high silanol group stabilizing effect.
- the reaction step is preferably performed at a temperature from room temperature to the boiling point of the solvent under suitable stirring conditions.
- the reaction time may be about 0.5 to 24 hours, preferably 1 to 10 hours, depending on the amount of raw material components used, reaction temperature, stirring conditions and the like.
- the obtained ink repellent agent (E2) can be added to the negative photosensitive resin composition of the present invention without removing the organic solvent. After removing the organic solvent by a usual method, the ink repellent agent (E2) may be isolated and then added to the negative photosensitive resin composition.
- the content ratio of the ink repellent agent (E) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass.
- the content ratio is at least the lower limit of the above range, the surface tension of the partition formed from the negative photosensitive resin composition can be reduced, and a partition excellent in ink repellency can be obtained. Adhesiveness of a partition and a base material becomes it favorable that it is below the upper limit of the said range.
- the negative photosensitive resin composition in the present invention usually contains a solvent (F).
- a solvent (F) When the negative photosensitive resin composition contains a solvent (F), the viscosity of the negative photosensitive resin composition is reduced, so that the negative photosensitive resin composition can be easily applied onto a substrate. Therefore, a uniform coating film of the negative photosensitive resin composition can be formed.
- a negative photosensitive resin composition does not contain a solvent (F)
- the coating film of a negative photosensitive resin composition becomes the same as the film
- the solvent (F) includes the alkali-soluble resin (A), the black organic pigment (B), the photopolymerization initiator (C), and a crosslinking agent (D) blended as necessary, which the negative photosensitive resin composition contains. ), An ink repellent agent (E), a thermosetting agent (I) described later, and other optional components are uniformly dissolved or dispersed to obtain an appropriate viscosity, and a negative photosensitive resin composition for a substrate on which partition walls are formed. There is no particular limitation as long as it has a function of uniformly and easily applying the product and does not have reactivity with these components.
- the solvent (F) for example, a solvent that can be used in the synthesis of the ink repellent agent (E1) or (E2) described above can be used.
- Other examples include chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, xylene and benzyl alcohol; water and the like. These may be used alone or in combination of two or more. From these various organic solvents, a solvent having the required performance is appropriately selected depending on the type of the negative photosensitive resin composition, the coating method on the substrate, and the like, and used as the solvent (F).
- the solvent (F) evaporates in the drying step of the coating film of the composition.
- the solvent (F) used in the negative photosensitive resin composition containing the ink repellent agent (E) for example, the solubility parameters of the ink repellent agent (E) to be used and Fedor are close, and the boiling point is relatively high. And a solvent having a boiling point of 165 ° C. or higher.
- R 51 represents an alkyl group having 1 to 10 carbon atoms
- R 52 represents an alkyl group having 2 to 10 carbon atoms
- s represents an integer of 1 to 10.
- Examples of the compound (5) include diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol ethyl isopropyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether and the like.
- diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol isopropyl methyl ether are preferable, and diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether are particularly preferable.
- the content of the solvent (F) in the negative photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass.
- the negative photosensitive resin composition in the present invention may contain fine particles (G) as necessary.
- the partition obtained from the negative photosensitive resin composition becomes a partition excellent in heat resistance in which thermal sagging is prevented.
- the fine particles (G) various inorganic and organic fine particles can be used, and those in which the basic polymer dispersant is negatively charged from the viewpoint of adsorption ability are preferably used.
- inorganic materials include silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO).
- organic system examples include polyethylene and polymethyl methacrylate (PMMA).
- PMMA polymethyl methacrylate
- the fine particles (G) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).
- the particle diameter of the fine particles (G) is preferably 1 ⁇ m or less, and particularly preferably 200 nm or less, because the surface smoothness of the partition walls is improved.
- the content ratio of fine particles (G) in the total solid content in the negative photosensitive resin composition is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and particularly preferably 7 to 10% by mass.
- the content ratio is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency due to post-baking, and when it is not more than the upper limit of the above range, the stability of the liquid of the negative photosensitive resin composition is good. become.
- the negative photosensitive resin composition in the present invention may contain a silane coupling agent (H) as necessary.
- a silane coupling agent (H) As necessary.
- the substrate adhesion of the cured film formed from the negative photosensitive resin composition can be improved.
- Specific examples of the silane coupling agent (H) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl.
- trimethoxysilane 3-mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and imidazolesilane. These may be used alone or in combination of two or more.
- the content ratio of the silane coupling agent (H) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
- the content ratio of the silane coupling agent (H) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
- the negative photosensitive resin composition in this invention may contain the thermosetting agent (I) as needed.
- the thermosetting agent (I) includes an amino resin, a compound having two or more epoxy groups, a compound having two or more hydrazino groups, a polycarbodiimide compound, a compound having two or more oxazoline groups, two or more Examples thereof include compounds having an aziridine group, polyvalent metals, compounds having two or more mercapto groups, and polyisocyanate compounds.
- an amino resin, a compound having two or more epoxy groups, and a compound having two or more oxazoline groups are particularly preferable from the viewpoint of improving chemical resistance of the formed partition wall.
- the content of the thermosetting agent (I) in the total solid content in the negative photosensitive resin composition is preferably 1 to 50% by mass, particularly preferably 1 to 30% by mass. Within the above range, the developability of the obtained negative photosensitive resin composition becomes good.
- the negative photosensitive resin composition in this invention may contain the phosphoric acid compound (J) as needed. Adhesiveness with a base material can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (J).
- the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
- the content ratio of the phosphoric acid compound (J) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 10% by mass, particularly preferably 0.3 to 1% by mass. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.
- the negative photosensitive resin composition in the present invention may contain a surfactant (K) as necessary.
- the thickness of the cured film becomes uniform.
- the ink repellent agent (E) described above also usually has an action as a surfactant.
- a negative photosensitive resin composition for forming a partition for an optical element that forms a pixel by a method other than the ink jet method usually does not contain an ink repellent, and therefore, a surfactant is preferably used.
- the surfactant (K) the same polymer as the ink repellent agent (E) may be used, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and an acrylic surfactant.
- the surfactant (K) a commercially available product may be used.
- BYK-Japan Japan BYK-306 (polyether-modified polydimethylsiloxane: 12% by mass, xylene: 68% by mass, monophenyl glycol: 20% by mass), BYK-307 (polyether-modified poly Dimethylsiloxane), BYK-323 (aralkyl-modified polymethylalkylsiloxane), BYK-320 (polyether-modified polymethylalkylsiloxane: 52 mass%, white spirit: 43 mass%, PGMEA: 5 mass%), BYK-350 ( Acrylic copolymer) and the like.
- the content ratio of the surfactant (K) in the total solid content in the negative photosensitive resin composition is preferably 0.01 to 30% by mass, particularly preferably 0.05 to 20% by mass. When the thickness is in the above range, the film thickness of the obtained negative photosensitive resin composition becomes uniform.
- the negative photosensitive resin composition in the present invention can further use a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like, if necessary. .
- the negative photosensitive resin composition of the present invention comprises an alkali-soluble resin (A) containing an alkali-soluble resin (A1) and an alkali-soluble resin (A2), a black organic pigment (B), and a photopolymerization initiator (C). Containing. Furthermore, a crosslinking agent (D), an ink repellent agent (E), and a solvent (F) are contained as needed. Furthermore, you may contain said fine particle (G), a thermosetting agent (I), a silane coupling agent (H), a phosphoric acid compound (J), surfactant (K), and another additive.
- the solid acid value of the negative photosensitive resin composition of the present invention is 10 to 50 mgKOH / g, preferably 20 to 45 mgKOH / g, and particularly preferably 34 to 45 mgKOH / g.
- the solid content acid value is at least the lower limit of the above range, the dispersibility of the black organic pigment (B) in the alkaline developer is good, and aggregation and sedimentation are difficult. Therefore, clogging of the filter does not occur when the alkaline developer is recycled, which can contribute to improvement of productivity.
- the amount is not more than the upper limit of the above range, the solubility of the unexposed portion of the film obtained using the negative photosensitive resin composition in the alkaline developer is good, and the pattern formation is good.
- Adjustment of the solid content acid value of the negative photosensitive resin composition is carried out by adjusting the acid value and blending amount of the components constituting the solid content of the above blended components, that is, the components excluding the solvent (F). Is called.
- the compounding amount of each component in the negative photosensitive resin composition has a preferable range as described above for each component from the viewpoint other than the acid value depending on the function of each component, the acid value within the range of the compounding amount. Is required to be adjusted.
- the solid content acid value of the negative photosensitive resin composition is within the above range by the alkali-soluble resin (A) whose blending amount is relatively large compared to other components and the acid value can be easily adjusted. It is adjusting.
- the alkali-soluble resin (A) having an acid value of 100 mgKOH / g is added to 10 to 10 to the total solid content of the negative photosensitive resin composition.
- the solid content acid value of the negative photosensitive resin composition of the present invention can be adjusted to 10 to 50 mgKOH / g.
- the negative photosensitive resin composition is used as a material for photolithography or the like, as in the case of a normal negative photosensitive resin composition.
- the obtained cured film can be used as a member of an optical element in which a cured film of a normal negative photosensitive resin composition is used.
- the negative photosensitive resin composition of the present invention it is preferable to select a composition and a blending ratio in accordance with applications and required characteristics.
- the preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.
- Alkali-soluble resin (A) It consists only of the following alkali-soluble resin (A1) and alkali-soluble resin (A2), and the mass-average molecular weight of either the alkali-soluble resin (A1) or the alkali-soluble resin (A2) is 10,000.
- Alkali-soluble resin (A1) resin in which acidic group and ethylenic double bond are introduced into bisphenol A type epoxy resin, resin in which acidic group and ethylenic double bond are introduced into bisphenol F type epoxy resin, phenol novolac Resin with acidic group and ethylenic double bond introduced into type epoxy resin, Resin with acidic group and ethylenic double bond introduced into cresol novolac type epoxy resin, Acid group and ethylenic type into trisphenolmethane type epoxy resin At least selected from the group consisting of a resin having a double bond introduced therein and a resin having an acidic group and an ethylenic double bond introduced into the epoxy resins represented by the above formulas (A1-2a) to (A1-2c).
- One resin 85 to 97% by mass with respect to the total amount of the alkali-soluble resin (A), the alkali-soluble resin (A2): Chain without containing an aromatic ring, and at least one resin selected from resins having an acidic group in the molecule, 3 to 15 wt% with respect to the total weight of the alkali-soluble resin (A)),
- Solvent (F) consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monopropyl ether, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, ⁇ -butyrolactone, and cyclohexanone At least one solvent selected from the group consisting of 50 to 99% by mass in the negative photosensitive resin composition;
- the alkali-soluble resin (A), the black organic pigment (B), the photopolymerization initiator (C) and the solvent (F) are the same as in the combination 1, and further, the crosslinking agent (D) and / or the ink repellent agent (E). Is blended as follows.
- the partition of this invention is a partition formed in order to provide a division on the substrate surface, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention.
- the partition wall of the present invention is suitably used for an optical element, and since the negative photosensitive resin composition contains a black colorant (B), the partition wall obtained has a plurality of substrate surfaces on the substrate surface.
- the present invention can be applied to a black matrix formed so as to be partitioned into compartments.
- the partition of the present invention is applied to, for example, a black matrix for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate.
- partition walls can be formed on fine lines close to the mask pattern, and at the same time, if contact holes are required on the partition walls, minute contact holes can be formed. It is. Furthermore, when the negative photosensitive resin composition contains the ink repellent agent (E), sufficient ink repellency can be imparted at the same time.
- the method for producing the partition for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.
- the negative photosensitive resin composition of the present invention is applied to the substrate surface to form a coating film (coating film forming process), and then the coating film is dried to form a film (drying process). Only the part which becomes the partition of the film is exposed and photocured (exposure process), and then the coating film other than the photocured part is removed to form the partition consisting of the photocured part of the coating (development). Step), and then, if necessary, the partition wall formed above is further thermally cured (post-baking step), whereby the partition wall for the optical element of the present invention can be produced. Moreover, you may put further the photocuring (post exposure process) of the said formed partition etc. between a image development process and a post-baking process.
- the material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc.
- Thermosetting plastic sheet such as epoxy resin, cured sheet of thermosetting resin such as unsaturated polyester, and the like can be used.
- a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.
- a post exposure may be performed from the back surface (board
- the partition walls are formed on the TFT array substrate in the form of a black matrix, such as a BOA type color filter, it is only necessary to prepare a substrate in which a predetermined member such as a TFT array is formed on the substrate surface in advance. .
- the coating method is not particularly limited as long as a coating film having a uniform film thickness is formed. Usually, spin coating, spraying, slit coating, roll coating, spin coating, bar coating, etc. The method used for the coating film formation of this is mentioned.
- the film thickness of the coating film is determined in consideration of the height of the partition wall finally obtained and the solid content concentration of the negative photosensitive resin composition.
- the film thickness of the coating film is preferably 500 to 2,000%, particularly preferably 550 to 1,000% of the height of the partition wall finally obtained.
- the thickness of the coating film is preferably from 0.3 to 100 ⁇ m, particularly preferably from 1 to 50 ⁇ m.
- the coating film formed on the substrate surface in the coating film forming step is dried to obtain a film.
- the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained.
- this ink repellent agent (E) transfers to the coating-film surface vicinity.
- pre-baking it is more preferable to use vacuum drying and heat drying together in order to efficiently dry the coating film without causing unevenness of the coating film appearance.
- the vacuum drying conditions vary depending on the type of each component, the blending ratio, and the like, but it is preferable to perform the drying at 10 to 500 Pa for 10 to 300 seconds. Heat drying is preferably performed at 50 to 120 ° C. for 10 to 2,000 seconds with a heating device such as a hot plate or oven together with the substrate.
- the negative photosensitive resin composition in the exposed portion is cured, and the negative photosensitive resin composition in the unexposed portion is not cured.
- the irradiation light include excimer lasers such as 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, X-ray, electron beam Etc.
- Light having a wavelength of 100 to 600 nm is preferable, electromagnetic waves having a distribution in the wavelength range of 300 to 500 nm are more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.
- a known ultra-high pressure mercury lamp or the like can be used as the irradiation device.
- Exposure is preferably 5 ⁇ 1,000mJ / cm 2, particularly preferably 50 ⁇ 400mJ / cm 2.
- the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition is sufficiently cured. A high resolution is obtained when it is not more than the upper limit of the above range.
- Development is performed with a developer, and the film of the negative photosensitive resin composition in the unexposed portion is removed.
- the alkali developer an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts can be used.
- an organic solvent such as a surfactant or alcohol can be added to the alkaline developer in order to improve solubility and remove residues.
- the development time time for contact with the developer
- Examples of the developing method include a liquid piling method, a dipping method, and a shower method.
- the solid component has the above characteristics so that the black organic pigment (B) contained in the composition has good dispersibility even in an alkaline developer.
- the filter is not clogged due to aggregation or sedimentation of the black organic pigment (B), and can contribute to improvement in productivity.
- post exposure process Next, you may perform post exposure as needed.
- the post-exposure may be performed from either the front surface where the partition walls are formed or the back surface (substrate side) where the partition walls are not formed. Moreover, you may expose from both front and back.
- Preferred exposure is at 50 mJ / cm 2 or more, 200 mJ / cm 2 or more, and more preferably 1,000 mJ / cm 2 or more, 2,000 mJ / cm 2 or more is particularly preferable.
- ultraviolet rays are preferable, and as the light source, a known ultra-high pressure mercury lamp or high-pressure mercury lamp can be used. These light sources are preferably used because they emit light of 600 nm or less that contributes to hardening of the partition walls, and emit less light 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 mercury lamp has an optical filter function for cutting light of 200 nm or less.
- a low pressure mercury lamp can also be used as the light source.
- a low-pressure mercury lamp has a high emission intensity at a wavelength of 200 nm or less, and oxidative decomposition of the partition walls is likely to occur due to the generation of ozone.
- the exposure amount is preferably 500 mJ / cm 2 or less, particularly preferably 300 mJ / cm 2 or less.
- the partition wall By performing heat treatment for 5 to 90 minutes with a heating device such as a hot plate or an oven, a pattern composed of partition walls and regions (dots) divided by the partition walls is formed.
- the heating temperature is preferably 150 to 250 ° C, particularly preferably 180 to 250 ° C.
- the partition walls are sufficiently cured, sufficient chemical resistance is obtained, and is included in the ink when the ink is applied during the subsequent pixel formation.
- the partition wall does not swell or the ink does not ooze due to the solvent.
- thermal decomposition of the partition wall is difficult to occur.
- the pattern formed from the negative photosensitive resin composition of the present invention preferably has an average partition wall width of 100 ⁇ m or less, particularly preferably 20 ⁇ m or less.
- the average distance between adjacent partition walls is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
- the average height of the partition walls is preferably 0.05 to 50 ⁇ m, and particularly preferably 0.2 to 10 ⁇ m.
- the partition wall of the present invention When the partition wall of the present invention is applied in the form of a black matrix to a so-called BOA type color filter in which a color filter is disposed on a TFT array substrate, for example, in order to connect a switching element such as a TFT and a pixel electrode, It is necessary to form a through hole penetrating the partition wall in the film thickness direction as a contact hole.
- the contact hole is formed by forming a mask having a predetermined pattern used in the above exposure process into a pattern capable of forming a contact hole.
- the size of the contact hole depends on the type and design of the optical element to be used, but if the negative photosensitive resin composition of the present invention is used, the major axis of the cross section having the maximum horizontal cross-sectional area in the through hole serving as the contact hole, that is, A minute contact hole having a maximum hole diameter of 20 ⁇ m or less can be formed. Therefore, the partition wall of the present invention is suitable as a partition wall for an optical element that requires such a minute contact hole.
- the minimum horizontal hole diameter in the through hole is preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
- the maximum hole diameter in the horizontal direction of the through hole is preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
- the partition of this invention can be utilized for optical elements, such as a color filter, and an organic EL element.
- the partition wall can be formed in a fine line pattern close to the mask pattern to be used, and at the same time, a minute contact hole can be formed in the fine partition wall
- the partition wall of the present invention is a black matrix. And is suitably used for a BOA type color filter. Since the color filter of the present invention employs a black matrix in the form of partition walls in which minute contact holes are formed in a minute line pattern, low power consumption can be achieved by forming this color filter on a TFT array substrate. A liquid crystal display device having high brightness can be obtained.
- the ink used for the photolithography method mainly includes a coloring component, an initiator, a binder resin component, and a solvent.
- a coloring component it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
- 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 and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
- the oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
- pixels can be formed in the region divided by the partition walls by injecting ink using an inkjet apparatus by an inkjet method.
- the color filter of the present invention is formed on the surface of the TFT array substrate, as described above, a substrate having a TFT array previously formed on the substrate is used, and the above-described color filter according to the present invention is formed at a predetermined position on the substrate surface.
- the partition wall surface on the substrate is coated with the ink made of the transparent colored photosensitive resin composition by the same method (photolithography method) as the partition wall. Pixels are formed so as to be positioned between them, and a color filter is manufactured.
- a pixel may be formed by injecting ink into an area partitioned by a partition wall on the base material by an ink jet method.
- the substrate surface exposed in the dots before injecting ink into the regions (dots) partitioned by the partition walls may be performed by a method such as a cleaning process using an alkaline aqueous solution, a UV cleaning process, a UV ozone cleaning process, an excimer cleaning process, a corona discharge process, or an oxygen plasma process.
- the ink jet device is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, a method in which ink is intermittently ejected using a piezoelectric element, an ink is heated, An apparatus using various methods such as a method of intermittent injection using foaming can be used.
- the pixel shape may be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.
- the partition wall is at a predetermined position set in consideration of the shape of the pixel and the positional relationship of the TFT array on the surface of the TFT array substrate. It is formed in a predetermined shape.
- the ink used for the ink jet method mainly includes a coloring component, a binder resin component, and a solvent.
- a coloring component it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
- 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 and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
- the oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
- the ink jet method after ink is injected into the dots by the ink jet device, the ink layer formed in the dots is subjected to treatment such as drying, heat curing, and ultraviolet curing as necessary. Pixels are formed.
- a protective film layer is formed as necessary.
- the protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer.
- a transparent electrode such as tin-doped indium tin oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary.
- a composition containing no ink repellent (E) is used as the negative photosensitive resin composition
- a hole injection layer is formed as necessary by vapor deposition. If necessary, a hole transport layer, a light emitting layer, a hole blocking layer if necessary, an electron transport layer if necessary, an electron injection layer if necessary, and the like are formed. Then, the pixel of an organic EL element is obtained by forming electrodes, such as aluminum, by a vapor deposition method etc.
- a hole injection layer is necessary if necessary by an inkjet method.
- a hole transport layer, a light emitting layer, a hole blocking layer as necessary, an electron transport layer as necessary, and an electron injection layer as necessary are formed.
- the pixel of an organic EL element is obtained by forming electrodes, such as aluminum, by a vapor deposition method etc.
- Examples 1 to 13 and 17 to 19 are examples, and examples 14 to 16 are comparative examples.
- ZCR1642 Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a) (trade name: ZCR-1642H, manufactured by Nippon Kayaku Co., Ltd., mass average molecular weight) (Mw): 5,800, solid content acid value: 100 mgKOH / g, solid content: 70% by mass, PGMEA: 30% by mass).
- ZFR1492 resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a bisphenol F skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name: ZFR-1492H, mass average molecular weight (Mw): 23,000, solid content Acid value: 100 mgKOH / g, solid content: 65% by mass, PGMEA: 35% by mass).
- CCR1159 Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a cresol novolak skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name: CCR-1159H, mass average molecular weight (Mw): 7,400, solid content Acid value: 100 mgKOH / g, solid content: 65% by mass, PGMEA: 35% by mass).
- EA7440 Resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a cresol novolak skeleton (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: EA-7440, mass average molecular weight (Mw): 4,000, solid (Partial acid value: 40.5 mg KOH / g, solid content: 60% by mass, PGMEA: 40% by mass).
- Alkali-soluble resin (A2)) UC3080 A resin obtained by copolymerization of styrene and acrylic acid in a molar ratio of styrene: acrylic acid in a ratio of 62:38 (manufactured by Toa Gosei Co., Ltd., trade name: UC-3080, mass average molecular weight (Mw): 14,000, acid Value: 230 mg KOH / g, solid content: 100% by mass).
- UC3900 a resin obtained by copolymerizing styrene and acrylic acid at a molar ratio of styrene: acrylic acid of 81:19 (manufactured by Toa Gosei Co., Ltd., trade name: UC-3900, mass average molecular weight (Mw): 4,600, acid Value: 108 mgKOH / g, solid content: 100% by mass).
- MSP9612 resin obtained by copolymerization of N-phenylmaleimide, benzylmethacrylate, methacrylic acid and styrene (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: MSP-9612, mass average molecular weight (Mw): 26,000, solid content acid value: 32 mgKOH / G, solid content: 30% by mass, PGMEA: 70% by mass).
- MSP9610 resin obtained by copolymerization of N-phenylmaleimide, benzyl methacrylate, methacrylic acid, and styrene (made by Shin-Nakamura Chemical Co., Ltd., trade name: MSP-9610, mass average molecular weight (Mw): 28,000, solid content acid value: 75 mgKOH / G, solid content: 30% by mass, PGMEA: 70% by mass).
- S2961 PGMEA dispersion of black organic pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: S2961, azomethine black organic pigment: 12% by mass, polymer dispersant: 7.2% by mass, PGMEA: 80.8% by mass Solid acid value: 7.2 mg KOH / g).
- MEK 2-butanone.
- MAA Methacrylic acid (corresponding to monomer (a4)).
- 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 represents an average value between molecules, and the value of k is about 9) (corresponding to the monomer (a5) compound (51)).
- 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 (It corresponds to the compound (51) of the monomer (a5).).
- 2-HEMA 2-hydroxyethyl methacrylate (corresponds to monomer (a3)).
- V-65 Azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65).
- AOI 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz AOI) (corresponds to compound (z1)).
- DBTDL Dibutyltin dilaurate.
- BHT 2,6-di-t-butyl-p-cresol.
- Compound used for synthesis of ink repellent agent (E2) Compound (e2-1-1): F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 (manufactured by Asahi Glass Co., Ltd.).
- the obtained crude copolymer solution was added to hexane for reprecipitation purification, and then vacuum-dried to obtain copolymer 1 (242 g).
- the copolymer 1 had a number average molecular weight (Mn) of 35,000 and a mass average molecular weight (Mw) of 91,000.
- Infrared spectroscopic analysis of the ink repellent agent (E1-1) revealed that the absorption band (1,635 cm ⁇ 1 ) derived from the C ⁇ C stretching vibration of the acryloyl group and the CH 2 in- plane bending vibration of the acryloyl group.
- absorption band derived from (1,409cm -1) and the absorption band derived from the CH 2 side outer bending vibration of an acryloyl group (810 cm -1) is present, also the absorption band derived from the NCO stretching vibration of AOI ( 2,274 cm ⁇ 1 ) had disappeared, confirming the presence of an acryloyl group in the ink repellent agent (E1-1).
- An ink repellent solution (E1-21) prepared by mixing the ink repellent agent (E1-2) obtained above and PGMEA at a mass ratio of 1: 9 was prepared and used in the following examples.
- the mass average molecular weight (Mw), number average molecular weight (Mn), and fluorine atom content of the obtained ink repellent agent (E2-1) are shown together with the charged composition (mol%) of the ink repellent agent (E2-1). It is shown in 2.
- the mixture was stirred at 40 ° C. for 5 hours to change the ink repellent agent (E2-2) into a PGME solution (concentration of ink repellent agent (E2-2): 10% by mass; hereinafter referred to as “(E2-2) liquid”). .).
- the components in the reaction solution were measured using gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit.
- the mass average molecular weight (Mw), number average molecular weight (Mn), and fluorine atom content of the obtained ink repellent agent (E2-2) are shown together with the charged composition (mol%) of the ink repellent agent (E2-2). It is shown in 2.
- Examples 1 to 19 Preparation of negative photosensitive resin composition, formation and evaluation of partition walls] Alkali-soluble resin (A1) (containing 30 to 40% by mass of PGMEA as a solvent), alkali-soluble resin (A2) (containing 0 to 70% by mass of PGMEA as a solvent) at the ratios shown in Table 3 and Table 4.
- Black organic pigment (B) (containing 80.5 to 80.8% by mass of PGMEA as a solvent), photopolymerization initiator (C1), photopolymerization initiator (C2), crosslinking agent (D) (PGGMA as a solvent 20 mass%), ink repellent agent (E) (90 mass% of PGMEA or PGME as a solvent), solvent (F) and surfactant (K) are separable at room temperature and equipped with a stirrer. It mix
- Type photosensitive resin composition was applied to form a coating film (coating film forming step). Next, it was dried on a hot plate at 100 ° C. for 2 minutes to obtain a glass substrate (1) having a film thickness of 3 ⁇ m (drying step). In addition, about the glass substrate (1), several sheets for optical density and developability evaluation and the following pattern formation were manufactured.
- the ultra-high pressure mercury lamp (Dainippon) Using an instrument made by Kaken Co., Ltd., apparatus name: MA-1200, an exposure dose of 50 mJ / cm 2 was irradiated on the basis of i-line (365 nm) (exposure process).
- the unexposed part is developed by being immersed in an inorganic alkali type developer (product name: Semi-clean DL-A4, 10-fold diluted aqueous solution) for 1 minute, and the unexposed part is washed away with water and dried. (Development process). Subsequently, the glass substrate (2) in which the pattern (black matrix) was formed was obtained by heating at 220 degreeC on a hotplate for 1 hour (post-baking process). About these, pattern formation property, developability, and ink repellency were measured and evaluated by the method shown below. The evaluation results are shown in Tables 3 and 4.
- an inorganic alkali type developer product name: Semi-clean DL-A4, 10-fold diluted aqueous solution
- the ink repellency was evaluated by the contact angle (degree) of PGMEA of the cured film on the glass substrate (2).
- 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 are in contact, and is defined as an angle including the liquid. The larger the angle, the better the ink repellency of the cured film.
- a contact angle of PGMEA of 35 degrees or more was evaluated as ⁇ (good), and a contact angle of less than 35 degrees was evaluated as x (defective). The contact angle was measured with DSA10 manufactured by Kruss.
- the film obtained from the negative photosensitive resin composition of the present invention has good solubility in an alkaline developer, and at the same time, good optical density. I understood. Further, a fine line width pattern can be formed from the negative photosensitive resin composition, and in particular, a fine contact hole can be formed. Furthermore, the ink repellency of the cured film formed from the negative photosensitive resin composition was also good.
- Example 14 in which the acid value in the solid content was less than 10 mgKOH / g, precipitation of the black organic pigment (B) was observed in the alkaline developer.
- Example 16 using only the alkali-soluble resin (A1) sedimentation was also observed.
- Example 15 using only the alkali-soluble resin (A2), the resolution of the lines and contact holes was poor. This is presumably because shape retention is difficult by not using the alkali-soluble resin (A1).
- the negative photosensitive resin composition of the present invention a partition and a black matrix having a fine line pattern and a fine contact hole can be produced.
- a black matrix is suitably used for a color filter, in particular, a BOA type color filter or an organic EL element capable of obtaining a high luminance image with low power consumption.
- the negative photosensitive resin composition of the present invention is excellent in solubility and dispersibility in a solid content of an alkali developer containing a black organic pigment, thereby increasing the recyclability of the alkali developer and increasing the productivity. It is possible to contribute to the improvement of industrial use, and industrial applicability is high.
- the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-247437 filed on November 11, 2011 are incorporated herein as the disclosure of the specification of the present invention. It is.
Abstract
Description
カラーフィルタ・オン・アレイ型のカラーフィルタでは、画素間を仕切るブラックマトリックスがアレイ基板上に形成されることから、このタイプのカラーフィルタはブラックマトリックス・オン・アレイ型(以下、「BOA型」ともいう。)のカラーフィルタとも呼ばれている。BOA型のカラーフィルタは、カラーフィルタとTFTアレイ基板が別体で製造され、位置合わせに精度が必要とされる通常のカラーフィルタと比較して、位置合わせなしで精度が確保できる。そのため、隔壁を細線化でき開口率が向上し、低消費電力と高輝度を両立した液晶表示装置が得られる。
特許文献3には、有機顔料を含有する画素形成用等の感光性樹脂組成物において、該組成物中での有機顔料の分散性を向上させるために、酸基あるいはアミノ基を有する特定の顔料分散剤を使用した感光性樹脂組成物が記載されている。
特許文献4には、光重合性化合物と黒色顔料とを含有するEL素子遮光膜形成用の感光性樹脂組成物が記載されている。
さらに、本発明者らの知見によれば、特許文献3に記載の感光性樹脂組成物は、有機溶媒中での有機顔料の分散性が不充分であり、有機溶媒を含む感光性樹脂組成物の貯蔵安定性が不充分である。
また、本発明者らの知見によれば、特許文献4に記載の感光性樹脂組成物では、黒色顔料としてカーボンブラックを使用しており、実施例では、アルカリ可溶性樹脂として主鎖に芳香族環を含まないアクリル共重合体を使用しているため、隔壁のラインの解像度が不充分である。
また、本発明は、該ネガ型感光性樹脂組成物を硬化することにより得られるBOA型の光学素子や有機EL素子に適用可能な隔壁及びブラックマトリックスならびに該ブラックマトリックスを有する光学素子の提供を目的とする。
[1]主鎖に芳香族環を含み、分子中に酸性基とエチレン性二重結合とを有するアルカリ可溶性樹脂(A1)と、主鎖に芳香族環を含まず、分子中に酸性基を有するアルカリ可溶性樹脂(A2)と、黒色有機顔料(B)と、光重合開始剤(C)とを含有するネガ型感光性樹脂組成物であって、該組成物における固形分酸価が10~50mgKOH/gであることを特徴とするネガ型感光性樹脂組成物。
[2]前記ネガ型感光性樹脂組成物における全固形分中のアルカリ可溶性樹脂(A1)とアルカリ可溶性樹脂(A2)の合計の含有割合が、5~80質量%である、上記[1]に記載のネガ型感光性樹脂組成物。
[3]前記ネガ型感光性樹脂組成物における全固形分中の黒色有機顔料(B)の含有割合が、20~65質量%である、上記[1]又は[2]に記載のネガ型感光性樹脂組成物。
[4]前記アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)のいずれかの質量平均分子量が10,000以上である、上記[1]~[3]のいずれかに記載のネガ型感光性樹脂組成物。
[5]前記光重合開始剤(C)が下式(1)で表される化合物を含む、上記[1]~[4]のいずれかに記載のネガ型感光性樹脂組成物。
R2は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基を示す。
[6]前記光重合開始剤(C)の全量中の前記式(1)で表される化合物の含有割合が、85~95質量%であり、前記ネガ型感光性樹脂組成物の全固形分量中の前記光重合開始剤(C)の含有割合が、3.5~7質量%である上記[5]に記載のネガ型感光性樹脂組成物。
[7]架橋剤(D)をさらに含み、該架橋剤(D)が1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、上記[1]~[6]のいずれかに記載のネガ型感光性樹脂組成物。
[8]撥インク剤(E)をさらに含む、上記[1]~[7]のいずれかに記載のネガ型感光性樹脂組成物。
[9]前記撥インク剤(E)が、1分子中に下式(3)で表される基又は下式(4)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とを有する撥インク剤(E)である、上記[8]に記載のネガ型感光性樹脂組成物。
-CFXRf (3)
式(3)中、Xは水素原子、フッ素原子、又はトリフルオロメチル基を示し、Rfは、エーテル性酸素原子を有していてもよい炭素原子数1~20のフルオロアルキル基、又はフッ素原子を示す。
-(SiR10R11O)n-SiR12R13R14 (4)
式(4)中、R10、R11、R12及びR13は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、又はアリール基を示し、R14は、水素原子、又は炭素原子数1~10のエーテル性酸素原子もしくは窒素原子を含んでいてもよいアルキル基を示し、nは1~200の整数を示す。
[10]前記撥インク剤(E)が、側鎖に基(3)を有し、主鎖がオルガノポリシロキサン鎖の化合物である、上記[8]に記載のネガ型感光性樹脂組成物。
-CFXRf (3)
式(1)中、Xは水素原子、フッ素原子、又はトリフルオロメチル基を示し、Rfはエーテル性酸素原子を有していてもよい炭素原子数1~20のフルオロアルキル基、又はフッ素原子を示す。
[11]溶媒(F)をさらに含む、上記[1]~[10]のいずれかに記載のネガ型感光性樹脂組成物。
[12]画素形成用に基板表面を複数の区画に仕切るように形成した隔壁であって、上記[1]~[10]のいずれかに記載のネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
[13]上記[12]に記載の隔壁が、基板表面を複数の区画に仕切るように形成されてなるブラックマトリックス。
[14]前記隔壁が、該隔壁の膜厚方向に貫通する貫通孔を有し、該貫通孔における水平方向の最大孔径が20μm以下であり、最小孔径が1μm以上である上記[13]に記載のブラックマトリックス。
[15]基板表面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光学素子であって、前記隔壁が上記[13]又は[14]に記載のブラックマトリックスからなることを特徴とする光学素子。
また、本発明によれば、該ネガ型感光性樹脂組成物を硬化することにより得られるBOA型の光学素子に適用可能な隔壁及びブラックマトリックスならびに該ブラックマトリックスを有する光学素子が提供できる。
本明細書における「(メタ)アクリロイル…」とは、「メタアクリロイル…」と「アクリロイル…」の総称である。(メタ)アクリル酸、(メタ)アクリレート、(メタ)アクリルアミド、(メタ)アリル…、(メタ)アクリル樹脂もこれと同様である。
本明細書における式(1)で表される化合物を、化合物(1)という。他の化合物も同様である。
本明細書における式(3)で表される基を、基(3)という。他の基も同様である。
本明細書における「全固形分」とは、ネガ型感光性樹脂組成物が含有する成分のうち、隔壁形成成分をいい、ネガ型感光性樹脂組成物を140℃で24時間加熱して溶媒を除去した、残存物である。具体的には、溶媒(F)等の隔壁形成過程における、加熱等により揮発する揮発性成分以外の全成分を示す。なお、全固形分の量は仕込み量からも計算できる。
本明細書においては、ネガ型感光性樹脂組成物を塗布した膜を「塗膜」、それを乾燥させた状態を「膜」、さらに、それを硬化させて得られる膜を「硬化膜」という。
基板表面を複数の区画に仕切るように形成された硬化膜を「隔壁」という。
ネガ型感光性樹脂組成物が黒色有機顔料を含有することから、「隔壁」が基板表面を複数の区画に仕切るように形成されたものを「ブラックマトリックス」とする。
本明細書における「インク」とは、乾燥硬化した後に、例えば光学的、電気的に機能を有する液状組成物を総称するものであり、従来から用いられている着色材料に限定されるものではない。
また、上記インクを注入して形成される「画素」についても同様に、隔壁で仕切られたそれぞれに光学的、電気的機能を有する区分を表すものとして用いられる。
本明細書における撥インク性とは、上記インクをはじくために、撥水性と撥油性の両方を適度に有する性質をいい、例えば、後述の方法で評価できる。
微小なコンタクトホールの、「微小」とは、該コンタクトホールを構成する貫通孔における水平方向の最大孔径が概ね20μm以下のサイズをいう。また、貫通孔における水平方向の最大孔径とは、貫通孔の水平断面のうちで最大面積を有する断面における長径をいい、最小孔径とは、貫通孔の水平断面のうちで最小面積を有する断面における短径をいう。
本明細書において、「黒色有機顔料」とは、広く可視光領域の波長(400~800nm)の光を吸収する、単独あるいは複数の有機顔料から構成される着色剤をいう。
以下、本発明について詳しく説明する。なお、本明細書において特に説明のない場合、%は質量%を表す。
本発明のネガ型感光性樹脂組成物は、主鎖に芳香族環を含み、分子中に酸性基とエチレン性二重結合とを有するアルカリ可溶性樹脂(A1)及び、主鎖に芳香族環を含まず、分子中に酸性基を有するアルカリ可溶性樹脂(A2)を含むアルカリ可溶性樹脂(A)を含有する。アルカリ可溶性樹脂(A)は、アルカリ可溶性樹脂(A1)、アルカリ可溶性樹脂(A2)以外のアルカリ可溶性樹脂を含んでもよいが、アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)のみで構成されることが好ましい。
また、アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)のいずれかの質量平均分子量が10,000以上であることが好ましい。アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)の組み合わせにおいて、質量平均分子量の上限は特に制限されず、各アルカリ可溶性樹脂においてそれぞれ後述する上限と同様にできる。
ネガ型感光性樹脂組成物における全固形分中のアルカリ可溶性樹脂(A)の含有割合は、5~80質量%が好ましく、10~60質量%が特に好ましい。なお、アルカリ可溶性樹脂(A)がアルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)以外のアルカリ可溶性樹脂を含む場合、その割合はアルカリ可溶性樹脂(A)の全量に対して、10質量%以下とする。
本発明におけるアルカリ可溶性樹脂(A1)は、主鎖に芳香族環を含み、分子中に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。アルカリ可溶性樹脂(A1)が分子中にエチレン性二重結合を有することで、ネガ型感光性樹脂組成物の露光部は、光重合開始剤から発生したラジカルにより重合して硬化する。硬化した露光部分はアルカリ現像液にて除去されない。また、アルカリ可溶性樹脂(A1)が分子中に酸性基を有することで、アルカリ現像液にて、硬化していないネガ型感光性樹脂組成物の未露光部を選択的に除去することができる。その結果、隔壁を形成することができる。なお、アルカリ可溶性樹脂(A1)は実質的に、後述の撥インク剤(E)が有する基(1)又は基(2)を含有しないことが好ましい。
前記エチレン性二重結合としては、特に制限されないが、(メタ)アクリロイル基、アリル基、ビニル基、ビニルオキシ基、ビニルオキシアルキル基等の付加重合性を有する二重結合が挙げられ、1種を単独で用いても2種以上を併用してもよい。なお、エチレン性二重結合中の水素原子の一部又は全てが、アルキル基、好ましくはメチル基で置換されていてもよい。
具体的には、主鎖に芳香族環を含むエポキシ樹脂と、カルボキシ基とエチレン性二重結合を有する化合物とを反応させることにより、該エポキシ樹脂にエチレン性二重結合が導入される。次に、エチレン性二重結合が導入された主鎖に、芳香族環を含むエポキシ樹脂に多価カルボン酸又はその無水物を反応させることにより、カルボキシ基を導入することができる。
アルカリ可溶性樹脂(A1)の酸価は、10~300mgKOH/gが好ましく、30~150mgKOH/gが特に好ましい。酸価が上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好になる。また、アルカリ可溶性樹脂(A1)の酸価が上記範囲であると、アルカリ可溶性樹脂(A)としての酸価を後述の範囲に調整しやすく、さらには、ネガ型感光性樹脂組成物の固形分酸価を本発明の範囲に調整しやすい。
アルカリ可溶性樹脂(A2)は、主鎖に芳香族環を含まず、分子中に酸性基を有する感光性樹脂である。分子中に酸性基を有することでアルカリ水溶液に可溶となり、未露光部を溶解させることができる。
前記酸性基としては特に制限されず、カルボキシ基、フェノール性水酸基、スルホ基、リン酸基等が挙げられるが、カルボキシ基が好ましい。1種を単独で用いても2種以上を併用してもよい。
アルカリ可溶性樹脂(A2)は、酸性基以外に必要に応じて、側鎖にエチレン性二重結合を有してもよい。該エチレン性二重結合としては、上記アルカリ可溶性樹脂(A1)が有するエチレン性二重結合と同様である。
酸性基とエチレン性二重結合等の反応性基を有する単量体を重合させる方法、酸性基を有しない単量体と、上記酸性基を有する単量体とを共重合させる方法等が挙げられる。なお、用いる単量体はいずれも、得られる(共)重合体が、主鎖に芳香族環を有しない構造となる単量体である。ただし、得られる(共)重合体は、側鎖に芳香族環を有するものであってもよい。
上記エチレン性二重結合としては、特に制限されないが、(メタ)アクリロイル基、アリル基、ビニル基、ビニルオキシ基、ビニルオキシアルキル基等の付加重合性を有する二重結合が挙げられ、これらは1種を単独で用いても2種以上を併用してもよい。なお、エチレン性二重結合基が有する水素原子の一部又は全てが、アルキル基、好ましくはメチル基で置換されていてもよい。
酸性基とエチレン性二重結合等の反応性基を有する単量体としては、酸性基としてカルボキシ基を有するとともに、エチレン性二重結合を有する化合物が好ましく、(メタ)アクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、ケイ皮酸及びこれらの塩等が好ましく、(メタ)アクリル酸が特に好ましい。
アルカリ可溶性樹脂(A2)の酸価は、20~300mgKOH/gの範囲が好ましく、パターン形状を維持するために、30~250mgKOH/gの範囲にあることが特に好ましい。また、アルカリ可溶性樹脂(A2)の酸価が上記範囲であると、アルカリ可溶性樹脂(A)としての酸価を後述の範囲に調整しやすく、さらには、ネガ型感光性樹脂組成物の固形分酸価を本発明の範囲に調整しやすい。
本発明におけるネガ型感光性樹脂組成物は、遮光剤として黒色有機顔料(B)を含む。
黒色有機顔料(B)としては、アントラキノン系黒色顔料、ペリレン系黒色顔料、アゾメチン系黒色顔料等が挙げられる。具体的には、C.I.ピグメントブラック1、6、7、12、20、31等の可視光領域の波長の光を広く吸収する単一の有機顔料からなる黒色有機顔料(B)が挙げられる。
また、透過型電子顕微鏡観察による平均2次粒子径としては、80~200nmが好ましく、100~200nmが特に好ましい。
高分子分散剤としては、ウレタン系、ポリイミド系、アルキッド系、エポキシ系、不飽和ポリエステル系、メラミン系、フェノール系、アクリル系、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の化合物が挙げられる。中でも特にウレタン系、ポリエステル系の化合物が好ましい。
本発明のネガ型感光性樹脂組成物において、通常、黒色有機顔料(B)は、黒色有機顔料(B)、高分子分散剤及び分散媒を含む分散液として使用される。該分散液は、例えば、黒色有機顔料(B)、高分子分散剤、分散媒を加えた混合物を公知の湿式粉砕分散装置、例えばペイントコンディショナー、ビーズミル等を用いて湿式粉砕分散処理することで製造できる。
用いる分散媒としては、後述のネガ型感光性樹脂組成物の溶媒(F)と同様のものが使用可能である。分散液における分散媒の配合量としては、通常、分散液全体の65~90質量%程度である。
本発明におけるネガ型感光性樹脂組成物は、光重合開始剤(C)を含む。
BOA型のカラーフィルタでは、スイッチング素子であるTFTと画素電極を接続するために、隔壁に貫通したコンタクトホールを製造する必要がある。隔壁は光透過率が低いため、従来のフォトリソ法を用いた場合、隔壁下部の光硬化性が悪く、高感度な光重合開始剤を用いないと、アルカリ現像時にパターンが溶解してしまい、良好なパターン形成が困難となる。しかし、高感度の光重合開始剤を用いると、未露光部もフォトマスクからの漏れ光等により光硬化してしまうため、微小なコンタクトホール形成に困難が生じる。良好なパターン形成と微小なコンタクトホール形成を両立するためには、光重合開始剤(C)を適宜選択することが重要である。
光重合開始剤(C1)は、下式(1)で表されるO-アシルオキシム系化合物からなる。
R2は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基を示す。
R2としては、炭素原子数1~10のアルキル基、又は炭素原子数2~5のアルコキシカルボニル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基等が挙げられる。中でも、炭素原子数1~6のアルキル基がより好ましく、ヘキシル基、メチル基が特に好ましい。
このような光重合開始剤としては、より高感度なO-アシルオキシム系化合物、例えば、アデカオプトマー N-1919、アデカクルーズ NCI-831、NCI-930(以上、ADEKA社製、いずれも商品名)、下式(2)で表される化合物(以下、「光重合開始剤(C2)」ともいう。)等が挙げられる。中でも、光重合開始剤(C2)が好ましい。
R4は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~30のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~30のフェニルアルキル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、又はシアノ基を示す。
R6、R7、R8及びR9は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、R61、OR62、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンジルカルボニル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、又は炭素原子数1~20のアミド基を示す。
R0は、R61、OR62、シアノ基又はハロゲン原子を示す。aは0~3の整数である。
式(2)中、R3は、水素原子、炭素原子数1~12のアルキル基、炭素原子数3~8のシクロアルキル基、炭素原子数2~5のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェノキシ基を示す。
R4は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基、又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基を示す。
R6、R7、R8及びR9は、それぞれ独立に、水素原子、炭素原子数1~12のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンジルカルボニル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、炭素原子数1~20のアミド基又はニトロ基を示す。
R0の個数を示すaは0である。
光重合開始剤(C2)として、国際公開第2008/078678号に記載のNo.1~71も使用できる。
R3としては、炭素原子数1~10のアルキル基、又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~12のフェニル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、フェニル基等が挙げられる。中でも、炭素原子数1~4のアルキル基がより好ましく、炭素原子数1~2のアルキル基がさらに好ましく、メチル基が特に好ましい。
R4としては、炭素原子数1~10のアルキル基、又は炭素原子数2~5のアルコキシカルボニル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基等が挙げられる。中でも、炭素原子数1~6のアルキル基がより好ましく、炭素原子数1~3のアルキル基がさらに好ましく、メチル基が特に好ましい。
R6、R8及びR9としては、水素原子又はニトロ基が好ましい。
R7としては、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンジルカルボニル基、又はニトロ基が好ましく、ベンゾイル基、2-メチルベンゾイル基、2-メチル-4-テトラヒドロピラニルメトキシベンゾイル基、2-メチル-5-テトラヒドロフラニルメトキシベンゾイル基、2-メチル-5-テトラヒドロピラニルメトキシベンゾイル基、ベンジルカルボニル基、1,3,5トリメチルベンジルカルボニル基、ニトロ基が特に好ましい。
R0の個数を示すaは、0である。
R3:フェニル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(2-1)、
R3:メチル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(2-2)、
R3:メチル基、R4:ブチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(2-3)、
R3:メチル基、R4:ヘプチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(2-4)、
R3:フェニル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(2-5)、
R3:メチル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(2-6)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(2-7)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-4-テトラヒドロピラニルメトキシベンゾイル基である化合物(2-8)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-5-テトラヒドロフラニルメトキシベンゾイル基である化合物(2-9)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-5-テトラヒドロピラニルメトキシベンゾイル基である化合物(2-10)。
光重合開始剤(C1)と光重合開始剤(C2)とを併用する場合、光重合開始剤(C)の全量中の光重合開始剤(C2)の含有割合は、光重合開始剤(C1)の配合量の残部、すなわち5~15質量%が好ましく、5~10質量%が特に好ましい。光重合開始剤(C)中の光重合開始剤(C2)の割合が上記範囲であると、光重合開始剤(C1)による上記効果が充分に得られるとともに、よりブラックマトリックス下部の光硬化性を高めることが可能である。
メチルフェニルグリオキシレート、9,10-フェナンスレンキノン等のα-ジケトン類;ベンゾイン等のアシロイン類;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のアシロインエーテル類;チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、2,4-ジイソプロピルチオキサントン、チオキサントン-4-スルホン酸等のチオキサントン類;ベンゾフェノン、4,4’-ビス(ジメチルアミノ)ベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン等のベンゾフェノン類;アセトフェノン、2-(4-トルエンスルホニルオキシ)-2-フェニルアセトフェノン、p-ジメチルアミノアセトフェノン、2,2’-ジメトキシ-2-フェニルアセトフェノン、p-メトキシアセトフェノン、2-メチル-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1-オン等のアセトフェノン類;アントラキノン、2-エチルアントラキノン、カンファーキノン、1,4-ナフトキノン等のキノン類;2-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸(n-ブトキシ)エチル、4-ジメチルアミノ安息香酸イソアミル、4-ジメチルアミノ安息香酸2-エチルヘキシル等のアミノ安息香酸類;フェナシルクロライド、トリハロメチルフェニルスルホン等のハロゲン化合物;アシルホスフィンオキシド類;ジ-t-ブチルペルオキシド等の過酸化物;トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、n-ブチルアミン、N-メチルジエタノールアミン、ジエチルアミノエチルメタクリレート等の脂肪族アミン類;2-メルカプトベンズイミダゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾチアゾール、1,4-ブタノールビス(3-メルカプトブチレート)、トリス(2-メルカプトプロパノイルオキシエチル)イソシアヌレート、ペンタエリスリトールテトラキス(3-メルカプトブチレート)等のチオール化合物等である。
本発明におけるネガ型感光性樹脂組成物は、ラジカル硬化を促進する任意成分として、架橋剤(D)を含んでもよい。架橋剤(D)としては、1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物が好ましい。ネガ型感光性樹脂組成物が架橋剤(D)を含むことにより、露光時におけるネガ型感光性樹脂組成物の硬化性が向上し、低い露光量でも隔壁を形成することができる。
本発明におけるネガ型感光性樹脂組成物は、必要に応じて撥インク剤(E)を含有する。撥インク剤(E)は、塗布膜の表面に偏在し、硬化膜表面に撥インク性の機能を与える化合物である。
-CFXRf (3)
式(3)中、Xは水素原子、フッ素原子、又はトリフルオロメチル基を示し、Rfはエーテル性酸素原子を有していてもよい炭素原子数1~20のフルオロアルキル基、又はフッ素原子を示す。
-(SiR10R11O)n-SiR12R13R14 (4)
式(4)中、R10、R11、R12及びR13は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、又はアリール基を示し、R14は水素原子、又は炭素原子数1~10のエーテル性酸素原子もしくは窒素原子を含んでいてもよいアルキル基を示し、nは1~200の整数を示す。
基(3)又は基(4)を有する側鎖は、重合反応によって直接形成しても、重合反応後の化学変換によって形成してもよい。また、エチレン性二重結合を有する側鎖は重合反応後の化学変換によって形成できる。
-CF3、-CF2CF3、-CF2CHF2、-(CF2)2CF3、-(CF2)3CF3、-(CF2)4CF3、-(CF2)5CF3、-(CF2)6CF3、-(CF2)7CF3、-(CF2)8CF3、-(CF2)9CF3、-(CF2)11CF3、-(CF2)15CF3、
-CF(CF3)O(CF2)5CF3、
-CF2O(CF2CF2O)pCF3(pは1~8の整数)、
-CF(CF3)O(CF2CF(CF3)O)qC6F13(qは1~4の整数)、
-CF(CF3)O(CF2CF(CF3)O)rC3F7(rは1~5の整数)。
基(4)において、R12、R13及びR14は、シロキサン結合の末端のケイ素原子に結合する基であり、R12及びR13としては、R10及びR11と同様とすることができ、好ましい態様も同様である。また、R14が、エーテル性酸素原子(-O-)又は窒素原子(-NR40-。R40は水素原子又は炭素原子数が1~5のアルキル基である。)を含んでいてもよい炭素原子数1~10のアルキル基である場合、炭素原子数1~5のアルキル基、エーテル性酸素原子を1個含む炭素原子数1~5のアルキル基等が好ましい。R14は、水素原子又は炭素原子数1~5のアルキル基であることが特に好ましい。nは1~200の整数が好ましく、2~100の整数が特に好ましい。
-(Si(CH3)2O)n-Si(CH3)2H、-(Si(CH3)2O)n-Si(CH3)2CH3、-(Si(CH3)2O)n-Si(CH3)2C2H5、-(Si(CH3)2O)n-Si(CH3)2C3H7、-(Si(CH3)2O)n-Si(CH3)2C4H9、-(Si(CH3)2O)n-Si(CH3)2C5H10、-(Si(CH3)2O)n-Si(CH3)2OH、-(Si(CH3)2O)n-Si(CH3)2OCH3、-(Si(CH3)2O)n-Si(CH3)2OC2H5、-(Si(C2H5)2O)n-Si(CH3)2H、-(Si(C2H5)2O)n-Si(C2H5)2H、-(Si(C2H5)2O)n-Si(C2H5)2H、-(Si(C2H5)2O)n-Si(C2H5)3、-(Si(C2H5)(CH3)O)n-Si(C2H5)2H。
酸性基を有する側鎖は、酸性基を有する単量体の重合反応によって形成してもよいし、重合反応後の化学変換によって形成してもよい。
CH2=CR21COO-Y-CFXRf (11)
式(11)中、R21は水素原子、メチル基、又はトリフルオロメチル基を示し、Yは炭素原子数1~6のフッ素原子を含まない2価の有機基を示し、Rfはエーテル性酸素原子を有していてもよい炭素原子数1~20の水素原子の少なくとも1つがフッ素原子に置換されたアルキル基、又はフッ素原子を示す。
単量体(11)において、-CFXRfの好ましい態様は、基(3)の好ましい態様と同様である。単量体(11)において、Yは、入手の容易さから、炭素原子数2~4のアルキレン基であることが好ましい。
CH2=CR21COOR22CFXRf
CH2=CR21COOR22NR23SO2CFXRf
CH2=CR21COOR22NR23COCFXRf
CH2=CR21COOCH2CH(OH)R24CFXRf
ここで、R21は水素原子、メチル基、又はトリフルオロメチル基を示し、R22は炭素原子数1~6のアルキレン基を示し、R23は水素原子又はメチル基を示し、R24は単結合又は炭素原子数1~4のアルキレン基を示し、Rfは上記と同じ意味を示す。
CH2=CR25COO-Z-(SiR10R11O)n-SiR12R13R14 (21)
式(21)中、R25は水素原子又はメチル基を示し、Zは炭素原子数1~6の2価の有機基を示し、R10、R11、R12及びR13は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、又はアリール基を示し、R14は水素原子、又は炭素原子数1~10のエーテル性酸素原子もしくは窒素原子(-NR41-。R41は水素原子又は炭素原子数が1~5のアルキル基である。)を含んでいてもよいアルキル基を示し、nは1~200の整数を示す。
単量体(21)において、R10、R11、R12、R13、R14、及びnの好ましい態様は、基(4)の好ましい態様と同様である。
-CH2-、-CH2CH2-、-CH(CH3)-、
-CH2CH2CH2-、-C(CH3)2-、-CH(CH2CH3)-、
-CH2CH2CH2CH2-、-CH(CH2CH2CH3)-、
-CH2(CH2)3CH2-、-CH(CH2CH(CH3)2)-等。
上記単量体(21)は1種を用いてもよく、2種以上を併用してもよい。
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。)、
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。)、
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。)。
カルボキシ基を有する単量体の具体例としては、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、ケイ皮酸、もしくはそれらの塩が挙げられる。
エポキシ基を有する単量体の具体例としては、グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチルアクリレートが挙げられる。
(1)反応性基としての水酸基に対し、化合物(z1)としてのエチレン性二重結合を有する酸無水物、
(2)反応性基としての水酸基に対し、化合物(z1)としてのイソシアネート基とエチレン性二重結合を有する化合物、
(3)反応性基としての水酸基に対し、化合物(z1)としての塩化アシル基とエチレン性二重結合を有する化合物、
(4)反応性基としての酸無水物基に対し、化合物(z1)としての水酸基とエチレン性二重結合を有する化合物、
(5)反応性基としてのカルボキシ基に対し、化合物(z1)としてのエポキシ基とエチレン性二重結合を有する化合物、
(6)反応性基としてのエポキシ基に対し、化合物(z1)としてのカルボキシ基とエチレン性二重結合を有する化合物。
化合物(z1)としてのイソシアネート基とエチレン性二重結合を有する化合物の具体例としては、2-(メタ)アクリロイルオキシエチルイソシアネート、1,1-ビス((メタ)アクリロイルオキシメチル)エチルイソシアネート等が挙げられる。
化合物(z1)としての塩化アシル基とエチレン性二重結合を有する化合物の具体例としては、(メタ)アクリロイルクロライドが挙げられる。
化合物(z1)としての水酸基とエチレン性二重結合を有する化合物の具体例としては、上記した水酸基を有する単量体の例が挙げられる。
化合物(z1)としてのエポキシ基とエチレン性二重結合を有する化合物の具体例としては、上記したエポキシ基を有する単量体の例が挙げられる。
化合物(z1)としてのカルボキシ基とエチレン性二重結合を有する化合物の具体例としては、上記したカルボキシ基を有する単量体の例が挙げられる。
上記の組み合わせとしては、(2)の組み合わせが好ましく、化合物(z1)として1,1-ビス((メタ)アクリロイルオキシメチル)エチルイソシアネートを用いることが特に好ましい。該組み合わせにすることで、撥インク剤(E)は、側鎖1つにつきエチレン性二重結合を2つ以上有する側鎖を有することとなり、撥インク剤(E)の隔壁表面への固定化が優れ、撥インク性に優れた隔壁が得られるからである。
酸性基を有する単量体(a4)としては、カルボキシ基を有する単量体、フェノール性水酸基を有する単量体、スルホ基を有する単量体等が挙げられる。
カルボキシ基を有する単量体としては、上記単量体(a3)において例示したのと同様の単量体が挙げられる。
酸性基を有する単量体(a4)としてカルボキシ基を有する単量体を用い、上記反応性基を有する単量体(a3)としてもカルボキシ基を有する単量体を用いるときは、最終的にエチレン性二重結合が導入されず、カルボキシ基として残るものを単量体(a4)とみなすこととする。
その他の単量体(a5)としては、ポリオキシアルキレン基を有する下式(51)で表される化合物(51)、又は下式(52)で表される化合物(52)であることが好ましい。これらは1種を単独で用いても、2種以上を併用してもよい。
CH2=CR26-COO-W-(R27O)m(R28O)jR29 …(51)
CH2=CR26-O-W-(R27O)m(R28O)jR29 …(52)
また、m+jは、6~50の整数が好ましく、8~30の整数が特に好ましい。m+jが上記範囲の下限値以上であると、現像工程の後に高圧水を使用したジェットリンス(Jet Rinse)工程を行った場合、撥インク性が低下しにくい。さらに、残膜が発生しにくい。m+jが上記範囲の上限値以下であると、ポストベーク時に、開口部に撥インク剤(E)がマイグレートすることなく、隔壁間開口部の親インク性が充分になり、インクジェット法を用いてインクを塗布したとき、開口部にインクが充分に濡れ拡がる。
CH2=CHCOO(CH2CH2O)mR29、
CH2=C(CH3)COO(CH2CH2O)mR29、
CH2=CHCOO(CH2CH2O)m(C3H6O)jR29、
CH2=C(CH3)COO(CH2CH2O)m(C3H6O)jR29、
CH2=CHCOO(C2H4O)m(C4H8O)jR29
が好ましい。
また、化合物(52)としては、
CH2=CHOCH2C6H10CH2O(CH2CH2O)mR29、
CH2=CHO(CH2)4O(CH2CH2O)mR29
が好ましい。
式中、m及びjは上記と同じ意味を示し、好ましい範囲も同様である。なお、C6H10は、シクロヘキシレン基である。C2H4、C3H6、C4H8は直鎖構造又は分岐構造のいずれかである。式中のR29は、上記と同じ意味を示し、好ましくは、炭素原子数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。
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。)、
ブレンマーPME-1000(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23である。)
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は約9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:式中のkは分子間の平均値を示し、kは約9である。)。
無機過酸化物としては、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム、過酸化水素、過炭酸塩等が挙げられる。
アゾ化合物としては、2,2’-アゾビスイソブチロニトリル、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビスイソ酪酸ジメチル、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩等が挙げられる。また、アゾ系重合開始剤として、市販品のV-65(商品名、和光純薬工業社製)等を使用することも可能である。
次に、得られた共重合体と化合物(z1)とを反応させる。
該反応には溶媒を用いるのが好ましい。溶媒は上述の共重合反応に用いる溶媒が用いられる。
また、重合禁止剤を配合することが好ましい。重合禁止剤としては、例えば、2,6-ジ-t-ブチル-p-クレゾールが挙げられる。
また、触媒や中和剤を加えてもよい。例えば、水酸基を有する共重合体と、イソシアネート基とエチレン性二重結合を有する化合物を反応させる場合、ジブチル錫ジラウレート等の錫化合物等を用いることができる。水酸基を有する共重合体と、塩化アシル基とエチレン性二重結合を有する化合物を反応させる場合、塩基性触媒を用いることができる。
単量体(a1)及び/又は単量体(a2)の割合は20~80質量%が好ましく、30~60質量%が特に好ましい。該割合が上記範囲の下限値以上であると、硬化膜からなる隔壁の表面張力を低減でき、隔壁に高い撥インク性を付与できる。上記範囲の上限値以下であると、隔壁と基材との密着性が良好になる。
単量体(a3)の割合は20~70質量%が好ましく、30~50質量%が特に好ましい。該範囲であると、エチレン性二重結合の導入による撥インク剤(E)の隔壁への固定化及び現像性が良好となる。
単量体(a4)の割合は1~20質量%が好ましく、1~10質量%が特に好ましい。該範囲であると、露光工程で固定化されなかった残存分子が現像工程において隔壁から洗い流されやすい。
その他の単量体(a5)を用いる場合には、その割合は5~45質量%が好ましく、5~35質量%が特に好ましい。該範囲であるとアルカリ溶解性、現像性が良好である。
単量体(a1)及び/又は単量体(a2):単量体(a3):単量体(a4):単量体(a5)=30~60質量%:30~50質量%:1~10質量%:9~35質量%。
なお、単量体(a3)と単量体(a4)の両方として、カルボキシ基を有する単量体を使用する場合は、撥インク剤(E)の酸価が後述する範囲となるように、共重合体と化合物(z1)の仕込み量を調節すればよい。
撥インク剤(E2)としては、フッ素原子を含有する加水分解性シラン化合物を含む1種以上の加水分解性シラン化合物が、部分加水分解縮合して得られる含フッ素シラン化合物が好ましい。
撥インク剤(E2)としては、下式(e2-1)で表される加水分解性シラン化合物(e2-1)(以下、「化合物(e2-1)」ともいう。)及び下式(e2-2)で表される加水分解性シラン化合物(e2-2)(以下、「化合物(e2-2)」ともいう。)を必須成分として含む、加水分解性シラン化合物混合物の部分加水分解縮合物が好ましい。
式(e2-1)中の記号は、以下の通りである。
RF:炭素原子数3~10のエーテル性酸素原子を含んでいてもよいペルフルオロアルキル基を有する1価の有機基、
X1:加水分解性基。
ただし、化合物内に3個存在するX1は、互いに異なっていても、同一であってもよい。
式(e2-2)中の記号は、以下の通りである。
RH:ペルフルオロアルキル基を有しない1価の有機基、
X2:加水分解性基、
p:0、1又は2である。
ただし、RH及びX2が、化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
また、撥インク剤(E2)は、シラノール基(すなわち、ケイ素原子に結合した水酸基)を有することが好ましい。シラノール基の数としては、ケイ素原子1個当たり、0.2~3.5個が好ましく、0.2~2.0個がより好ましく、0.5~1.5個が特に好ましい。上記範囲の下限値以上であると、撥インク剤(E2)の溶媒への溶解性やネガ型感光性樹脂組成物中の他の成分への相溶性が良好であり、作業性が向上する。上記範囲の上限値以下であると、ネガ型感光性樹脂組成物を用いて隔壁を形成する際に、基材表面からの撥インク剤(E2)の蒸発を防止できる。
なお、撥インク剤(E2)中のシラノール基数は、29Si-NMRにより測定されるシラノール基を有するSi基と、シラノール基を有しないSi基とのピーク面積の比により算出される。
部分加水分解縮合物は、さらなる縮合や加水分解の結果、最終的に溶媒に溶解しない高分子量硬化物になる性質を有する。部分加水分解縮合物は、多量化の程度の異なるオリゴマーの混合物であってもよい。
部分加水分解縮合物は、例えば、加水分解性シラン化合物を酸触媒と水の存在下、所定の反応温度条件下で、所定の時間撹拌する等により作製することができる。得られる部分加水分解縮合物の多量体化の程度は、酸濃度、反応温度、反応時間等により適宜、調整可能である。
なお、下記シラン化合物の割合を示すモル比は、下記シラン化合物の少なくともいずれかが、部分加水分解縮合物である場合には、上記モル比は、各シラン化合物に由来するケイ素原子の数の比である。
化合物(e2-1)を用いることにより、硬化膜に撥水性と撥油性(すなわち撥インク性)を付与できる。
化合物(e2-1)としては、下式(e2-11)で表される化合物がより好ましい。
Rf-CFX-Q1-SiX1 3 ・・・(e2-11)
(式(e2-11)中の記号は、以下の通りである。
X、Rf及びX1は上記と同様であり、Q1は、炭素原子数1~10のフッ素原子を含まない2価の有機基である。ただし、式(e2-11)中の3個のX1は、それぞれ互いに異なっていても同一であってもよい。)
Q1としては、i1が2又は3である-(CH2)i1-がより好ましく、-(CH2)2-が特に好ましい。
基(1)がエーテル性酸素原子を含む炭素原子数4~9のペルフルオロアルキル基である場合、上記Q1としては、-(CH2)i1-、-CH2O(CH2)i2-、-SO2NR1-(CH2)i3-、-(C=O)-NR1-(CH2)i4-で表される基(i1~i4及びR1は上記と同様)が好ましい。この場合においても、-(CH2)2-が特に好ましい。
F(CF2)4CH2CH2Si(OCH3)3、F(CF2)4CH2CH2Si(OCH2CH3)3、F(CF2)4CH2CH2SiCl3、F(CF2)6CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH2CH3)3、F(CF2)6CH2CH2SiCl3、F(CF2)8CH2CH2Si(OCH3)3。
CF3OCF3CF2CF2CH2CH2Si(OCH3)3、F(CF2)2OCF2CF2OCF2CF2OCF2CF2OCF2CH2CH2Si(OCH2CH3)3、CF3OCF(CF3)CF2CH2CH2CH2Si(OCH3)3。
F(CF2)2OCF2CF2OCF2CH2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2CH2CH2Si(OCH3)3。
F(CF2)3OCF2CF2CH2CH2SiCl3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3、F(CF2)3OCF(CF3)CF2OCF2(CF3)CF2CH2CH2Si(OCH3)3。
加水分解性シラン化合物の混合物に含まれる加水分解性シラン化合物として、化合物(e2-1)は、1種を単独で用いても2種以上を併用してもよい。
また、前記加水分解性シラン化合物の混合物は、化合物(e2-1)の部分加水分解縮合物を含有していてもよい。しかし、部分加水分解縮合物であるよりも化合物(e2-1)単体であることが好ましい。
化合物(e2-2)を用いることにより、撥インク剤(E2)は、炭化水素系の溶媒に溶解しやすくなり、基材の表面にネガ型感光性樹脂組成物の塗膜を形成する際に、比較的安価な溶媒を選択できる。
式(e2-2)において、RHは炭素原子数1~6のアルキル基が好ましく、炭素原子数1~4のアルキル基がより好ましく、メチル基又はエチル基がさらに好ましく、メチル基が特に好ましい。アルキル基以外のRHとしては、ビニル基やアリル基などのアルケニル基、フェニル基やシクロアルキル基などの環を有する炭化水素基が挙げられる。
X2は加水分解性基であり、上式(e2-1)中のX1と好ましい態様を含めて同様である。pは0、1又は2である。ただし、pが2の場合の2個のRH1、及び(4-p)個のX2は、それぞれ互いに異なっていても、同一であってもよい。
化合物(e2-2)の具体例としては、以下の化合物が挙げられる。
Si(OCH3)4、Si(OCH2CH3)4、CH3Si(OCH3)3、CH3Si(OCH2CH3)3、CH3CH2Si(OCH3)3、CH3CH2Si(OCH2CH3)3、(CH3)2Si(OCH3)2、(CH3)2Si(OCH2CH3)2、Si(OCH3)4の部分加水分解縮合物(例えば、コルコート社製のメチルシリケート51(商品名))、Si(OCH2CH3)4の部分加水分解縮合物(例えば、コルコート社製のエチルシリケート40、エチルシリケート48(いずれも商品名))。
加水分解性シラン化合物混合物中の化合物(e2-2)の含有量は、化合物(e2-1)の1モルに対して化合物(e2-2)の0.1~9モルが好ましく、0.5~9モルが特に好ましい。
さらに、化合物(e2-1)及び化合物(e2-2)以外の加水分解性シラン化合物(以下、「化合物(e2-3)」ともいう。)や化合物(e2-3)の部分加水分解縮合物を含んでいてもよい。
化合物(e2-3)としては、加水分解性基を有する2官能性又は3官能性のシラン化合物であり、化合物(e2-1)及び化合物(e2-2)と共縮合する化合物であれば、公知のシラン化合物を使用できる。
化合物(e2-3)としては、前記式(e2-2)において、RHの代わりに炭素原子数7以上の炭化水素基や反応性基で置換された炭化水素基を有する構造のシラン化合物であることが好ましい。ただし、式(e2-2)においてpが2である場合、2つのRHの1つはRHであってもよい。反応性基としては、(メタ)アクリロイルオキシ基、アミノ基、炭化水素基置換アミノ基、エポキシ基などが好ましい。特に(メタ)アクリロイルオキシ基等のエチレン性二重結合を有する反応性基が好ましい。
好ましい化合物(e2-3)は、エチレン性二重結合を有する反応性基を有する加水分解性シラン化合物であり、(メタ)アクリロイルオキシ基置換アルキル基を有するトリアルコキシシランやジアルコキシシランが特に好ましい。エチレン性二重結合を有する化合物(e2-3)を使用することにより、エチレン性二重結合を有する撥インク剤(E2)が得られる。
CH2=C(CH3)COO(CH2)3Si(OCH3)3、
CH2=C(CH3)COO(CH2)3Si(OCH2CH3)3、
CH2=CHCOO(CH2)3Si(OCH3)3、
CH2=CHCOO(CH2)3Si(OCH2CH3)3、
[CH2=C(CH3)COO(CH2)3]CH3Si(OCH3)2、
[CH2=C(CH3)COO(CH2)3]CH3Si(OCH2CH3)2、
(C6H5)NH(CH2)3Si(OCH3)3。
本発明の加水分解性シラン化合物混合物に含まれる加水分解性シラン化合物として、化合物(e2-3)は、1種を単独で用いても2種以上を併用してもよい。
本発明の加水分解性シラン化合物の混合物中の化合物(e2-3)の配合量は、化合物(e2-1)及び化合物(e2-2)の合計量の1モルに対して、5モル以下が好ましく、4モル以下が特に好ましい。
1官能性のシラン化合物としては、前記式(e2-2)において、pが3である構造の化合物やヘキサアルキルジシロキサンが好ましい。これら化合物におけるアルキル基は、炭素数4以下が好ましく、メチル基又はエチル基であることがより好ましい。
(組み合わせ1)
化合物(e2-1):2-(ペルフルオロヘキシル)エチルトリメトキシシラン及び2-(ペルフルオロブチル)エチルトリメトキシシランから選ばれる少なくとも1種。
化合物(e2-2):テトラエトキシシラン又はテトラエトキシシランとメチルトリエトキシシラン。
(組み合わせ2)
化合物(e2-1):2-(ペルフルオロヘキシル)エチルトリメトキシシラン及び2-(ペルフルオロブチル)エチルトリメトキシシランから選ばれる少なくとも1種。
化合物(e2-2):テトラエトキシシラン又はテトラエトキシシランとメチルトリエトキシシラン。
1官能性のシラン化合物:ヘキサメチルジシロキサン又はトリメチルメトキシシラン
(組み合わせ3)
化合物(e2-1):2-(ペルフルオロヘキシル)エチルトリメトキシシラン及び2-(ペルフルオロブチル)エチルトリメトキシシランから選ばれる少なくとも1種。
化合物(e2-2):テトラエトキシシラン又はテトラエトキシシランとメチルトリエトキシシラン。
化合物(e2-3):3-アクリロイルオキシプロピルトリメトキシシラン又は3-メタクリロイルオキシプロピルトリメトキシシラン
(組み合わせ4)
化合物(e2-1):2-(ペルフルオロヘキシル)エチルトリメトキシシラン及び2-(ペルフルオロブチル)エチルトリメトキシシランから選ばれる少なくとも1種。
化合物(e2-2):テトラエトキシシラン又はテトラエトキシシランとメチルトリエトキシシラン。
化合物(e2-3):3-アクリロイルオキシプロピルトリメトキシシラン又は3-メタクリロイルオキシプロピルトリメトキシシラン
1官能性のシラン化合物:ヘキサメチルジシロキサン又はトリメチルメトキシシラン
(組み合わせ5)
化合物(e2-1):2-(ペルフルオロヘキシル)エチルトリメトキシシラン及び2-(ペルフルオロブチル)エチルトリメトキシシランから選ばれる少なくとも1種。
化合物(e2-2):テトラエトキシシラン又はテトラエトキシシランとメチルトリエトキシシラン。
化合物(e2-3):3-グリシジルオキシプロピルトリメトキシシラン
1官能性のシラン化合物:ヘキサメチルジシロキサン又はトリメチルメトキシシラン
本発明のネガ型感光性樹脂組成物における撥インク剤(E2)は、上述した加水分解性シラン化合物の混合物を加水分解し、部分縮合させる(以下、「反応工程」ともいう。)ことで製造できる。加水分解及び部分縮合は、上述の通り、加水分解性基の加水分解反応によるシラノール基の生成とシラノール基同士の脱水縮合反応によるシロキサン結合を生成する反応である。反応工程には、加水分解性シラン化合物を加水分解縮合させる反応に通常用いる反応条件を、特に制限なく適用することができる。例えば、水、触媒、有機溶媒等を用いることができる。
撥インク剤(E2)は、上述した加水分解性シラン化合物を含む混合物を、加水分解及び縮合反応させることで製造できる。該反応には、通常用いられる塩酸、硫酸、硝酸、リン酸等の無機酸、酢酸、シュウ酸、マレイン酸等の有機酸を触媒として用いるのが好ましく、塩酸、硫酸、硝酸等が特に好ましい。用いる触媒の量としては、加水分解性シラン化合物を含む混合物の全量に対して、0.01~10質量%が好ましく、0.1~1質量%が特に好ましい。該反応には溶媒を用いてもよい。溶媒としては、有機溶媒が好ましく、有機溶媒としては、上述した撥インク剤(E1)の合成で使用可能な溶媒等が使用できる。有機溶媒は1種を単独で用いても2種以上を併用してもよい。
反応工程において、有機溶媒の量は、加水分解性シラン化合物の混合物の100質量部に対して、25~9,900質量部が好ましく、100~1,900質量部が特に好ましい。
本発明におけるネガ型感光性樹脂組成物は、通常溶媒(F)を含有する。ネガ型感光性樹脂組成物が溶媒(F)を含むと、ネガ型感光性樹脂組成物の粘度が低減するため、ネガ型感光性樹脂組成物の基材上への塗布がしやすい。よって、均一なネガ型感光性樹脂組成物の塗膜が形成できる。なお、ネガ型感光性樹脂組成物が溶媒(F)を含まない場合には、ネガ型感光性樹脂組成物の塗膜が、ネガ型感光性樹脂組成物の膜と同じものとなる。
このような各種有機溶媒から、ネガ型感光性樹脂組成物の種類や基板への塗工方法等により、それぞれ求められる性能を有する溶媒が適宜選択され、溶媒(F)として用いられる。
R51O(C2H4O)sR52 (5)
式(5)中、R51は、炭素原子数が1~10のアルキル基、R52は、炭素原子数が2~10のアルキル基をそれぞれ示し、sは1~10の整数を示す。
化合物(5)としては、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジエチレングリコールエチルイソプロピルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールブチルエチルエーテル等が挙げられる。
式(5)中、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールイソプロピルメチルエーテルが好ましく、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテルが特に好ましい。
本発明におけるネガ型感光性樹脂組成物は、必要に応じて微粒子(G)を含んでいてもよい。ネガ型感光性樹脂組成物が微粒子(G)を含むことにより、ネガ型感光性樹脂組成物から得られる隔壁は、熱垂れが防止された耐熱性に優れる隔壁となる。
微粒子(G)としては、各種無機系、有機系の微粒子が使用可能であるが、塩基性高分子分散剤を吸着能の点から、マイナスに帯電しているものが好ましく用いられる。
微粒子(G)の粒子径は、隔壁の表面平滑性が良好となることから、平均粒子径が1μm以下であることが好ましく、200nm以下が特に好ましい。
本発明におけるネガ型感光性樹脂組成物は、必要に応じてシランカップリング剤(H)を含んでいてもよい。ネガ型感光性樹脂組成物がシランカップリング剤(H)を含むことで、ネガ型感光性樹脂組成物から形成される硬化膜の基材密着性を向上させることができる。
シランカップリング剤(H)の具体例としては、テトラエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、ヘプタデカフルオロオクチルエチルトリメトキシシラン、ポリオキシアルキレン鎖含有トリエトキシシラン、イミダゾールシラン等が挙げられる。これらは1種を用いても2種以上を併用してもよい。
本発明におけるネガ型感光性樹脂組成物は、必要に応じて熱硬化剤(I)を含んでいてもよい。ネガ型感光性樹脂組成物が熱硬化剤(I)を含むことで、隔壁の耐熱性及び耐透水性を向上させることができる。
熱硬化剤(I)としては、アミノ樹脂、2個以上のエポキシ基を有する化合物、2個以上のヒドラジノ基を有する化合物、ポリカルボジイミド化合物、2個以上のオキサゾリン基を有する化合物、2個以上のアジリジン基を有する化合物、多価金属類、2個以上のメルカプト基を有する化合物、ポリイソシアネート化合物等が挙げられる。中でも、形成された隔壁の耐薬品性が向上する点から、アミノ樹脂、2個以上のエポキシ基を有する化合物、2個以上のオキサゾリン基を有する化合物が特に好ましい。
本発明におけるネガ型感光性樹脂組成物は、必要に応じてリン酸化合物(J)を含んでいてもよい。ネガ型感光性樹脂組成物がリン酸化合物(J)を含むことで、基材との密着性を向上させることができる。
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。
本発明におけるネガ型感光性樹脂組成物は、必要に応じて、界面活性剤(K)を含んでいてもよい。ネガ型感光性樹脂組成物が界面活性剤(K)を含むことで、硬化膜の厚さが均一になる。
界面活性剤(K)は市販品を用いてもよい。いずれもビックケミー・ジャパン社製の商品名で、BYK-306(ポリエーテル変性ポリジメチルシロキサン:12質量%、キシレン:68質量%、モノフェニルグリコール:20質量%)、BYK-307(ポリエーテル変性ポリジメチルシロキサン)、BYK-323(アラルキル変性ポリメチルアルキルシロキサン)、BYK-320(ポリエーテル変性ポリメチルアルキルシロキサン:52質量%、ホワイトスピリット:43質量%、PGMEA:5質量%)、BYK-350(アクリル系共重合物)等が挙げられる。
本発明におけるネガ型感光性樹脂組成物は、さらに必要に応じて、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、紫外線吸収剤等を使用することができる。
本発明のネガ型感光性樹脂組成物は、アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)を含むアルカリ可溶性樹脂(A)と、黒色有機顔料(B)と、光重合開始剤(C)とを含有する。さらに、必要に応じて、架橋剤(D)、撥インク剤(E)及び溶媒(F)を含有する。さらに、上記の微粒子(G)、熱硬化剤(I)、シランカップリング剤(H)、リン酸化合物(J)、界面活性剤(K)及びその他の添加剤を含有してもよい。
本発明においては、他の成分に比べて配合量が比較的大きく、かつ酸価の調整が容易なアルカリ可溶性樹脂(A)により、ネガ型感光性樹脂組成物の固形分酸価を上記範囲に調整している。例えば、アルカリ可溶性樹脂(A)以外の固形分成分が酸価を有しない場合、酸価が100mgKOH/gのアルカリ可溶性樹脂(A)を、ネガ型感光性樹脂組成物の全固形分に10~50質量%となる量配合することで、上記本発明のネガ型感光性樹脂組成物の固形分酸価を10~50mgKOH/gに調整できる。
本発明のネガ型感光性樹脂組成物は、用途や要求特性に合わせて、組成と配合比を選択することが好ましい。
本発明のネガ型感光性樹脂組成物における各種配合成分の好ましい組成を以下に示す。
アルカリ可溶性樹脂(A):以下のアルカリ可溶性樹脂(A1)とアルカリ可溶性樹脂(A2)のみからなり、アルカリ可溶性樹脂(A1)とアルカリ可溶性樹脂(A2)のいずれかの質量平均分子量が10,000以上であり、アルカリ可溶性樹脂(A)としての酸価が10~350mgKOH/gである樹脂であって、ネガ型感光性樹脂組成物における全固形分中に10~60質量%、
(アルカリ可溶性樹脂(A1):ビスフェノールA型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、ビスフェノールF型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、フェノールノボラック型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、クレゾールノボラック型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、トリスフェノールメタン型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、及び上記式(A1-2a)~(A1-2c)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からなる群から選ばれる少なくとも1つの樹脂であって、アルカリ可溶性樹脂(A)の全量に対して85~97質量%、アルカリ可溶性樹脂(A2):主鎖に芳香族環を含まず、分子中に酸性基を有する樹脂から選ばれる少なくとも1つの樹脂であって、アルカリ可溶性樹脂(A)の全量に対して3~15質量%)、
光重合開始剤(C):光重合開始剤(C)の全量に対して、光重合開始剤(C1)を85~100質量%、及び該光重合開始剤(C)の全量に対して光重合開始剤(C2)を0~15質量%含有し、ネガ型感光性樹脂組成物における全固形分中に3.5~7.0質量%、
界面活性剤(K):フッ素系界面活性剤、シリコーン系界面活性剤及びアクリル系界面活性剤からなる群から選ばれる少なくとも1つの界面活性剤であって、ネガ型感光性樹脂組成物における全固形分中に0.05~20質量%。
アルカリ可溶性樹脂(A)、黒色有機顔料(B)、光重合開始剤(C)及び溶媒(F)は組み合わせ1と同様であり、さらに、架橋剤(D)及び/又は撥インク剤(E)を以下の通り配合する。
架橋剤(D):1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物であって、ネガ型感光性樹脂組成物における全固形分中に2~15質量%、
撥インク剤(E):撥インク剤(E1)又は撥インク剤(E2)であって、ネガ型感光性樹脂組成物における全固形分中に0.01~30質量%。
本発明の隔壁は、基板表面に区画を設けるために形成される隔壁であって、上記本発明のネガ型感光性樹脂組成物の硬化膜からなる。
本発明の隔壁は、光学素子の用途に好適に用いられ、上記ネガ型感光性樹脂組成物が黒色着色剤(B)を含有することから、得られる隔壁は、該隔壁が基板表面を複数の区画に仕切るように形成されてなるブラックマトリックスへの適用が可能である。
本発明の隔壁は、例えば、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、光学素子用のブラックマトリックスに適用される。
本発明のネガ型感光性樹脂組成物を用いて、本発明の光学素子用の隔壁を製造する方法としては、例えば、以下の方法が挙げられる。
基板のネガ型感光性樹脂組成物の塗布面は、塗布前に予めアルコール洗浄、紫外線/オゾン洗浄等で洗浄することが好ましい。
また、BOA型のカラーフィルタのように、隔壁をブラックマトリックスの形態でTFTアレイ基板上に形成する場合には、基板表面に予めTFTアレイ等の所定の部材が形成されたものを準備すればよい。
塗布方法としては、膜厚が均一な塗膜が形成される方法であれば特に制限されず、スピンコート法、スプレー法、スリットコート法、ロールコート法、回転塗布法、バー塗布法等、通常の塗膜形成に用いられる方法が挙げられる。
塗膜の膜厚は、最終的に得られる隔壁の高さとネガ型感光性樹脂組成物の固形分濃度を勘案して決められる。塗膜の膜厚は、最終的に得られる隔壁の高さの500~2,000%が好ましく、550~1,000%が特に好ましい。塗膜の膜厚は0.3~100μmが好ましく、1~50μmが特に好ましい。
上記塗膜形成工程で基板表面に形成された塗膜を乾燥し、膜を得る。乾燥によって、塗膜を構成するネガ型感光性樹脂組成物に含まれる溶媒を含む揮発成分が揮発、除去され、粘着性のない膜が得られる。また、ネガ型感光性樹脂組成物が撥インク剤(E)を含有する場合には、該撥インク剤(E)が塗膜表面近傍に移行する。
乾燥方法としては、真空乾燥や加熱乾燥(プリベーク)を採用することが好ましい。また、塗膜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より好ましい。
真空乾燥の条件は、各成分の種類、配合割合等によっても異なるが、10~500Paで10~300秒間行うことが好ましい。
加熱乾燥は、基板とともに塗膜をホットプレート、オーブン等の加熱装置により、50~120℃で10~2,000秒間行うことが好ましい。
得られた膜の一部に所定パターンのマスクを介して露光を行う。露光部のネガ型感光性樹脂組成物は硬化し、未露光部のネガ型感光性樹脂組成物は硬化しない。照射する光としては、可視光、紫外線、遠紫外線、KrFエキシマレーザ、ArFエキシマレーザ、F2エキシマレーザ、Kr2エキシマレーザ、KrArエキシマレーザ、Ar2エキシマレーザ等のエキシマレーザ、X線、電子線等が挙げられる。波長100~600nmの光が好ましく、波長300~500nmの範囲に分布を有する電磁波がより好ましく、i線(365nm)、h線(405nm)及びg線(436nm)が特に好ましい。
照射装置としては、公知の超高圧水銀灯等を用いることができる。露光量は、5~1,000mJ/cm2が好ましく、50~400mJ/cm2が特に好ましい。露光量が上記範囲の下限値以上であると、ネガ型感光性樹脂組成物の硬化が充分である。上記範囲の上限値以下であると、高い解像度が得られる。
現像液により現像し、未露光部分のネガ型感光性樹脂組成物の膜を除去する。アルカリ現像液としては、無機アルカリ類、アミン類、アルコールアミン類、第4級アンモニウム塩等のアルカリ類を含むアルカリ水溶液を用いることができる。またアルカリ現像液には、溶解性の向上や残渣除去のために、界面活性剤やアルコール等の有機溶媒を添加することができる。
現像時間(現像液に接触させる時間)は、5~180秒間が好ましい。また現像方法は液盛り法、ディッピング法、シャワー法等が挙げられる。現像後、高圧水洗や流水洗浄を行い、圧縮空気や圧縮窒素で風乾させることによって、基板上の水分を除去できる。
ここで、現像処理に用いたアルカリ現像液は、通常、フィルタ処理等の後、現像に再利用される。本発明のネガ型感光性樹脂組成物においては、アルカリ現像液中においても、該組成物が含有する黒色有機顔料(B)が良好な分散性を有するように、固形分成分に上記特徴を持たせたものであり、黒色有機顔料(B)の凝集・沈降等によるフィルタの目詰まりが生じず、生産性の向上に寄与することが可能である。
次に、必要に応じてポスト露光を行ってもよい。ポスト露光は隔壁が形成されている表面、又は隔壁が形成されていない裏面(基板側)のいずれから行ってもよい。また、表裏両面から露光してもよい。好ましい露光量としては、50mJ/cm2以上であり、200mJ/cm2以上がより好ましく、1,000mJ/cm2以上がさらに好ましく、2,000mJ/cm2以上が特に好ましい。
続いて、隔壁を加熱することが好ましい。ホットプレート、オーブンなどの加熱装置により、5~90分間加熱処理をすることによって、隔壁及び隔壁で区分された領域(ドット)とからなるパターンが形成される。
加熱温度は150~250℃が好ましく、180~250℃が特に好ましい。加熱温度が上記範囲の下限値以上であると、隔壁の硬化が充分であり、充分な耐薬品性が得られ、その後の画素を形成する際にインクを塗布した場合に、そのインクに含まれる溶媒により隔壁が膨潤したり、インクが滲んでしまうことがない。上記範囲の上限値以下であると、隔壁の熱分解が生じにくい。
本発明のカラーフィルタは、微細なラインパターンに微小なコンタクトホールが形成された隔壁をブラックマトリックスの形態で採用していることから、このカラーフィルタをTFTアレイ基板上に形成すれば、低消費電力で高輝度を有する液晶表示装置が得られる。
ネガ型感光性樹脂組成物として撥インク剤(E)を含有しない組成物を用いた場合、上記のように基板表面に隔壁を、該隔壁が基板表面を複数の区画に仕切るように形成されてなるブラックマトリックスの形態で形成した後、この隔壁表面に、透明着色感光性樹脂組成物からなるインクを用いて、隔壁と同様な方法(フォトリソグラフィ法)で、隔壁間に位置するように画素を形成して、カラーフィルタを製造する。
バインダー樹脂成分としては、透明で耐熱性に優れた樹脂が好ましく、アクリル樹脂、メラミン樹脂、ウレタン樹脂等が挙げられる。水性のインクは、溶剤として水及び必要に応じて水溶性有機溶媒を含み、バインダー樹脂成分として水溶性樹脂又は水分散性樹脂を含み、必要に応じて各種助剤を含む。また、油性のインクは、溶剤として有機溶剤を含み、バインダー樹脂成分として有機溶剤に可溶な樹脂を含み、必要に応じて各種助剤を含む。
画素の形状は、ストライプ型、モザイク型、トライアングル型、4画素配置型等の公知のいずれの配列とすることも可能である。なお、本発明のカラーフィルタをTFTアレイ基板表面に形成する場合には、上記隔壁は、この画素の形状とTFTアレイ基材表面のTFTアレイの位置関係を考慮して設定された所定の位置に所定の形状で形成される。
バインダー樹脂成分としては、透明で耐熱性に優れた樹脂が好ましく、アクリル樹脂、メラミン樹脂、ウレタン樹脂等が挙げられる。水性のインクは、溶剤として水及び必要に応じて水溶性有機溶媒を含み、バインダー樹脂成分として水溶性樹脂又は水分散性樹脂を含み、必要に応じて各種助剤を含む。また、油性のインクは、溶剤として有機溶剤を含み、バインダー樹脂成分として有機溶剤に可溶な樹脂を含み、必要に応じて各種助剤を含む。
なお、インクジェット法においては、上記インクジェット装置でドットにインクを注入した後、ドット内に形成されたインク層に対して、必要に応じて、乾燥、加熱硬化、紫外線硬化等の処理を行うことで画素が形成される。
さらに必要に応じて、カラーフィルタを用いて製造される液晶パネル等の高品位化のためにフォトスペーサ(Photo Spacer)を隔壁上に形成することが好ましい。
隔壁を形成する前に、ガラス等の透明基板にスズドープ酸化インジウム錫(ITO)等の透明電極をスパッタ法等によって製膜し、必要に応じて所望のパターンに透明電極をエッチングする。
ネガ型感光性樹脂組成物として撥インク剤(E)を含有しない組成物を用いた場合、上記のように基板表面に隔壁を形成した後、蒸着法によって必要に応じ正孔注入層、必要に応じ正孔輸送層、発光層、必要に応じ正孔阻止層、必要に応じ電子輸送層、必要に応じ電子注入層などを形成する。その後,アルミニウム等の電極を蒸着法等によって形成することによって、有機EL素子の画素が得られる。
なお、例1~13及び例17~19が実施例であり、例14~16が比較例である。
(数平均分子量(Mn)及び質量平均分子量(Mw))
ゲルパーミエーションクロマトグラフィー法(東ソー社製、装置名:HLC-8220GPC)により、ポリスチレンを標準物質として測定した。
測定条件;
(撥インク剤(E)中のフッ素原子の含有率、エチレン性二重結合の量、酸価)
撥インク剤(E)中のフッ素原子の含有率は、1,4-ジトリフルオロメチルベンゼンを標準物質として、19F NMR測定(日本電子社製、装置名:JNM-AL300、溶媒:重アセトン)により算出した。
撥インク剤(E)中のエチレン性二重結合の量は、1,4-ジトリフルオロメチルベンゼンを標準物質として、1H NMR測定により算出した。
撥インク剤(E)の酸価(mgKOH/g)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。
合成例及び実施例で用いた化合物の略語は以下の通りである。
(アルカリ可溶性樹脂(A1))
ZAR2001:ビスフェノールA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(日本化薬社製、商品名:ZAR-2001H、質量平均分子量(Mw):16,000、固形分酸価:100mgKOH/g、固形分:70質量%、PGMEA:30質量%)。
ZCR1642:上式(A1-2a)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(日本化薬社製、商品名:ZCR-1642H、質量平均分子量(Mw):5,800、固形分酸価:100mgKOH/g、固形分:70質量%、PGMEA:30質量%)。
ZFR1492:ビスフェノールF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(日本化薬社製、商品名:ZFR-1492H、質量平均分子量(Mw):23,000、固形分酸価:100mgKOH/g、固形分:65質量%、PGMEA:35質量%)。
CCR1159:クレゾールノボラック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(日本化薬社製、商品名:CCR-1159H、質量平均分子量(Mw):7,400、固形分酸価:100mgKOH/g、固形分:65質量%、PGMEA:35質量%)。
EA7440:クレゾールノボラック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(新中村化学工業社製、商品名:EA-7440、質量平均分子量(Mw):4,000、固形分酸価:40.5mgKOH/g、固形分:60質量%、PGMEA:40質量%)。
UC3080:スチレンとアクリル酸をスチレン:アクリル酸のモル比で62:38の割合で共重合した樹脂(東亜合成社製、商品名:UC-3080、質量平均分子量(Mw):14,000、酸価:230mgKOH/g、固形分:100質量%)。
UC3900:スチレンとアクリル酸をスチレン:アクリル酸のモル比で81:19の割合で共重合した樹脂(東亜合成社製、商品名:UC-3900、質量平均分子量(Mw):4,600、酸価:108mgKOH/g、固形分:100質量%)。
MSP9612:N-フェニルマレイミドとベンジルメタクリレートとメタクリル酸とスチレンを共重合した樹脂(新中村化学社製、商品名:MSP-9612、質量平均分子量(Mw):26,000、固形分酸価:32mgKOH/g、固形分:30質量%、PGMEA:70質量%)。
MSP9610:N-フェニルマレイミドとベンジルメタクリレートとメタクリル酸とスチレンを共重合した樹脂(新中村化学社製、商品名:MSP-9610、質量平均分子量(Mw):28,000、固形分酸価:75mgKOH/g、固形分:30質量%、PGMEA:70質量%)。
DINA:黒色有機顔料のPGMEA分散液(DIC社製、商品名:DINA混色BM、有彩色の有機顔料混合物(黒色):15質量%、高分子分散剤:4.5質量%、PGMEA:80.5質量%、固形分酸価:0mgKOH/g)。
S2961:黒色有機顔料のPGMEA分散液(大日精化工業社製、商品名:S2961、アゾメチン系黒色有機顔料:12質量%、高分子分散剤:7.2質量%、PGMEA:80.8質量%、固形分酸価:7.2mgKOH/g)。
OXE01:1.2-オクタンジオン,1-[4-(フェニルチオ)フェニル]-,2-(0-ベンゾイルオキシム)(式(1)で表される化合物において、R1:フェニル基、R2:ヘキシル基で示される。BASF社製、商品名:OXE01)。
(光重合開始剤(C2))
OXE02:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)(式(2)で表される化合物において、R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、及びR9:水素原子、R7:2-メチルベンゾイル基で示される。BASF社製、商品名:OXE02。)。
(架橋剤(D))
UX5002:多官能ウレタンアクリレートオリゴマー(日本化薬社製、商品名:KAYARAD UX-5002D-P20、固形分:80質量%、PGMEA:20質量%)。
(界面活性剤(K))
BYK-307:商品名(ビックケミー・ジャパン社製。ポリエーテル変性ポリジメチルシロキサン)。
MEK:2-ブタノン。
C6FMA:CH2=C(CH3)COOCH2CH2(CF2)6F(単量体(a1)に該当する。)。
MAA:メタクリル酸(単量体(a4)に該当する。)。
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。)(単量体(a5)の化合物(51)に該当する。)。
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。)(単量体(a5)の化合物(51)に該当する。)。
2-HEMA:2-ヒドロキシエチルメタクリレート(単量体(a3)に該当する。)。
V-65:アゾ系重合開始剤(和光純薬工業社製、商品名:V-65)。
AOI:2-アクリロイルオキシエチルイソシアネート(昭和電工社製、商品名:カレンズAOI)(化合物(z1)に該当する。)。
DBTDL:ジブチル錫ジラウレート。
BHT:2,6-ジ-t-ブチル-p-クレゾール。
(撥インク剤(E2)の合成に用いた化合物)
化合物(e2-1-1):F(CF2)6CH2CH2Si(OCH3)3(旭硝子社製)。
化合物(e2-2-1):Si(OCH2CH3)4(コルコート社製)。
化合物(e2-3-1):CH2=CHCOO(CH2)3Si(OCH3)3(東京化成工業社製)。
1官能性のシラン化合物(1):トリメチルメトキシシラン、(CH3)3Si(OCH3)(東京化成工業社製)。
PGME:プロピレングリコールモノメチルエーテル。
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。
(溶媒(F))
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。
以下の方法で撥インク剤(E1)に分類される撥インク剤(E1-1)を合成した。
撹拌機を備えた内容積2L(リットル)のオートクレーブに、MEK(700g)、C6FMA(140g)、MAA(15g)、PME400(60g)、2-HEMA(85g)及び重合開始剤V-65(2g)を仕込み、窒素ガス中で撹拌しながら、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をヘキサンに加えて再沈精製した後、真空乾燥し、共重合体1(242g)を得た。
該共重合体1は、数平均分子量(Mn)が35,000、質量平均分子量(Mw)が91,000であった。
温度計、撹拌機、加熱装置を備えた内容量300mLのガラス製フラスコに、共重合体1(40g)、AOI(12g)、DBTDL(0.05g)、BHT(0.2g)及びMEK(130g)を仕込み、撹拌しながら、40℃で24時間反応させ、撥インク剤(E1-1)の溶液を得た。得られた撥インク剤(E1-1)のMEK溶液をヘプタンに加え再沈精製し、真空乾燥し、撥インク剤(E1-1)(65.6g)を得た。数平均分子量(Mn)は38,000であった。撥インク剤(E1-1)の赤外分光分析を行ったところ、アクリロイル基のC=C伸縮振動に由来する吸収帯(1,635cm-1)、アクリロイル基のCH2面内変角振動に由来する吸収帯(1,409cm-1)、及びアクリロイル基のCH2面外変角振動に由来する吸収帯(810cm-1)が存在すること、またAOIのNCO伸縮振動に由来する吸収帯(2,274cm-1)が消失していたことから、撥インク剤(E1-1)中にアクリロイル基が存在することが確認された。
得られた撥インク剤(E1-1)の質量平均分子量(Mw)、数平均分子量(Mn)、フッ素原子の含有率、エチレン性二重結合の量(C=C量、×10-3mol/g)、酸価(mgKOH/g)を表1に示した。
得られた撥インク剤(E1-1)とPGMEAを質量比で1:9の割合で混合した撥インク剤溶液(E1-11)を調製し、以下の各例に用いた。
以下の方法で、撥インク剤(E1)に分類される撥インク剤(E1-2)を合成した。
共重合体1の合成において、原料の配合を表1のように変更した以外は同様の共重合反応により、共重合体2を得た。次に、撥インク剤(E1-1)の合成において、原料の配合を表1のように変更した以外は同様の反応により、撥インク剤(E1-2)を得た。得られた撥インク剤(E1-2)の質量平均分子量(Mw)、数平均分子量(Mn)、フッ素原子の含有率、エチレン性二重結合の量(C=C量、×10-3mol/g)、酸価(mgKOH/g)を表1に示した。
上記で得られた撥インク剤(E1-2)とPGMEAを質量比で1:9の割合で混合した撥インク剤溶液(E1-21)を調製し、以下の各例に用いた。
以下の方法で、撥インク剤(E2)に分類される撥インク剤(E2-1)を合成した。
撹拌機を備えた1,000cm3の三口フラスコに、化合物(e2-1-1)の11.8g、化合物(e2-2-1)の29.4g、化合物(e3-1-1)の29.4g、及び1官能性のシラン化合物(1)の29.4gを入れて、加水分解性シラン化合物の混合物を得た。次いで、該混合物にPGMEAの564.7gを入れて、溶液(原料溶液)とした。
得られた原料溶液に、40℃で、撹拌しながら、1.0質量%塩酸水溶液を52.0g滴下した。滴下終了後、40℃で5時間撹拌して、撥インク剤(E2-1)をPGMEA溶液(撥インク剤(E2-1)濃度:10質量%。以下、「(E2-1)液」という。)として得た。なお、反応液中の成分をガスクロマトグラフィを使用して測定し、原料としての各化合物が検出限界以下になったことを確認した。
得られた撥インク剤(E2-1)の質量平均分子量(Mw)、数平均分子量(Mn)、フッ素原子の含有率を、撥インク剤(E2-1)の仕込み組成(モル%)とともに表2に示す。
以下の方法で、撥インク剤(E2)に分類される撥インク剤(E2-1)を合成した。
撹拌機を備えた1,000cm3の三口フラスコに、化合物(e2-1-1)の16.7g、化合物(e2-2-1)の41.7g、及び化合物(e3-1-1)の41.7gを入れて、加水分解性シラン化合物の混合物を得た。次いで、該混合物にPGMEの564.7gを入れて、溶液(原料溶液)とした。
得られた原料溶液に、40℃で、撹拌しながら、1.0質量%硝酸水溶液を65.7g滴下した。滴下終了後、40℃で5時間撹拌して、撥インク剤(E2-2)をPGME溶液(撥インク剤(E2-2)濃度:10質量%。以下、「(E2-2)液」という。)として得た。なお、反応液中の成分をガスクロマトグラフィを使用して測定し、原料としての各化合物が検出限界以下になったことを確認した。
得られた撥インク剤(E2-2)の質量平均分子量(Mw)、数平均分子量(Mn)、フッ素原子の含有率を、撥インク剤(E2-2)の仕込み組成(モル%)とともに表2に示す。
表3及び表4に示す割合で、アルカリ可溶性樹脂(A1)(溶媒としてPGMEAを30~40質量%含む。)、アルカリ可溶性樹脂(A2)(溶媒としてPGMEAを0~70質量%含む。)、黒色有機顔料(B)(溶媒としてPGMEAを80.5~80.8質量%含む。)、光重合開始剤(C1)、光重合開始剤(C2)、架橋剤(D)(溶媒としてPGMEAを20質量%含む。)、撥インク剤(E)(溶媒としてPGMEA又はPGMEを90質量%含む。)、溶媒(F)及び界面活性剤(K)を、常温下、撹拌機を備えたセパラブルフラスコ中で配合し、ネガ型感光性樹脂組成物を得た。
ガラス基板(旭硝子社製、商品名:AN100、横×縦(7.5mm×7.5mm)、厚さ0.7mm)上にスピンナー(ミカサ社製、装置名:MS-A200)を用いてネガ型感光性樹脂組成物を塗布し、塗膜を形成した(塗膜形成工程)。次に、100℃、2分間ホットプレート上で乾燥し、膜厚3μmの膜を形成したガラス基板(1)を得た(乾燥工程)。なお、ガラス基板(1)については、光学濃度及び現像性の評価用と以下のパターン形成用の複数枚を製造した。
次いで、未露光部分を無機アルカリタイプ現像液(横浜油脂工業社製、商品名:セミクリーンDL-A4の10倍希釈水溶液)に1分間浸漬して現像し、未露光部を水により洗い流し、乾燥させた(現像工程)。
次いで、ホットプレート上、220℃で1時間加熱することにより、パターン(ブラックマトリックス)が形成されたガラス基板(2)を得た(ポストベーク工程)。これらについて、パターン形成性、現像性、撥インク性を以下に示す方法で測定、評価した。評価結果を表3及び表4に示す。
上記ガラス基板(1)の表面から剥がした膜の80mgを、上記現像工程で用いたアルカリ現像液と同等のアルカリ濃度のNaHCO3水溶液(1質量%)の25gに溶解し24時間静置後、目視で沈殿物の有無を観察した。沈殿物が観察されなかったものを○(良好)、観察されたものを×(不良)とした。
(光学濃度)
上記ガラス基板(1)について、伊原電子工業社製のIhca-T5にて、光学濃度を測定した。膜厚3μmで光学濃度が3以上のものを○(良好)、3未満のものを×(不良)とした。
上記ガラス基板(2)について、幅10μm、長さ10mmの線状のパターンが残ったものを○(良好)、残らなかったものを×(不良)としてパターンの有無を評価した。
(コンタクトホール解像度)
上記ガラス基板(2)について、隔壁上部における直径が20μmの円形の空孔が現像により、底部において残渣等残らずに直径1μm以上で貫通したものを○(良好)、貫通しなかったものを×(不良)として、パターンの有無を評価した。
撥インク性は、上記ガラス基板(2)上の硬化膜のPGMEAの接触角(度)により評価した。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、液体を含む方の角度で定義した。この角度が大きいほど硬化膜の撥インク性が優れることを意味する。PGMEAの接触角35度以上を○(良好)、35度未満を×(不良)とした。
接触角の測定は、Kruss社製のDSA10により行った。
上記ネガ型感光性樹脂組成物を調製後、5℃で3ヶ月間静置保管した。保管後のネガ型感光性樹脂組成物の上層と下層から採取した液により上記ガラス基板(1)と同様に膜を作製し、その光学濃度が0.5以下であるものを○(良好)、0.5を超えるものを×(不良)とした。
また、該ネガ型感光性樹脂組成物から微細な線幅のパターンが形成でき、特に微小なコンタクトホールの形成も可能であった。さらに、該ネガ型感光性樹脂組成物から形成された硬化膜の撥インク性も良好であった。
一方、固形分中の酸価が10mgKOH/g未満である例14は、アルカリ現像液中で黒色有機顔料(B)の沈降が見られた。また、アルカリ可溶性樹脂(A1)のみを用いた例16においても、沈降が見られた。これは、アルカリ可溶性樹脂(A)により黒色有機顔料(B)が充分に被覆されていないためと推定している。
アルカリ可溶性樹脂(A2)のみを用いた例15では、ライン及びコンタクトホールの解像度が不良であった。これは、アルカリ可溶性樹脂(A1)を用いないことで形状保持が困難であるためと推定している。
また、本発明のネガ型感光性樹脂組成物は、黒色有機顔料を含む固形分のアルカリ現像液への溶解性・分散性に優れることから、アルカリ現像液のリサイクル利用性が増大し、生産性の向上に寄与することが可能となり、産業上の利用可能性が高い。
なお、2011年11月11日に出願された日本特許出願2011-247437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。
Claims (15)
- 主鎖に芳香族環を含み、分子中に酸性基とエチレン性二重結合とを有するアルカリ可溶性樹脂(A1)と、主鎖に芳香族環を含まず、分子中に酸性基を有するアルカリ可溶性樹脂(A2)と、黒色有機顔料(B)と、光重合開始剤(C)とを含有するネガ型感光性樹脂組成物であって、該組成物における固形分酸価が10~50mgKOH/gであることを特徴とするネガ型感光性樹脂組成物。
- 前記ネガ型感光性樹脂組成物における全固形分中のアルカリ可溶性樹脂(A1)とアルカリ可溶性樹脂(A2)の合計の含有割合が、5~80質量%である、請求項1に記載のネガ型感光性樹脂組成物。
- 前記ネガ型感光性樹脂組成物における全固形分中の黒色有機顔料(B)の含有割合が、20~65質量%である、請求項1又は2に記載のネガ型感光性樹脂組成物。
- 前記アルカリ可溶性樹脂(A1)及びアルカリ可溶性樹脂(A2)のいずれかの質量平均分子量が10,000以上である、請求項1~3のいずれか一項に記載のネガ型感光性樹脂組成物。
- 前記光重合開始剤(C)が下式(1)で表される化合物を含む、請求項1~4のいずれか一項に記載のネガ型感光性樹脂組成物。
R2は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基又はベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基を示す。 - 前記光重合開始剤(C)の全量中の前記式(1)で表される化合物の含有割合が、85~95質量%であり、前記ネガ型感光性樹脂組成物の全固形分量中の前記光重合開始剤(C)の含有割合が、3.5~7質量%である請求項5に記載のネガ型感光性樹脂組成物。
- 架橋剤(D)をさらに含み、該架橋剤(D)が1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、請求項1~6のいずれか一項に記載のネガ型感光性樹脂組成物。
- 撥インク剤(E)をさらに含む、請求項1~7のいずれか一項に記載のネガ型感光性樹脂組成物。
- 前記撥インク剤(E)が、1分子中に下式(3)で表される基又は下式(4)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とを有する撥インク剤(E)である、請求項8に記載のネガ型感光性樹脂組成物。
-CFXRf (3)
式(3)中、Xは水素原子、フッ素原子、又はトリフルオロメチル基を示し、Rfはエーテル性酸素原子を有していてもよい炭素原子数1~20のフルオロアルキル基、又はフッ素原子を示す。
-(SiR10R11O)n-SiR12R13R14 (4)
式(4)中、R10、R11、R12及びR13は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、又はアリール基を示し、R14は、水素原子、又は炭素原子数1~10のエーテル性酸素原子もしくは窒素原子を含んでいてもよいアルキル基を示し、nは1~200の整数を示す。 - 前記撥インク剤(E)が、側鎖に基(3)を有し、主鎖がオルガノポリシロキサン鎖の化合物である、請求項8に記載のネガ型感光性樹脂組成物。
-CFXRf (3)
式(1)中、Xは水素原子、フッ素原子、又はトリフルオロメチル基を示し、Rfは、エーテル性酸素原子を有していてもよい炭素原子数1~20のフルオロアルキル基、又はフッ素原子を示す。 - 溶媒(F)をさらに含む、請求項1~10のいずれか一項に記載のネガ型感光性樹脂組成物。
- 画素形成用に基板表面を複数の区画に仕切るように形成した隔壁であって、請求項1~10のいずれか一項に記載のネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
- 請求項12に記載の隔壁が、基板表面を複数の区画に仕切るように形成されてなるブラックマトリックス。
- 前記隔壁が、該隔壁の膜厚方向に貫通する貫通孔を有し、該貫通孔における水平方向の最大孔径が20μm以下であり、最小孔径が1μm以上である請求項13に記載のブラックマトリックス。
- 基板表面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光学素子であって、前記隔壁が請求項13又は14に記載のブラックマトリックスからなることを特徴とする光学素子。
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CN103946747B (zh) | 2018-06-05 |
TW201329635A (zh) | 2013-07-16 |
JP6115471B2 (ja) | 2017-04-19 |
CN103946747A (zh) | 2014-07-23 |
KR101921368B1 (ko) | 2018-11-22 |
KR20140097117A (ko) | 2014-08-06 |
JPWO2013069789A1 (ja) | 2015-04-02 |
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