CN114450630A - Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device - Google Patents

Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device Download PDF

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CN114450630A
CN114450630A CN202080067602.2A CN202080067602A CN114450630A CN 114450630 A CN114450630 A CN 114450630A CN 202080067602 A CN202080067602 A CN 202080067602A CN 114450630 A CN114450630 A CN 114450630A
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山川朋子
利光惠理子
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Mitsubishi Chemical Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Abstract

The invention provides a photosensitive resin composition capable of ensuring sufficient ink repellency even under low exposure. The photosensitive resin composition of the present invention contains: (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent, wherein the alkali-soluble resin (C) contains an alkali-soluble resin (C-1) having a partial structure represented by the general formula (C1), and the liquid repellent (D) contains a fluorine-containing resin having a crosslinking group. (in the formula (c1), Rc11Represents a hydrogen atom or a methyl group, Rc12Represents an optionally substituted 2-valent hydrocarbon group, n represents an integer of 2 or 3, and the benzene ring in the formula (c1) is optionally further substituted with an optional substituent, each represents a bonding arm. )

Description

Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device
Technical Field
The present invention relates to a photosensitive resin composition, and further relates to a cured product obtained by curing the photosensitive resin composition; a partition wall formed of a cured product; organic electroluminescent element, color filter and image display device having partition walls.
The present application claims priority based on japanese patent application No. 2019-201108, filed in japan on 11/6/2019, the contents of which are incorporated herein by reference.
Background
In recent years, in order to reduce power consumption and widen a color gamut of a display, a color filter in which a pixel is formed using luminescent nanocrystal particles such as quantum dots has been studied.
As a method for manufacturing a color filter, a photolithography method and an inkjet method are known, and the latter method can reduce the loss of ink materials (see, for example, patent document 1).
In the case of manufacturing a color filter including luminescent nanocrystal particles by an ink jet method, an ink including luminescent nanocrystal particles is ejected to a region (pixel portion) surrounded by a partition wall prepared in advance to form a pixel.
In addition, an organic electroluminescent element used in an organic electroluminescent display or the like is manufactured by forming partition walls (banks) on a substrate and laminating various functional layers in regions surrounded by the partition walls. An ink jet method is known as a method of stacking a functional layer in the partition walls.
In both of the partition walls for color filters and the partition walls for organic electroluminescent elements, which contain luminescent nanocrystal particles, when ink is ejected by ink jet, it is necessary to prevent mixing of ink between adjacent pixel portions, and the like, and high ink repellency is required.
As a material for forming partition walls having ink repellency by photolithography, patent document 2 describes that a colored photosensitive resin composition having high ink repellency and good linearity is obtained by using two specific alkali-soluble resins in combination.
Patent documents 3 and 4 describe photosensitive resin compositions containing a specific resin.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2019-086745
Patent document 2: international publication No. 2019/146685
Patent document 3: japanese patent laid-open publication No. 2016-047919
Patent document 4: japanese patent laid-open publication No. 2017-190403
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted studies and found that it is difficult to secure sufficient ink repellency in a case where the exposure amount of the photosensitive resin composition described in patent document 2 is low.
On the other hand, patent documents 3 and 4 do not describe a liquid repellent, and are not clear about ink repellency when a liquid repellent is used.
Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of ensuring sufficient ink repellency even at a low exposure amount.
Another object of the present invention is to provide a cured product obtained by curing the photosensitive resin composition, a partition wall formed of the cured product, and an image display device including the partition wall.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific alkali-soluble resin in a photosensitive resin composition containing a liquid repellent, and have completed the present invention.
That is, the gist of the present invention is as follows.
[1] A photosensitive resin composition comprising: (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent,
the alkali-soluble resin (C) contains an alkali-soluble resin (C-1) having a partial structure represented by the general formula (C1),
the liquid repellent (D) contains a fluorine atom-containing resin having a crosslinking group,
[ chemical formula 1]
Figure BDA0003564604270000031
(in the formula (c1), Rc11Represents a hydrogen atom or a methyl group,
Rc12represents a 2-valent hydrocarbon group optionally having a substituent,
n represents an integer of 2 or 3,
the benzene ring in formula (c1) is optionally further substituted with an optional substituent,
each represents a bond arm. )
[2]Above-mentioned [1]The photosensitive resin composition, wherein, in the general formula (c1), Rc12Is a group represented by the following general formula (c 1-1).
[ chemical formula 2]
Figure BDA0003564604270000032
[3] The photosensitive resin composition according to [1] or [2], wherein a content ratio of the alkali-soluble resin (C-1) in the alkali-soluble resin (C) is 60% by mass or more.
[4] The photosensitive resin composition according to any one of the above [1] to [3], further comprising (E) a colorant.
[5] The photosensitive resin composition according to item [4], wherein the content of the colorant (E) is 50% by mass or less in the entire solid content of the photosensitive resin composition.
[6] The photosensitive resin composition according to [4] or [5], wherein the colorant (E) contains at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.
[7] The photosensitive resin composition according to any one of the above [4] to [6], wherein the colorant (E) contains a violet pigment.
[8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7 ].
[9] A partition wall comprising the cured product according to [8 ].
[10] An organic electroluminescent element comprising the partition wall as recited in [9 ].
[11] A color filter comprising luminescent nanocrystal particles, comprising the partition wall according to [9 ].
[12] An image display device comprising the partition wall as recited in [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive resin composition capable of ensuring sufficient ink repellency even at a low exposure amount can be provided.
Drawings
FIG. 1 is a schematic cross-sectional view of an example of a color filter having barrier ribs according to the present invention.
Description of the symbols
1 green luminescent nanocrystalline particles
2 red-emitting nanocrystalline particles
10 substrate
20 partition wall
30 red pixel
40 green pixel
50 blue pixel
100 color filter
Detailed Description
The present invention will be described in detail below. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these embodiments within the scope not exceeding the gist thereof.
In the present invention, "(meth) acryloyl group" means "either or both of an acryloyl group and a methacryloyl group", and "all solid components" means all components except the solvent in the photosensitive resin composition. In the present invention, the numerical range expressed by using "to" means a range including numerical values described before and after "to" as the lower limit value and the upper limit value thereof.
In the present invention, the meaning of the "(co) polymer" includes both a homopolymer (homopolymer) and a copolymer (copolymer), and the meaning of the "acid (anhydride)", "… acid (anhydride)" includes both an acid and an anhydride thereof.
In the present invention, the partition wall material refers to a dam material, a wall material, and similarly, the partition wall refers to a dam, a wall, and a wall.
In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) based on GPC (gel permeation chromatography) and converted to polystyrene.
In the present invention, the acid value is calculated by neutralization titration, and represents an acid value in terms of an effective solid content, unless otherwise specified.
In the present invention, the partition walls are, for example, portions for defining the functional layer (organic layer, light emitting portion) in the active-drive-type organic electroluminescent element, and can be used for forming pixels including the functional layer and the partition walls by discharging ink, which is a material for forming the functional layer, to the defined regions (pixel regions) and drying the ink. The present invention can also be used as a portion for dividing a pixel portion in a color filter including light-emitting nanocrystal particles, and can be used for forming a pixel by ejecting ink to the divided region and drying the ink.
[1] Photosensitive resin composition
The photosensitive resin composition of the present invention contains, as essential components, (a) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent, and may further contain other components as required, for example, (E) a colorant, (F) a dispersant, and the like.
[1-1] Components and compositions of photosensitive resin compositions
The components constituting the photosensitive resin composition of the present invention and the composition thereof will be explained in order.
[1-1-1] (A) component: ethylenically unsaturated compounds
The photosensitive resin composition of the present invention contains (a) an ethylenically unsaturated compound. The inclusion of the ethylenically unsaturated compound (a) is considered to improve the curability of the coating film and improve the ink repellency.
The ethylenically unsaturated compound used herein is a compound having 1 or more ethylenically unsaturated bonds in the molecule, but is preferably a compound having 2 or more ethylenically unsaturated bonds in the molecule from the viewpoints of polymerizability, crosslinkability, and the ability to increase the difference in solubility of the developer between an exposed portion and a non-exposed portion accompanying the polymerizability, and the like, and is more preferably an unsaturated bond derived from a (meth) acryloyloxy group, that is, a (meth) acrylate compound.
In the present invention, a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated bonds in 1 molecule is particularly preferably used. The number of the ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and still more preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 or less. For example, the number of the cells is preferably 2 to 15, more preferably 2 to 10, further preferably 3 to 8, and particularly preferably 5 to 7. When the lower limit value is not less than the above-mentioned lower limit value, the polymerizability is improved and the ink repellency tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the developability tends to be more favorable.
Specific examples of the ethylenically unsaturated compound include: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyol such as an aliphatic polyol or an aromatic polyol with an unsaturated carboxylic acid or a polycarboxylic acid.
Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include: acrylic esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic esters obtained by replacing the acrylic esters of the above exemplified compounds with methacrylic esters, itaconic esters similarly replaced with itaconic esters, crotonic esters similarly replaced with crotonic esters, and maleic esters replaced with maleic esters.
Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: acrylate and methacrylate of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, etc.
Esters obtained by esterification of a polyhydric compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polycarboxylic acid are not necessarily a single compound, and typical examples thereof include: the condensation product of acrylic acid, phthalic acid and ethylene glycol, the condensation product of acrylic acid, maleic acid and diethylene glycol, the condensation product of methacrylic acid, terephthalic acid and pentaerythritol, and the condensation product of acrylic acid, adipic acid, butanediol and glycerol.
Further, as examples of the polyfunctional olefinic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ninghamu chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kasei chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi chemical corporation).
Among these, from the viewpoint of adhesion of the partition walls to the substrate and ink repellency, the ethylenically unsaturated compound (a) is preferably an ester or urethane (meth) acrylate of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tri (meth) acryloyloxymethylethyl phthalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, a dibasic anhydride adduct of dipentaerythritol penta (meth) acrylate, or a dibasic anhydride adduct of pentaerythritol tri (meth) acrylate.
These compounds may be used alone or in combination of two or more.
In the present invention, the molecular weight of the ethylenically unsaturated compound (a) is not particularly limited, and is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less, from the viewpoint of ink repellency and formation of a high-definition partition wall having a fine line width. For example, it is preferably 100 to 1000, more preferably 150 to 1000, further preferably 200 to 1000, further preferably 300 to 700, further preferably 400 to 700, and particularly preferably 500 to 700.
(A) The number of carbon atoms of the ethylenically unsaturated compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably 40 or less, further preferably 35 or less, particularly preferably 30 or less, from the viewpoint of ink repellency and residue suppression. For example, preferably 7 to 50, more preferably 10 to 50, and further preferably "" に and ましい.
From the viewpoint of ink repellency and formation of fine and high-definition partition walls with fine line width, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferred, and among them, from the viewpoint of formation of fine and high-definition partition walls with fine line width, trifunctional or higher ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and anhydride adducts of trifunctional or higher ester (meth) acrylates such as 2,2, 2-tris (meth) acryloyloxymethylethyl phthalate, and dibasic anhydride adducts of dipentaerythritol penta (meth) acrylate are more preferred.
The content of the ethylenically unsaturated compound (a) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and further preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, and further preferably 30% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, even more preferably 10 to 60% by mass, even more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass. When the lower limit is not less than the upper limit, a high-definition partition wall having a narrow line width tends to be formed.
The content of the ethylenically unsaturated compound (a) is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, further particularly preferably 25 parts by mass or more, and most preferably 30 parts by mass or more, and is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, further preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (C). For example, it is preferably 1 to 150 parts by mass, more preferably 5 to 150 parts by mass, further preferably 10 to 100 parts by mass, further preferably 15 to 100 parts by mass, further preferably 20 to 70 parts by mass, particularly preferably 25 to 50 parts by mass, and most preferably 30 to 40 parts by mass. When the lower limit is not less than the lower limit, ink repellency tends to be improved, and when the upper limit is not more than the upper limit, a high-definition partition wall having a narrow line width tends to be formed.
[1-1-2] (B) component: photopolymerization initiator
The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated compound (a) by actinic rays, for example, an ethylenically unsaturated bond of the ethylenically unsaturated compound (a).
The photosensitive resin composition of the present invention can use a photopolymerization initiator generally used in the art as the (B) photopolymerization initiator. Examples of such photopolymerization initiators include: metallocene compounds containing a titanocene compound as described in Japanese patent laid-open Nos. 59-152396 and 61-151197; hexaarylbiimidazole derivatives as described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503
Figure BDA0003564604270000081
Oxadiazole derivatives, halomethyl s-triazine derivatives, N-aryl- α -amino acids such as N-phenylglycine, N-aryl- α -amino acid salts, N-aryl- α -amino acid esters, and other radical activators, α -aminoalkylphenone derivatives; oxime ester compounds described in, for example, Japanese patent application laid-open Nos. 2000-80068 and 2006-36750.
Specifically, for example, as the metallocene compound, there can be mentioned: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5, 6-pentafluorophenyl) titanium, dicyclopentadienyl bis (2,3,5, 6-tetrafluorophenyl) titanium, dicyclopentadienyl bis (2,4, 6-trifluorophenyl) titanium, dicyclopentadienyl bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl bis (2, 4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl [2, 6-difluoro-3- (1-propyl) phenyl ] titanium.
Examples of the diimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, and (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer.
As halomethylation
Figure BDA0003564604270000091
Oxadiazole derivatives, for example: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-
Figure BDA0003564604270000092
Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-
Figure BDA0003564604270000093
Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl) ]-1,3,4-
Figure BDA0003564604270000094
Diazole, 2-trichloromethyl-5-furyl-1, 3,4-
Figure BDA0003564604270000095
Diazole.
Examples of the halomethyl s-triazine derivatives include: 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine.
Examples of α -aminoalkylphenone derivatives include: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone.
The oxime ester compounds are effective as photopolymerization initiators in particular from the viewpoint of sensitivity and platemaking property, and for example, the use of an alkali-soluble resin containing a phenolic hydroxyl group is disadvantageous in terms of sensitivity, and such an oxime ester compound having excellent sensitivity is particularly useful. The oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in combination in its structure, and therefore, it is highly sensitive even in a small amount, stable against thermal reaction, and a photosensitive resin composition having high sensitivity can be obtained in a small amount.
Examples of the oxime ester compounds include compounds represented by the following general formula (IV).
[ chemical formula 3]
Figure BDA0003564604270000101
In the formula (IV), R21aRepresents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
R21bRepresents an optional substituent containing an aromatic ring.
R22aRepresents an alkanoyl group optionally having a substituent, or an aroyl group optionally having a substituent.
n represents an integer of 0 or 1.
R21aThe number of carbon atoms of the alkyl group in (b) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the alkyl group include: methyl, ethyl, propyl, cyclopentylethyl.
Examples of the substituent optionally contained in the alkyl group include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group, N-acetyl-N-acetoxyamino group. The alkyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
As R21aAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, and is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. For example, the amount of the surfactant is preferably 5 to 30, more preferably 5 to 20, and still more preferably 5 to 12.
Specific examples of the aromatic ring group include: of these, phenyl, naphthyl, pyridyl and furyl are preferable, and phenyl or naphthyl is more preferable, and phenyl is even more preferable, from the viewpoint of developability.
Examples of the substituent optionally having an aromatic ring group include: the hydroxyl group, the carboxyl group, the halogen atom, the amino group, the amide group, the alkyl group, the alkoxy group, and the group formed by linking these substituents are preferably an alkyl group, an alkoxy group, and a group formed by linking these substituents, and more preferably an alkoxy group formed by linking these substituents, from the viewpoint of developability.
Of these, R is from the viewpoint of sensitivity21aPreferred is an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
As R21bPreferred examples thereof include optionally substituted carbazolyl groups, optionally substituted thioxanthone groups and optionally substituted diphenylsulfide groups. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.
R22aThe number of carbon atoms of the alkanoyl group in (b) is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of alkanoyl groups include: acetyl, propionyl and butyryl.
Examples of the substituent optionally contained in the alkanoyl group include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, and amide group. The alkanoyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
R22aThe number of carbon atoms of the aroyl group in (2) is not particularly limited, but is preferably 7 or more, more preferably 8 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of aroyl groups include: benzoyl, naphthoyl.
Examples of the substituent optionally contained in the aroyl group include: hydroxyl, carboxyl, halogen atom, amino, amido and alkyl. The aroyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
Of these, R is from the viewpoint of sensitivity22aPreferred is an alkanoyl group optionally having a substituent, more preferred is an unsubstituted alkanoyl group, and further preferred is an acetyl group.
The photopolymerization initiator may be used alone or in combination of two or more. For the purpose of improving the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended as necessary with the photopolymerization initiator. Examples of the sensitizing dye include: JP-A-4-221958, JP-A-4-219756, xanthene dye described in JP-A-4-219756, JP-A-3-239703, coumarin dye having a heterocyclic ring described in JP-A-5-289335, 3-oxocoumarin compound described in JP-A-3-239703, JP-A-5-289335, tolylpyrrole dye described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-05, JP-A-59-56403, JP-A-88058, Dyes having a dialkylaminobenzene skeleton as described in Japanese patent laid-open Nos. H2-69, 57-168088, 5-107761, 5-210240 and 4-288818.
Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Further preferred are, for example: benzophenone compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzo
Figure BDA0003564604270000121
Azole, 2- (p-diethylaminophenyl) benzo
Figure BDA0003564604270000122
Azole, 2- (p-dimethylaminophenyl) benzo [4,5 ]]Benzo (b) is
Figure BDA0003564604270000123
Azole, 2- (p-dimethylaminophenyl) benzo [6,7 ]]Benzo (b) is
Figure BDA0003564604270000124
Oxazole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-
Figure BDA0003564604270000125
P-dialkylaminophenyl group-containing compounds such as oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Of these, 4' -dialkylaminobenzophenones are particularly preferable.
The sensitizing pigment can be used alone or in combination of two or more
Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as N-butylamine and N-methyldiethanolamine. The polymerization accelerator may be used alone or in combination of two or more.
The content of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 3% by mass or more, and further preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 7% by mass or less, and most preferably 5% by mass or less, in the entire solid content of the photosensitive resin composition. For example, the amount of the organic solvent is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 7% by mass, and particularly preferably 3 to 5% by mass. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The blending ratio of the photopolymerization initiator (B) to the ethylenically unsaturated compound (a) in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, with respect to 100 parts by mass of the ethylenically unsaturated compound (a). For example, it is preferably 1 to 200 parts by mass, more preferably 5 to 200 parts by mass, still more preferably 10 to 100 parts by mass, yet more preferably 15 to 50 parts by mass, and particularly preferably 20 to 30 parts by mass. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
A chain transfer agent may be used in combination with the photopolymerization initiator. Examples of the chain transfer agent include: mercapto compound and carbon tetrachloride. Among these, compounds having a mercapto group are more preferably used because of the tendency to have a high chain transfer effect. This is considered to be because the S-H bond energy is small and the bond is likely to be broken, so that the hydrogen abstraction reaction and the chain transfer reaction are likely to occur. The use of a chain transfer agent is effective for improving sensitivity and surface curability.
The mercapto group-containing compound may have a plurality of mercapto groups in the molecule, and examples thereof include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo
Figure BDA0003564604270000131
Mercapto compounds having an aromatic ring such as oxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercaptonaphthalene, and 1, 4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol dimercaptoacetate, ethylene glycol bisAliphatic mercapto compounds such as (3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and the like.
Among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione is preferable.
From the viewpoint of sensitivity, aliphatic mercapto compounds are preferable, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione are preferable, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.
The mercapto group-containing compound may be used singly or in combination of two or more.
Among these, from the viewpoint of increasing the taper angle, it is selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzimidazole
Figure BDA0003564604270000132
One or more kinds of azoles are suitably used in combination with a photopolymerization initiator as a photopolymerization initiator systemPreferably. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used.
From the viewpoint of sensitivity, one or two or more selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are preferable. From the viewpoint of sensitivity, it is preferable that the compound is selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenz
Figure BDA0003564604270000141
One or more kinds of azoles, one or more kinds selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and a photopolymerization initiator are used in combination.
The content ratio of the chain transfer agent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and further preferably 0.8% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, still more preferably 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass. When the lower limit is not less than the lower limit, ink repellency tends to be improved, and when the upper limit is not more than the upper limit, a high-definition partition wall having a narrow line width tends to be formed.
The content of the chain transfer agent in the photosensitive resin composition relative to the photopolymerization initiator (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less, relative to 100 parts by mass of the photopolymerization initiator (B). For example, it is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 15 to 100 parts by mass, and particularly preferably 20 to 50 parts by mass. When the lower limit is not less than the lower limit, ink repellency tends to be improved, and when the upper limit is not more than the upper limit, a high-definition partition wall having a narrow line width tends to be formed.
[1-1-3] (C) component: alkali soluble resin
The photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin (C) is not particularly limited as long as it can be developed with an alkali developing solution.
The alkali-soluble resin (C) in the photosensitive resin composition of the present invention contains an alkali-soluble resin (C-1) having a partial structure represented by the following general formula (C1).
[ chemical formula 4]
Figure BDA0003564604270000151
(in the formula (c1), Rc11Represents a hydrogen atom or a methyl group,
Rc12represents a 2-valent hydrocarbon group optionally having a substituent,
n represents an integer of 2 or 3,
the benzene ring in formula (c1) is optionally further substituted with an optional substituent,
each represents a bond arm. )
The alkali-soluble resin (C-1) is a resin having a partial structure represented by the formula (C1), and it is considered that the hydrophobicity of the film is easily improved by having a benzene ring in the main chain, and particularly, the crosslinking density is improved by having 2 or more crosslinking groups in the side chain, and the liquid repellent easily remains on the film surface after development, and the ink repellency is improved.
(Rc12)
In the formula (c1), Rc12Represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of heat resistance. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and further preferably 20 or less, more preferably 15 or less, even more preferably 10 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene. Among these, methylene is preferable from the viewpoint of heat resistance.
Specific examples of the branched aliphatic group having a valence of 2 include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. For example, the number of cells is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 to 5. When the lower limit value is not less than the above-mentioned lower limit value, the ink repellency tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the developability tends to be improved.
Specific examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring, or a dicyclopentane ring. Among these, from the viewpoint of heat resistance, a group obtained by removing 2 hydrogen atoms from a dicyclopentane ring or an adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. The aliphatic group having a valence of 2 is preferably unsubstituted from the viewpoint of ease of synthesis.
Further, as the aromatic ring group having a valence of 2, there may be mentioned: a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and further preferably 20 or less, more preferably 15 or less, further preferably 10 or less. For example, the amount of the surfactant is preferably 4 to 20, more preferably 5 to 15, and still more preferably 6 to 10. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group having a valence of 2, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene ring, or aromatic ring,
Figure BDA0003564604270000163
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group having a valence of 2 include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole ring having 2 free valences,
Figure BDA0003564604270000161
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0003564604270000162
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,
Figure BDA0003564604270000164
Pyridine ring, quinazoline ring, quinazolinone ring and azulene ring. Of these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally having a 2-valent aromatic ring group include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The aromatic ring group having a valence of 2 is preferably unsubstituted from the viewpoint of curability.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
The number of the aromatic ring groups having a valence of 2 is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the above-described lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the following formulae (c1-1) to (c 1-6). Among these, the group represented by the formula (c1-1) is preferable from the viewpoint of developability and ink repellency. Each of the symbols in the formula represents a bonding arm.
[ chemical formula 5]
Figure BDA0003564604270000181
As mentioned above, the benzene ring in formula (c1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is not particularly limited, and may be 1 or 2 or more.
The benzene ring in the formula (c1) is preferably unsubstituted from the viewpoint of curability.
(n)
In formula (c1), n represents an integer of 2 or 3. From the viewpoint of adhesion to the substrate, n is preferably 2.
From the viewpoint of developing solubility, the partial structure represented by the formula (c1) is preferably a partial structure represented by the following formula (c 2).
[ chemical formula 6]
Figure BDA0003564604270000191
(in the formula (c2), Rc11、Rc12And n is the same as in the aforementioned formula (c1),
Rc13represents a hydrogen atom or a polybasic acid residue,
the benzene ring in formula (c2) is optionally further substituted with an optional substituent,
each represents a bond arm. )
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethyltetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
The alkali-soluble resin (C-1) may have a partial structure represented by the following general formula (C3) in addition to the partial structure represented by the formula (C1). The alkali-soluble resin (C-1) tends to have a partial structure represented by the formula (C3), whereby the number of crosslinked sites can be easily adjusted, and the developability tends to be improved.
[ chemical formula 7]
Figure BDA0003564604270000192
(in the formula (c3), Rc14Represents a hydrogen atom or a methyl group,
Rc15represents a 2-valent hydrocarbon group optionally having a substituent,
the benzene ring in formula (c3) is optionally further substituted with an optional substituent,
each represents a bond arm. )
As R in formula (c3)c15As R in the formula (c1), R can be preferably usedc12Those listed. In addition, as the substituent optionally having the benzene ring in the formula (c3), those exemplified as the substituent optionally having the benzene ring in the formula (c1) can be preferably used.
From the viewpoint of developing solubility, the partial structure represented by the formula (c3) is preferably a partial structure represented by the following formula (c 4).
[ chemical formula 8]
Figure BDA0003564604270000201
(in the formula (c4), Rc14And Rc15As in the case of the formula (c3) above,
Rc16represents a hydrogen atom or a polybasic acid residue,
the benzene ring in formula (c4) is optionally further substituted with an optional substituent,
denotes the bond arm. )
As R in formula (c4) c16As R in the formula (c2), R can be preferably usedc13Those listed.
In addition, from the viewpoint of developability and ink repellency, the alkali-soluble resin (C-1) preferably contains both the partial structure represented by formula (C1) and the partial structure represented by formula (C3).
The proportion of the formula (c1) relative to the total number of moles of the partial structure represented by the formula (c1) and the partial structure represented by the formula (c3) is not particularly limited, but is preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more, and is usually 100 mol% or less, preferably 90 mol% or less, and more preferably 80 mol% or less. For example, the amount is preferably 20 to 100 mol%, more preferably 40 to 90 mol%, and further preferably 50 to 80 mol%. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
From the viewpoint of developability and ink repellency, the alkali-soluble resin (C-1) preferably contains both a partial structure represented by formula (C2) and a partial structure represented by formula (C4).
The proportion of the formula (c2) relative to the total number of moles of the partial structure represented by the formula (c2) and the partial structure represented by the formula (c4) is not particularly limited, but is preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more, and is usually 100 mol% or less, preferably 90 mol% or less, and more preferably 80 mol% or less. For example, the amount is preferably 20 to 100 mol%, more preferably 40 to 90 mol%, and still more preferably 50 to 80 mol%. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The partial structures represented by the above formulae (C1), (C2), (C3) and (C4) contained in 1 molecule of the alkali-soluble resin (C-1) may be one type or two or more types, respectively.
The number of partial structures represented by the formula (C1) contained in 1 molecule of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. For example, the number of cells is preferably 1 to 10, more preferably 2 to 10, and further preferably 3 to 8. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The number of partial structures represented by the formula (C2) contained in 1 molecule of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, and is preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less. For example, the number of cells is preferably 1 to 15, more preferably 2 to 10, and further preferably 3 to 5. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the alkali-soluble resin (C-1) are shown below.
[ chemical formula 9]
Figure BDA0003564604270000211
[ chemical formula 10]
Figure BDA0003564604270000221
[ chemical formula 11]
Figure BDA0003564604270000222
Among these, the alkali-soluble resin of the formula (C-1-1) is more preferable from the viewpoint of ink repellency.
The method for producing the alkali-soluble resin (C-1) is not particularly limited, and for example, it can be produced as follows: an ethylenically unsaturated monocarboxylic acid or ester compound is added to an epoxy resin having a partial structure represented by the following formula (c5), optionally reacted with a compound containing an isocyanate group, and further reacted with a polybasic acid or an anhydride thereof. For example, the carboxyl group of the unsaturated monocarboxylic acid and the epoxy group of the epoxy resin may be subjected to ring-opening addition to add an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-), and the hydroxyl group formed at this time may be added to one carboxyl group of the polybasic acid anhydride. There may be mentioned a method of adding a polyhydric alcohol simultaneously with the addition of a polybasic acid anhydride.
[ chemical formula 12]
Figure BDA0003564604270000231
(in the formula (c5), Rc12And n is the same as in the aforementioned formula (c1),
the benzene ring in formula (c5) is optionally further substituted with an optional substituent,
each represents a bond arm. )
The alkali-soluble resin (C-1) can be produced by the methods described in Japanese patent application laid-open Nos. 2016-47919 and 2017-190403.
The acid value of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 30mgKOH/g or more, still more preferably 40mgKOH/g or more, and yet more preferably 50mgKOH/g or more, and is preferably 150mgKOH/g or less, more preferably 140mgKOH/g or less, still more preferably 130mgKOH/g or less, and yet more preferably 120mgKOH/g or less. For example, it is preferably 20 to 150mgKOH/g, more preferably 30 to 140mgKOH/g, further preferably 40 to 130mgKOH/g, and particularly preferably 50 to 120 mgKOH/g. When the lower limit value is not less than the above-described lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved.
The weight average molecular weight (Mw) of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, and is preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, and particularly preferably 8000 or less. For example, the concentration is preferably 1000 to 20000, more preferably 1000 to 15000, further preferably 2000 to 10000, and particularly preferably 3000 to 8000. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, development performance tends to be improved.
The double bond equivalent of the alkali-soluble resin (C-1) is not particularly limited, but is preferably 600 or less, more preferably 500 or less, further preferably 450 or less, particularly preferably 400 or less, and is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, particularly preferably 300 or more. When the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the content is preferably 100 to 600, more preferably 150 to 500, still more preferably 200 to 450, and particularly preferably 300 to 400. When the lower limit value or more is set, the developability tends to be improved.
The double bond equivalent of the alkali-soluble resin (C-1) can be calculated by the following formula.
(double bond equivalent of alkali soluble resin (C-1))
(molecular weight of alkali-soluble resin (C-1))/(number of ethylenically unsaturated double bonds equivalent to 1 molecule of alkali-soluble resin (C-1))
The alkali-soluble resin (C) in the photosensitive resin composition of the present invention may further contain an alkali-soluble resin other than the alkali-soluble resin (C-1) (hereinafter, may be referred to as "other alkali-soluble resin"). The addition of another alkali-soluble resin is preferable because the developability tends to be improved.
The other alkali-soluble resin preferably contains an epoxy (meth) acrylate resin (C-2) other than (C-1) (hereinafter, may be referred to as "epoxy (meth) acrylate resin (C-2)") from the viewpoint of developing solubility. On the other hand, from the viewpoint of ink repellency, it is preferable to contain an acrylic copolymer resin (C-3) having an ethylenically unsaturated group in the side chain (hereinafter, sometimes referred to as "acrylic copolymer resin (C-3)").
First, the epoxy (meth) acrylate resin (C-2) will be described in detail.
[ epoxy (meth) acrylate resin (C-2) ]
The epoxy (meth) acrylate resin (C-2) is obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin not having a partial structure represented by formula (C5), optionally reacting an isocyanate group-containing compound, and then further reacting a polybasic acid or an anhydride thereof. Examples thereof include: the resin is obtained by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, thereby adding an ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) and simultaneously adding a carboxyl group of a polybasic acid anhydride to a hydroxyl group generated at that time. Further, a resin obtained by adding a polyhydric alcohol simultaneously with the addition of a polybasic acid anhydride.
Further, a resin obtained by reacting a compound having a functional group capable of reacting with a carboxyl group of the resin obtained by the above reaction is also included in the epoxy (meth) acrylate resin (C-2).
Here, specific examples of the epoxy resin include: bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenol novolac epoxy resin, triphenol epoxy resin, epoxy resin polymerized from phenol and dicyclopentadiene, dihydroxyfluorene epoxy resin, dihydroxyalkyleneoxyfluorene epoxy resin, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, and diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane. As the epoxy resin, a compound having an aromatic ring in the main chain as described above can be preferably used.
Among these, from the viewpoint of heat resistance, bisphenol a epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, polymerized epoxy resins of phenol and dicyclopentadiene, and diglycidyl etherate of 9, 9-bis (4' -hydroxyphenyl) fluorene are preferable, and bisphenol a epoxy resins are more preferable.
As the epoxy resin, for example: bisphenol A-type epoxy resins (e.g., "JeR (registered trademark, the same below)" 828 "," JeR1001 "," JeR1002 "," JeR1004 ", manufactured by Mitsubishi Chemical corporation," NER-1302 "(epoxy equivalent 323, softening point 76 ℃ C.), bisphenol F-type resins (e.g.," JeR807 "," JeR4004P "," JeR4005P "," JeR4007P ", manufactured by Mitsubishi Chemical corporation," NER-7406 "(epoxy equivalent 350, softening point 66 ℃ C.), bisphenol S-type epoxy resins, biphenyl glycidyl ethers (e.g.," Jeryx-4000 ", manufactured by Mitsubishi Chemical corporation), phenol novolac-type epoxy resins (e.g.," EPPN-201 ", manufactured by Mitsubishi Chemical corporation," Jer152 "," Jer154 ", manufactured by Mitsubishi Chemical corporation," DEN-438 ", manufactured by Mitsubishi Chemical corporation), (o-, m-, and P-) cresol novolak-type epoxy resins (for example, "EOCN (registered trademark), the same as below) -102S", "EOCN-1020", "EOCN-104S", manufactured by Nippon chemical Co., Ltd., "TEPIC (registered trademark)"), triphenol methane-type epoxy resins (for example, "EPPN (registered trademark, the same as below) -501", "EPPN-502", "EPPN-503", manufactured by Nippon chemical Co., Ltd.), alicyclic epoxy resins (for example, "Celloxide (registered trademark, the same as below) 2021P", "Celloxide EHPE", manufactured by Daseiko chemical Co., Ltd.), and epoxy resins obtained by glycidating a phenol resin produced by reacting dicyclopentadiene with phenol (for example, "EXA-7200", manufactured by DIC Co., Ltd.), "NC-7300", "XD-1000" manufactured by Nippon Kagaku K.K., biphenyl type epoxy resin (for example, "NC-7000" manufactured by Nippon Kagaku K.K.), and "E-201" manufactured by Osaka organic chemical industry Co., Ltd. Among these, preferred are "XD-1000" manufactured by Nippon chemical Co., Ltd, "NC-3000" manufactured by Nippon chemical Co., Ltd, "ESF-300" manufactured by Nikkaido Kagaku K.K., and "E-201" manufactured by Osaka organic chemical industry Co., Ltd.
Examples of ethylenically unsaturated monocarboxylic acids include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, a reaction product of (meth) acrylic acid and epsilon-caprolactone. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.
Examples of the polybasic acid (anhydride) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof. Among these, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable, and succinic anhydride and tetrahydrophthalic anhydride are more preferable, from the viewpoint of suppressing degassing from a cured product and ensuring long-term reliability.
By using the polyol, the molecular weight of the epoxy (meth) acrylate resin (C-2) tends to be increased, and a balance between the molecular weight and the viscosity tends to be obtained by introducing a branch into the molecule. Further, the introduction rate of an acid group into a molecule tends to be increased, and a balance between sensitivity and adhesion tends to be easily obtained.
The polyol is preferably one or two or more polyols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol.
As the epoxy (meth) acrylate resin (C-2), in addition to those described above, epoxy (meth) acrylate resins described in Korean laid-open patent publication No. 10-2013-0022955 can be cited.
The epoxy (meth) acrylate resin (C-2) preferably contains at least one selected from the group consisting of an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i) but not having a partial structure represented by the formula (C1) (hereinafter, sometimes referred to as "epoxy (meth) acrylate resin (C-2-1)") and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii) but not having a partial structure represented by the formula (C1) (hereinafter, sometimes referred to as "epoxy (meth) acrylate resin (C-2-2)") from the viewpoint of developing solubility.
[ chemical formula 13]
Figure BDA0003564604270000261
(in the formula (i), RaRepresents a hydrogen atom or a methyl group,
Rbrepresents a 2-valent hydrocarbon group optionally having a substituent,
the phenyl ring in formula (i) is optionally further substituted with an optional substituent,
each represents a bond arm. )
[ chemical formula 14]
Figure BDA0003564604270000271
(in the formula (ii), RcEach independently represents a hydrogen atom or a methyl group,
Rdrepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain,
Reand RfEach independently represents an optionally substituted aliphatic group having a valence of 2,
l and m each independently represent an integer of 0 to 2,
each represents a bond arm. )
The epoxy (meth) acrylate resin (C-2-1) will be described in detail.
[ chemical formula 15]
Figure BDA0003564604270000272
(in the formula (i), RaRepresents a hydrogen atom or a methyl group,
Rbrepresents a 2-valent hydrocarbon group optionally having a substituent,
the phenyl ring in formula (i) is optionally further substituted with an optional substituent,
each represents a bond arm. )
As R in formula (i)bAs R in the formula (c1), R can be preferably usedc12Those listed.
The benzene ring in the formula (i) is optionally further substituted with an optional substituent, and as the substituent, for example: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be one or 2 or more.
From the viewpoint of developing solubility, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1).
[ chemical formula 16]
Figure BDA0003564604270000281
(in the formula (i-1), RaAnd RbAnd R of formula (i)aAnd RbThe meaning is the same as that of the prior art,
RYrepresents a hydrogen atom or a polybasic acid residue,
the benzene ring in the formula (i-1) is optionally further substituted with an optional substituent.
Each represents a bond arm. )
As R in formula (i-1)YAs R in the formula (c2), R can be preferably usedc13Those listed.
The benzene ring in the formula (i-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be one or 2 or more.
The number of the repeating unit structures represented by the formula (i-1) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-1) may be one, or 2 or more.
The number of partial structures represented by formula (i) contained in 1 molecule of epoxy (meth) acrylate resin (C-2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and further preferably 10 or less, and even more preferably 8 or less. For example, the number of the cells is preferably 1 to 10, more preferably 2 to 10, and further preferably 3 to 8. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
The number of partial structures represented by the formula (i-1) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. For example, the number of cells is preferably 1 to 10, more preferably 2 to 10, and further preferably 3 to 8. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
Specific examples of the epoxy (meth) acrylate resin (C-2-1) are shown below.
[ chemical formula 17]
Figure BDA0003564604270000291
[ chemical formula 18]
Figure BDA0003564604270000292
[ chemical formula 19]
Figure BDA0003564604270000293
[ chemical formula 20]
Figure BDA0003564604270000294
[ chemical formula 21]
Figure BDA0003564604270000301
[ chemical formula 22]
Figure BDA0003564604270000302
[ chemical formula 23]
Figure BDA0003564604270000303
Next, the epoxy (meth) acrylate resin (C-2-2) will be described in detail.
[ chemical formula 24]
Figure BDA0003564604270000304
(in the formula (ii), RcEach independently represents a hydrogen atom or a methyl group,
Rdrepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain,
Reand RfEach independently represents an optionally substituted 2-valent aliphatic group, l and m each independently represents an integer of 0 to 2,
each represents a bond arm. )
(Rd)
In the formula (ii), RdRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The aliphatic ring group has preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more carbon atoms, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less carbon atoms. For example, the amount of the organic solvent is preferably 4 to 40, more preferably 4 to 30, still more preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of heat resistance.
The number of rings included in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and further preferably 10 or less, more preferably 5 or less, and further preferably 4 or less. For example, the number of the cells is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 4. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 40, more preferably 6 to 40, further preferably 8 to 30, further preferably 10 to 20, and particularly preferably 12 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0003564604270000311
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring. Among these, the fluorene ring is preferable from the viewpoint of heat resistance.
Among the 2-valent hydrocarbon groups having a cyclic hydrocarbon group as a side chain, the 2-valent hydrocarbon group is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of improving developability, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of heat resistance. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. For example, the amount of the surfactant is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene. Among these, methylene is preferred from the viewpoint of heat resistance.
Specific examples of the branched aliphatic group having a valence of 2 include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these, from the viewpoint of heat resistance, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. The aliphatic group having a valence of 2 is preferably unsubstituted from the viewpoint of ease of synthesis.
The aromatic ring group having a valence of 2 includes an aromatic ring group having a valence of 2 and an aromatic heterocyclic group having a valence of 2. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and further preferably 30 or less, more preferably 20 or less, further preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group having a valence of 2, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene ring, or aromatic ring,
Figure BDA0003564604270000331
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group having a valence of 2 include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Figure BDA0003564604270000332
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0003564604270000333
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a benzimidazole ring, a pyridine ring, a compound, a,
Figure BDA0003564604270000334
Pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the aromatic ring group having a valence of 2 include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The aromatic ring group having a valence of 2 is preferably unsubstituted from the viewpoint of curability.
Examples of the group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the heat resistance tends to be improved.
The number of the aromatic ring groups having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the above formulae (c1-1) to (c 1-6). Among these, the group represented by the formula (c1-3) is preferable from the viewpoint of film strength.
The bonding mode of the cyclic hydrocarbon group as the side chain of these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the side chain is a cyclic hydrocarbon group having 1 carbon atom of the aliphatic group or aromatic group substituted for 1 hydrogen atom.
(Re、Rg)
In the formula (ii), ReAnd RgEach independently represents a 2-valent aliphatic group optionally having a substituent.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of heat resistance.
The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 3 to 15, and still more preferably 6 to 10. When the lower limit value is not less than the lower limit value, adhesion to a substrate and ink repellency tend to be improved, and when the upper limit value is not more than the upper limit value, deterioration of sensitivity and reduction of a film during development tend to be easily suppressed, thereby improving resolution.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferred from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include those having a structure having, as a side chain, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group on the linear aliphatic group having a valence of 2.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and further preferably 12 or less, and more preferably 10 or less. For example, the number of the cells is preferably 1 to 12, more preferably 1 to 10, and further preferably 2 to 10. When the lower limit value is not less than the lower limit value, adhesion to a substrate and ink repellency tend to be improved, and when the upper limit value is not more than the upper limit value, deterioration of sensitivity and reduction of a film during development tend to be easily suppressed, thereby improving resolution.
Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring, or a dicyclopentadiene ring. Among these, from the viewpoint of heat resistance, a group obtained by removing 2 hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. The aliphatic group having a valence of 2 is preferably unsubstituted from the viewpoint of ease of synthesis.
(l、m)
In the formula (ii), l and m each independently represent an integer of 0 to 2. When the lower limit value is set to be equal to or higher than the lower limit value, the adhesion with the substrate tends to be improved, and when the upper limit value is set to be lower than the lower limit value, the developability tends to be good. From the viewpoint of developability, l and m are preferably 0. On the other hand, from the viewpoint of adhesion to the substrate, l and m are preferably 1 or more.
The partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of film strength and ink repellency.
[ chemical formula 25]
Figure BDA0003564604270000351
(in the formula (ii-1), Rc、Re、RfL and m are as defined above for formula (ii),
Rαrepresents an optionally substituted 1-valent cyclic hydrocarbon group,
n is an integer of 1 or more,
the benzene ring in the formula (ii-1) is optionally further substituted with an optional substituent,
each represents a bond arm. )
(Rα)
In the formula (ii-1), RαRepresents an optionally substituted 1-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. For example, the number of cells is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The aliphatic ring group has preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more carbon atoms, and further preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less carbon atoms. For example, the amount of the surfactant is preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of having both ink repellency and developability.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. For example, the number of the cells is preferably 1 to 10, more preferably 2 to 10, and further preferably 3 to 5. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and further preferably 30 or less, more preferably 20 or less, further preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring. Among these, the fluorene ring is preferable from the viewpoint of having both ink repellency and developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; a carboxyl group. The cyclic hydrocarbon group is preferably unsubstituted from the viewpoint of ease of synthesis.
n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, it is preferably 1 to 3, more preferably 2 to 3. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Of these, R is preferable from the viewpoint of having both ink repellency and developabilityαIs a 1-valent aliphatic ring group, and is more preferably an adamantyl group.
As described above, the benzene ring in the formula (ii-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be one or two or more. The benzene ring in the formula (ii-1) is preferably unsubstituted from the viewpoint of curability.
Specific examples of the partial structure represented by the formula (ii-1) are shown below.
[ chemical formula 26]
Figure BDA0003564604270000371
[ chemical formula 27]
Figure BDA0003564604270000372
[ chemical formula 28]
Figure BDA0003564604270000373
[ chemical formula 29]
Figure BDA0003564604270000374
[ chemical formula 30]
Figure BDA0003564604270000375
From the viewpoint of development adhesion, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2).
[ chemical formula 31]
Figure BDA0003564604270000381
(in the formula (ii-2), Rc、Re、RfL and m are as defined above for formula (ii),
Rβrepresents an optionally substituted 2-valent cyclic hydrocarbon group,
the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent,
each represents a bond arm. )
(Rβ)
In the formula (ii-2), RβRepresents an optionally substituted 2-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, and more preferably 5 or less. For example, the number of the cells is preferably 1 to 10, more preferably 2 to 5. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
The aliphatic ring group has preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more carbon atoms, and further preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less carbon atoms. For example, the amount of the surfactant is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of having both ink repellency and developability.
The number of rings included in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. For example, the number of cells is preferably 1 to 10, more preferably 2 to 10, and further preferably 3 to 5. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and particularly preferably 10 or more, and further preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring. Among these, the fluorene ring is preferable from the viewpoint of ink repellency and developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; a nitro group; a cyano group; a carboxyl group. The cyclic hydrocarbon group is preferably unsubstituted from the viewpoint of ease of synthesis.
Among these, R is preferable from the viewpoint of heat resistance and compatibility between ink repellency and developabilityβIs a 2-valent aliphatic ring group, and more preferably a 2-valent adamantyl ring group. On the other hand, from the viewpoint of heat resistance and compatibility between ink repellency and developability, R is preferableβIs a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
The benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be one or two or more. The benzene ring in the formula (ii-2) is preferably unsubstituted from the viewpoint of curability.
Specific examples of the partial structure represented by the formula (ii-2) are shown below.
[ chemical formula 32]
Figure BDA0003564604270000391
[ chemical formula 33]
Figure BDA0003564604270000401
[ chemical formula 34]
Figure BDA0003564604270000402
[ chemical formula 35]
Figure BDA0003564604270000403
On the other hand, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.
[ chemical formula 36]
Figure BDA0003564604270000404
(in the formula (ii-3), Rc、Rd、Re、RfL and m are as defined above for formula (ii),
RZrepresents a hydrogen atom or a polybasic acid residue. )
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethyltetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
The partial structure represented by the formula (ii-3) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-2) may be one kind, or two or more kinds.
The number of partial structures represented by the formula (ii) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, the number of the cells is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 10. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The number of partial structures represented by the formula (ii-1) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, the number of the cells is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 10. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The number of partial structures represented by the formula (ii-2) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, the number of cells is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 3 to 10. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the developability tends to be improved.
The number of partial structures represented by the formula (ii-3) contained in 1 molecule of the epoxy (meth) acrylate resin (C-2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, the number of the cells is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 3 to 10. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be improved.
The acid value of the epoxy (meth) acrylate resin (C-2) is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, further preferably 70mgKOH/g or more, particularly preferably 80mgKOH/g or more, and further preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, further preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less, and particularly preferably 110mgKOH/g or less. For example, it is preferably 10 to 200mgKOH/g, more preferably 30 to 180mgKOH/g, further preferably 50 to 150mgKOH/g, further preferably 70 to 120mgKOH/g, and particularly preferably 80 to 110 mgKOH/g. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency and the film strength tend to be improved.
The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (C-2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 3500 or more, and is preferably 30000 or less, more preferably 15000 or less, further preferably 10000 or less, further preferably 8000 or less, particularly preferably 5000 or less. For example, the concentration is preferably 1000 to 30000, more preferably 1000 to 15000, still more preferably 2000 to 10000, still more preferably 3000 to 8000, and particularly preferably 3500 to 5000. When the lower limit value is not less than the above-mentioned lower limit value, the ink repellency and the film strength tend to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the residue tends to be reduced.
Next, the acrylic copolymer resin (C-3) will be described in detail.
[ acrylic copolymer resin (C-3) ]
The acrylic copolymer resin (C-3) has an ethylenically unsaturated group in a side chain. By having an ethylenically unsaturated group, the film is less likely to be reduced by an alkali developing solution during development by photocuring by exposure, and the surface smoothness is improved. Further, the soft backbone tends to improve adhesion to the substrate.
(partial structural Unit represented by the general formula (1))
The partial structure of the acrylic copolymer resin (C-3) having a side chain having an ethylenically unsaturated group is not particularly limited, and preferably has a partial structural unit represented by the following general formula (1), for example, from the viewpoints of ease of radical emission and adhesion to a substrate, which are associated with flexibility of the film.
[ chemical formula 37]
Figure BDA0003564604270000431
(in the formula (1), Ra1And Ra2Each independently represents a hydrogen atom or a methyl group, and represents a bonding arm. )
Among the partial structural units represented by the formula (1), a repeating unit represented by the following general formula (1') is preferable from the viewpoint of sensitivity and alkali developability.
[ chemical formula 38]
Figure BDA0003564604270000432
(in the formula (1'), Ra1And Ra2Each independently represents a hydrogen atom or a methyl group, RxRepresents a hydrogen atom or a polybasic acid residue. )
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethyltetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable from the viewpoint of patterning characteristics.
When the acrylic copolymer resin (C-3) contains a partial structural unit represented by the general formula (1), the content ratio thereof is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and further preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, further preferably 75 mol% or less, and particularly preferably 70 mol% or less with respect to the total repeating units. For example, the amount is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, further preferably 30 to 80 mol%, further preferably 40 to 75 mol%, and particularly preferably 50 to 70 mol%. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (1'), the content thereof is not particularly limited, and is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, further preferably 30 mol% or more, particularly preferably 35 mol% or more, and further preferably 80 mol% or less, more preferably 75 mol% or less, further preferably 70 mol% or less, and particularly preferably 65 mol% or less, of all the repeating units. For example, the amount of the organic solvent is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, further preferably 25 to 75 mol%, further preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%. When the lower limit value is not less than the lower limit value, ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, development adhesion tends to be easily ensured.
(repeating unit represented by the general formula (2))
When the acrylic copolymer resin (C-3) contains a partial structural unit represented by the general formula (1), the other repeating units are not particularly limited, and it is preferable that the acrylic copolymer resin (C-3) further contains a repeating unit represented by the following general formula (2), for example, from the viewpoint of development adhesion.
[ chemical formula 39]
Figure BDA0003564604270000441
(in the formula (2), Ra3Represents a hydrogen atom or a methyl group,
Ra4represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, or an alkenyl group optionally having a substituent. )
(Ra4)
In the formula (2), Ra4Represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, or an alkenyl group optionally having a substituent.
As Ra4Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, particularly preferably 12 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 5 to 14, and particularly preferably 8 to 12. When the lower limit value is not less than the above-mentioned lower limit value, the film strength tends to be high and the development adhesion tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the residue tends to be reduced.
Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl and dodecyl. Among these, from the viewpoint of developability, dicyclopentyl group or dodecyl group is preferable, and dicyclopentyl group is more preferable.
Examples of the substituent optionally contained in the alkyl group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As Ra4As the aromatic ring group in (3), there may be mentioned an aromatic ring group having a valence of 1 and an aromatic heterocyclic group having a valence of 1. The number of carbon atoms is preferably 6 or more, and also preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. For example, it is preferably 6 to 24, more preferably 6 to 246 to 22, more preferably 6 to 20, and particularly preferably 6 to 18. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0003564604270000451
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0003564604270000452
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0003564604270000453
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a benzimidazole ring, a pyridine ring, a compound, a,
Figure BDA0003564604270000461
Pyridine ring, quinazoline ring, quinazolinone ring and azulene ring. Among these, from the viewpoint of developability, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
Further, as the substituent optionally having an aromatic ring group, there may be mentioned, for example: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As Ra4Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, the amount of the surfactant is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Examples of the substituent optionally contained in the alkenyl group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo-ethylene glycol group, phenyl group, carboxyl group, and from the viewpoint of developability, hydroxy group and oligo-ethylene glycol group are preferable.
As Ra4Among the above, from the viewpoints of developability and film strength, an alkyl group and an alkenyl group are preferable, and an alkyl group is more preferable.
When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (2), the content ratio thereof is not particularly limited, and is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, and further preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less, in all the repeating units. For example, the amount is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
(repeating unit represented by the general formula (3))
When the acrylic copolymer resin (C-3) contains a partial structural unit represented by the general formula (1), it is preferable that the acrylic copolymer resin (C-3) contains a repeating unit represented by the following general formula (3) as another repeating unit that can be contained, from the viewpoint of heat resistance and film strength.
[ chemical formula 40]
Figure BDA0003564604270000471
(in the above formula (3), Ra5Represents a hydrogen atom or a methyl group,
Ra6represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent,
t represents an integer of 0 to 5. )
(Ra6)
In the formula (3), Ra6Represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent.
As Ra6Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 3 to 14, and particularly preferably 5 to 12. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl and dodecyl. Among these, from the viewpoints of developability and film strength, dicyclopentyl group and dodecyl group are preferable, and dicyclopentyl group is more preferable.
Examples of the substituent optionally contained in the alkyl group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As Ra6Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, the amount of the surfactant is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Examples of the substituent optionally contained in the alkenyl group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo-ethylene glycol group, phenyl group, carboxyl group, and from the viewpoint of developability, hydroxy group and oligo-ethylene glycol group are preferable.
As Ra6Examples of the alkynyl group in (3) include a linear, branched or cyclic alkynyl group. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. For example, the amount of the surfactant is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Examples of the substituent optionally contained in the alkynyl group include: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As Ra6Examples of the halogen atom in (1) include a fluorine atom and chlorineAmong these, a fluorine atom is preferred from the viewpoint of developability.
As Ra6Examples of the alkoxy group in (1) include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Examples of the substituent optionally having an alkoxy group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferable.
As Ra6The alkylthio group in (1) may be a straight-chain, branched or cyclic alkylthio group. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
Examples of the substituent optionally having an alkyl group in the alkylthio group include: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As Ra6Among the above, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
In formula (3), t represents an integer of 0 to 5, and preferably t is 0 from the viewpoint of ease of production.
When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (3), the content ratio thereof is not particularly limited, and is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 2 mol% or more, particularly preferably 5 mol% or more, and further preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less, of the total repeating units. For example, the amount is preferably 0.5 to 50 mol%, more preferably 0.5 to 40 mol%, further preferably 1 to 30 mol%, further preferably 2 to 20 mol%, and particularly preferably 5 to 15 mol%. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, residue tends to be reduced.
(repeating unit represented by the general formula (4))
When the acrylic copolymer resin (C-3) has a partial structural unit represented by the general formula (1), it is preferable that the acrylic copolymer resin further contains a repeating unit represented by the following general formula (4) as another repeating unit that may be contained, from the viewpoint of developability.
[ chemical formula 41]
Figure BDA0003564604270000491
(in the above formula (4), Ra7Represents a hydrogen atom or a methyl group. )
When the acrylic copolymer resin (C-3) contains the repeating unit represented by the general formula (4), the content ratio thereof is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less, in all the repeating units. For example, the amount is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the developability adhesiveness tends to be improved.
The acid value of the acrylic copolymer resin (C-3) is not particularly limited, but is preferably 30mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 50mgKOH/g or more, yet more preferably 60mgKOH/g or more, and is preferably 150mgKOH/g or less, more preferably 140mgKOH/g or less, still more preferably 130mgKOH/g or less, and yet more preferably 120mgKOH/g or less. For example, it is preferably 30 to 150mgKOH/g, more preferably 40 to 140mgKOH/g, still more preferably 50 to 130mgKOH/g, and particularly preferably 60 to 120 mgKOH/g. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the developability adhesiveness tends to be improved.
The weight average molecular weight (Mw) of the acrylic copolymer resin (C-3) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 4000 or more, still more preferably 6000 or more, particularly preferably 7000 or more, and most preferably 8000 or more, and is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, and particularly preferably 10000 or less. For example, the range is preferably 1000 to 30000, more preferably 2000 to 30000, further preferably 4000 to 20000, further preferably 6000 to 20000, further preferably 7000 to 15000, and particularly preferably 8000 to 10000. When the lower limit value is not less than the lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, development property tends to be good.
Specific examples of the acrylic copolymer resin (C-3) include those described in, for example, Japanese patent application laid-open Nos. 8-297366 and 2001-89533.
The alkali-soluble resin (C) in the present invention may further contain an alkali-soluble resin other than the epoxy (meth) acrylate resin (C-2) and the acrylic copolymer resin (C-3) as another alkali-soluble resin.
(C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, further preferably 60mgKOH/g or more, and is preferably 300mgKOH/g or less, more preferably 200mgKOH/g or less, further preferably 100mgKOH/g or less, and particularly preferably 80mgKOH/g or less. For example, it is preferably 30 to 300mgKOH/g, more preferably 30 to 200mgKOH/g, further preferably 50 to 100mgKOH/g, and particularly preferably 60 to 80 mgKOH/g. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the developability adhesiveness tends to be improved.
When the alkali-soluble resin (C) is a mixture of two or more types, the acid value is a weighted average value obtained according to the content ratio.
The content ratio of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, further particularly preferably 50% by mass or more, and most preferably 60% by mass or more, and further preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount of the organic solvent is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 80% by mass, particularly preferably 50 to 70% by mass, most preferably 60 to 70% by mass. When the lower limit value is not less than the lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
The content of the alkali-soluble resin (C-1) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, and further preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 65% by mass or less, of the total solid content of the photosensitive resin composition. For example, it is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, further preferably 40 to 80% by mass, further preferably 50 to 70% by mass, and particularly preferably 60 to 65% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the ink repellency and the development adhesion tend to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the residue tends to be reduced.
(C) The content of the alkali-soluble resin (C-1) in the alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and usually 100% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the ink repellency and the development adhesion tend to be improved.
The total of the content ratio of the ethylenically unsaturated compound (a) and the content ratio of the alkali-soluble resin (C) in the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, particularly preferably 80% by mass or more, and further preferably 95% by mass or less, more preferably 92% by mass or less, and further preferably 90% by mass or less. For example, the amount is preferably 10 to 95% by mass, more preferably 30 to 95% by mass, still more preferably 60 to 92% by mass, and particularly preferably 80 to 90% by mass. When the lower limit value is not less than the upper limit value, the adhesion of the partition walls to the substrate tends to be improved, and when the upper limit value is not more than the lower limit value, the light shielding property and the ink repellency tend to be improved.
[1-1-4] (D) liquid repellent
The photosensitive resin composition of the present invention contains a fluorine atom-containing resin having a crosslinking group as (D) the liquid repellent. It is considered that the surface of the obtained partition wall can be imparted with ink repellency by containing a fluorine atom-containing resin having a crosslinking group, and therefore color mixing of the obtained partition wall together with pixels can be prevented.
Examples of the crosslinking group include an epoxy group and an ethylenically unsaturated group, and the ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid repellent to the developer.
It is considered that the use of a liquid repellent having a crosslinking group accelerates the crosslinking reaction occurring on the surface of the coating film formed when exposed to light, and the liquid repellent hardly flows out during the development treatment, and as a result, the partition walls obtained can exhibit high ink repellency.
Further, the liquid repellent (D) as the fluorine atom-containing resin tends to be oriented on the surface of the partition wall, and to prevent ink leakage and color mixing. More specifically, there is a tendency that: the group having fluorine atoms repels ink, thereby playing a role of preventing ink leakage and color mixing caused by ink entering adjacent regions across partition walls.
The fluorine-atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having either or both of the perfluoroalkyl group and the perfluoroalkylene ether chain, the fluorine atom-containing resin tends to be more easily oriented on the surfaces of the partition walls, to exhibit higher ink repellency, and to further prevent bleeding of ink and color mixing.
Examples of the perfluoroalkyl group include: perfluorobutyl, perfluorohexyl, perfluorooctyl. Examples of the perfluoroalkylene ether chain include: -CF2-O-、-(CF2)2-O-、-(CF2)3-O-、-CF2-C(CF3)O-、-C(CF3)-CF2O-and 2-valent radicals having these repeating units.
Specific examples of the fluorine atom-containing resin having a crosslinking group include: an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy (meth) acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy (meth) acrylate resin having an epoxy group and a perfluoroalkylene ether chain, an epoxy (meth) acrylate resin having an ethylenically unsaturated group and a perfluoroalkyl group, and an epoxy (meth) acrylate resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain. Among these, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain is more preferable.
As commercially available products of these fluorine atom-containing resins having a crosslinking group, there may be used "Megafac (registered trademark, the same shall apply hereinafter)" F116 "," Megafac F120 "," Megafac F142D "," Megafac F144D "," Megafac F150 "," Megafac F160 "," Megafac F171 "," Megafac F172 "," Megafac F173 "," Megafac F177 "," Megafac F178A "," Megafac F178K "," Megafac F179 "," Megafac F183 "," Megafac F184 "," Megafac F191 "," Megafac F812 "," Megafac F815 "," Megafac F824 "," Megafac F833 "," Megafac RS101 "," Megafac RS102 "," Megafac RS105 "," Megafac RS201 "," Megafac RS 301-gafac RS301 "," Megafac RS 301-401 "or Megafac RS 72" by DIC, Examples of the fluorinated organic compound include commercially available fluorinated organic compounds under the trade names "Megafac RS-90", "DEFENSA (registered trademark, the same shall apply hereinafter)" MCF300 "," DEFENSA MCF310 "," DEFENSA MCF312 "," DEFENSA MCF323 ", Fluorad FC 430", "Fluorad FC 431", "FC-4430", "FC 4432", ASAHI GUARD (registered trademark) AG710 "," Surflon (registered trademark, the same shall apply hereinafter) "S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106", and the like.
Of these, as the acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group, "Megafac RS-72-K", "Megafac RS-78" and "Megafac RS-90" can be preferably used.
The content ratio of fluorine atoms in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 25% by mass or more, and further preferably 50% by mass or less, more preferably 35% by mass or less in the fluorine atom-containing resin having a crosslinking group. For example, the amount is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, still more preferably 20 to 35% by mass, and particularly preferably 25 to 35% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, the outflow to the pixel portion tends to be suppressed, and when the upper limit value is set to be equal to or lower than the upper limit value, the contact angle tends to be high.
The molecular weight of the fluorine atom-containing resin having a crosslinking group is not particularly limited, and may be a low molecular weight compound or a high molecular weight product. The high molecular weight material is preferable because fluidity due to post baking can be suppressed and outflow from the partition walls can be suppressed. In the case of a fluorine atom-containing resin high molecular weight material having a crosslinking group, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more, more preferably 500 or more, preferably 100000 or less, more preferably 10000 or less. For example, it is preferably 100 to 100000, more preferably 500 to 10000.
The content of the liquid repellent (D) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by mass. When the lower limit is not less than the lower limit, ink repellency tends to be improved, and when the upper limit is not more than the lower limit, a uniform coating film tends to be easily obtained when ink is applied to the pixel portion after the partition walls are formed.
The content ratio of the fluorine atom-containing resin having a crosslinking group in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and further preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by mass. When the lower limit value is not less than the lower limit value, ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, a uniform coating film tends to be easily obtained when ink is applied to the pixel portion after the partition walls are formed.
In the photosensitive resin composition of the present invention, (D) a liquid repellent may be used together with a surfactant. The surfactant can be used for the purpose of, for example, improving coatability when forming a coating solution of the photosensitive resin composition and developability of a coating film, and among them, a silicone surfactant and a fluorine surfactant having no crosslinking group are preferable.
In particular, the silicone surfactant is preferable, and the polyether-modified silicone surfactant is more preferable, because it has an action of removing the residue of the photosensitive resin composition from unexposed portions during development and has a function of exhibiting wettability.
As the fluorine-based surfactant having no crosslinking group, a compound having a fluoroalkyl group or a fluoroalkylene group at least at any position of a terminal, a main chain, and a side chain is suitable.
Examples of commercially available products of these include: BM-1000 and BM-1100 manufactured by BM Chemie, Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F470, Megafac F475, Megafac F554, Megafac F559, FC430 manufactured by 3M Japan, DFX-18 manufactured by Neos, and the like.
Further, examples of the silicone surfactant include: commercially available products such as "DC 3 PA", "SH 7 PA", "DC 11 PA", "SH 21 PA", "SH 28 PA", "SH 29 PA", "8032 Additive", "SH 8400", BYK (registered trademark, the same hereinafter) 323 "and" BYK330 "from Dow Corning Toray corporation.
The surfactant may contain surfactants other than the fluorine-based surfactant and the silicone-based surfactant, and examples of the other surfactant include nonionic, anionic, cationic, and amphoteric surfactants.
Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitol fatty acid esters.
Examples of commercially available products of these include: polyoxyethylene surfactants such as "Emargen (registered trademark, the same applies hereinafter)" 104P "and" Emargen A60 "manufactured by Kao corporation.
Examples of anionic surfactants include: alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, polyoxyethylene alkylethersulfonic acid salts, alkylsulfuric acid ester salts, higher alcohol sulfuric acid ester salts, aliphatic alcohol sulfuric acid ester salts, polyoxyethylene alkylethersulfuric acid salts, polyoxyethylene alkylphenylether sulfuric acid salts, alkylphosphoric acid ester salts, polyoxyethylene alkyletherphosphoric acid salts, polyoxyethylene alkylphenylether phosphoric acid ester salts, and special polymer surfactants. Among them, a specific polymer surfactant is preferable, and a specific polycarboxylic acid type polymer surfactant is more preferable.
As their commercially available products, there may be mentioned, for example, "Emal (registered trademark, the same shall apply hereinafter) 10" manufactured by Kao corporation, for example, "Pelex (registered trademark) NB-L" manufactured by Kao corporation, for example, among alkyl naphthalene sulfonates, and "Homogenol (registered trademark, the same shall apply hereinafter) L-18" and "Homogenol L-100" manufactured by Kao corporation, for example, among special polymer surfactants.
Examples of the cationic surfactant include: quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Further, as the amphoteric surfactant, for example, there can be mentioned: betaine type compounds, imidazolium salts, imidazolines, and amino acids.
Of these, quaternary ammonium salts are preferable, and stearyl trimethylammonium salt is more preferable.
Examples of commercially available products of these include "acetamide (registered trademark) 24" manufactured by kao corporation, and examples of quaternary ammonium salts include "Quartamin (registered trademark) 24P" and "Quartamin 86W" manufactured by kao corporation.
The surfactant may be used alone or in combination of two or more. Examples thereof include: a combination of a silicone surfactant and a fluorine surfactant, a combination of a silicone surfactant and a special polymer surfactant, and a combination of a fluorine surfactant and a special polymer surfactant. Among these, a combination of a silicone surfactant and a fluorine surfactant is preferable.
In the combination of the silicone surfactant and the fluorine surfactant, for example: a combination of "DFX-18" manufactured by Neos, BYK-300 or BYK-330 manufactured by BYK-Chemie, and "S-393" manufactured by AGC Seimi Chemical; it is believed that a combination of "KP 340" manufactured by NI silicone corporation and "F-554" or "F-559" manufactured by DIC corporation; a combination of "SH 7 PA" manufactured by Dow Corning Toray and "DS-401" manufactured by Dajin Kabushiki Kaisha; l-77 manufactured by NUC and FC4430 manufactured by 3M Japan.
[1-1-5] (E) colorant
The photosensitive resin composition of the present invention may further contain (E) a colorant. By containing the colorant (E), appropriate light absorption can be obtained, and in particular, appropriate light blocking properties can be obtained in the case of use for forming a light-blocking member including colored partition walls.
The type of the colorant (E) used in the present invention is not particularly limited, and pigments or dyes may be used. Among these, pigments are preferably used from the viewpoint of durability.
(E) The pigment contained in the colorant may be one kind or two or more kinds. In particular, two or more kinds are preferable from the viewpoint of uniformly shielding light in the visible region.
The type of pigment that can be used as the colorant (E) is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, organic pigments are preferably used from the viewpoint of controlling the transmission wavelength of the photosensitive resin composition to effectively cure the same.
Examples of the organic pigment include an organic coloring pigment and an organic black pigment. The organic coloring pigment is an organic pigment that exhibits a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.
Among the organic pigments, organic coloring pigments are preferably used from the viewpoint of ultraviolet absorptivity.
The organic coloring pigment may be used alone or in combination of two or more. In particular, in the case of use for light-shielding applications, it is more preferable to use a combination of organic color pigments having different colors, and it is further preferable to use a combination of organic color pigments which exhibit a color close to black.
The chemical structure of these organic pigments is not particularly limited, and examples thereof include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, bisindolinone
Figure BDA0003564604270000561
Oxazines, indanthrene and perylenes. Specific examples of pigments that can be used are shown below by the pigment numbers. The terms "c.i. pigment red 2" and the like listed below refer to the pigment index (c.i.).
As the red pigment, there can be mentioned: c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:2, 53:1, 53:2, 53:3, 57:1, 57:2, 58:4, 60, 63:1, 63:2, 64:1, 68, 69, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101:1, 104, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 169, 151, 166, 168, 149, 170, 172, 176, 187, 188, 207, 188, 194, 185, 194, 187, 185, 194, 187, 194, 185, 194, 187, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 207, 194, 187, 207, 194, 185, 194, 187, 194, 200, 194, 200, 194, 187, 194, 200, 194, 200, 194, 200, 194, 200, 194, 216. 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.
Among them, c.i. pigment red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferable, and c.i. pigment red 177, 209, 224, 254 are more preferable, from the viewpoint of light-shielding property and dispersibility.
In addition, c.i. pigment red 177, 254 and 272 are preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive resin composition is cured by ultraviolet light, it is preferable to use a pigment having a low ultraviolet absorption rate as the red pigment, and from the viewpoint of the above, c.i. pigment red 254 and 272 are more preferably used.
As orange (orange) pigments, mention may be made of: c.i. pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
Among them, c.i. pigment orange 13, 43, 64, 72 is preferably used from the viewpoint of dispersibility and light-shielding properties, and c.i. pigment orange 43, 64, 72 is more preferably used, and when the photosensitive resin composition is cured by ultraviolet light, it is preferable to use a pigment orange having a low ultraviolet absorption rate, and from the viewpoint of the above, c.i. pigment orange 64, 72 is more preferably used.
As the blue pigment, there can be mentioned: pigment blue 1, 1:2, 9, 14, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56:1, 60, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
Among them, from the viewpoint of light-shielding properties, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferable, and c.i. pigment blue 15:6 is more preferable.
In view of dispersibility and light-shielding properties, c.i. pigment blue 15:6, 16, and 60 is preferably used, and c.i. pigment blue 15:6 and 60 is more preferably used, and in the case where the photosensitive resin composition is cured by ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorption rate, and from the above viewpoint, c.i. pigment blue 60 is more preferably used.
As the violet pigment, there can be mentioned: c.i. pigment violet 1, 1:1, 2:2, 3:1, 3:3, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
Among them, c.i. pigment violet 19 and 23 are preferable, and c.i. pigment violet 23 is more preferable, from the viewpoint of light-shielding properties.
In addition, c.i. pigment violet 23, 29 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive resin composition is cured by ultraviolet light, a violet pigment having a low ultraviolet absorption rate is preferably used, and from the viewpoint of the above, c.i. pigment violet 29 is more preferably used.
Examples of the organic coloring pigment that can be used in addition to the red pigment, orange pigment, blue pigment, and violet pigment include green pigment and yellow pigment.
As the green pigment, there can be mentioned: c.i. pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.
Among them, c.i. pigment green 7 and 36 can be preferably cited.
As the yellow pigment, there can be mentioned: pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 188, 193, 198, 195, 185, 188, 193, 194, 198, 197, 200, 204, 197, 200, 194, 204, 199, 204, 197, 200, 204, 199, 204, 197, 204, 200, 199, 204, 200, and 204, 200, 150, 204, 150, 109, 207. 208.
Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150, 180 are more preferable.
Among these, at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a violet pigment is preferably used from the viewpoint of light-shielding properties and ink repellency.
Among these, at least one or more of the following pigments are preferably contained from the viewpoint of light-shielding properties and ink repellency.
Red pigment: c.i. pigment red 177, 254, 272
Orange pigment: c.i. pigment orange 64, 72
Blue pigment: c.i. pigment blue 15: 6. 16, 60
A violet pigment: c.i. pigment violet 23, 29
When two or more organic color pigments are used in combination, the combination of the organic color pigments is not particularly limited, and it is preferable that the colorant (E) contains at least one selected from a red pigment and an orange pigment and at least one selected from a blue pigment and a violet pigment from the viewpoint of light-shielding property.
The combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, for example, the following are listed: a combination of red and blue pigments, a combination of blue and orange pigments and a violet pigment.
In addition, it is preferable to contain a violet pigment as the (E) colorant from the viewpoint of light-shielding property of blue light.
From the viewpoint of light-shielding properties, it is preferable to use an organic black pigment as the (E) colorant. In particular, from the viewpoint of suppressing absorption of ultraviolet rays and improving ink repellency, it is preferable to use an organic black pigment (hereinafter, sometimes referred to as "organic black pigment represented by the general formula (a)") containing at least one selected from the group consisting of a compound represented by the general formula (a) (hereinafter, also referred to as "compound (a)"), a geometric isomer of the compound (a), a salt of the compound (a), and a salt of the geometric isomer of the compound (a 1).
[ chemical formula 42]
Figure BDA0003564604270000591
(in the formula (A), R11And R16Each independently represents a hydrogen atom, CH3、CF3Fluorine atom or chlorine atom;
R12、R13、R14、R15、R17、R18、R19and R20Each independently represents a hydrogen atom, a halogen atom, R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N＝CH2、N＝CHR21、N＝CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21Or SO2NR21R22；
Is selected from R12And R13、R13And R14、R14And R15、R17And R18、R18And R19And R19And R20Can be directly bonded to each other or through an oxygen atom, a sulfur atom, NH or NR21Bridging to bond each other;
R21and R22Each independently is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The compound (a) and the geometric isomer of the compound (a) have the following core structure (in which the substituent in the structural formula is omitted), and the trans-trans isomer may be the most stable.
[ chemical formula 43]
Figure BDA0003564604270000601
When the compound (a) is anionic, it is preferably a salt obtained by compensating the charge of any known suitable cation, for example, a metal, organic, inorganic or metal organic cation, specifically a tertiary amine such as an alkali metal, alkaline earth metal, transition metal, primary amine, secondary amine or trialkylamine, or a quaternary ammonium or organometallic complex compound such as tetraalkylammonium. When the geometric isomer of the compound (a) is anionic, the same salt is preferable.
Among the substituents of the general formula (a) and their definitions, the following substituents are preferred from the viewpoint of having a tendency to increase the shielding rate. This is because the following substituents are not absorbed and do not affect the hue of the pigment.
R12、R14、R15、R17、R19And R20Each independently preferably being a hydrogen atomA fluorine atom or a chlorine atom, and more preferably a hydrogen atom.
R13And R18Each independently preferably represents a hydrogen atom or NO2、OCH3、OC2H5Bromine atom, chlorine atom, CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2Alpha-naphthyl, beta-naphthyl, SO3H or SO3 -More preferably a hydrogen atom or SO 3H is particularly preferably a hydrogen atom.
R11And R16Each independently is preferably a hydrogen atom, CH3Or CF3More preferably, a hydrogen atom.
Preferably selected from R11And R16、R12And R17、R13And R18、R14And R19And R15And R20At least one of the combinations of (1) is the same, more preferably R11And R16Same, R12And R17Same, R13And R18Same, R14And R19Are identical and R15And R20The same is true.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2, 2-dimethylpropyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 1,1,3, 3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
Cycloalkyl having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornyl, norcarane, carane-yl, methyl-ethyl, methyl-propyl, methyl-butyl, methyl-propyl, methyl-butyl, cyclopentyl, cyclohexyl, methyl-hexyl, methyl-pentyl,
Figure BDA0003564604270000612
Alkyl, norpinanyl, pinanyl, 1-adamantyl, 2-adamantyl.
Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl and 2-
Figure BDA0003564604270000613
-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, dodecenyl.
Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl and 1-p-cyclonen
Figure BDA0003564604270000614
Ene-8-yl, 4(10) -limonene-10-yl, 2-norbornene-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norcarene-diene-3-yl, camphyl.
Examples of the alkynyl group having 2 to 12 carbon atoms include a 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1, 4-pentadiyn-3-yl group, 1, 3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1, 3-hexadiyn-5-yl group, 1-octyn-8-yl group, 1-nonyn-9-yl group, 1-decyn-10-yl group, and the like, 1-dodecyn-12-yl.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The organic black pigment represented by the general formula (a) is preferably an organic black pigment containing at least one selected from a compound represented by the following general formula (B) (hereinafter, also referred to as "compound (B)") and a geometric isomer of the compound (B).
[ chemical formula 44]
Figure BDA0003564604270000611
Specific examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably used after being dispersed by a dispersant, a solvent, or a method described later. If the sulfonic acid derivative of the compound (a), particularly the sulfonic acid derivative of the compound (B), is present during dispersion, the dispersibility and the storage stability may be improved, and therefore, the organic black pigment preferably contains these sulfonic acid derivatives.
Examples of the organic black pigment other than the organic black pigment represented by the general formula (a) include aniline black and perylene black.
As a colorant other than these organic pigments, inorganic black pigments can be cited. In addition, an inorganic black pigment may be further used in addition to the organic pigment.
As the inorganic black pigment, there can be mentioned: carbon black, acetylene black, lamp black, bone black, graphite, iron black, Xeronine black, titanium black, and the like. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties. Examples of the carbon black include the following carbon blacks.
Mitsubishi chemical corporation: MA7, MA8, MA11, MA77, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, # 30550, #3250, #3400, #3600, #3750, #3950, #4000, #4010, # 7B, # 9B, OIL11B, OIL30B, OIL31B, and OIL31B
Manufactured by Degussa corporation: printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color FW1, Color Black2, Color 2 FW2V, Color 18, Color 18, Color Black FW 160, Color FW 170, Color FW200 FW S
Manufactured by Cabot corporation: monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCA (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8
Manufactured by Birla corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
Carbon black coated with a resin may be used as the carbon black. When carbon black coated with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. As the carbon black coated with a resin, for example, carbon black described in japanese patent application laid-open No. h 09-71733 can be preferably used. Resin-coated carbon black is preferably used in view of volume resistance and dielectric constant.
As the carbon black to be subjected to the coating treatment with the resin, the total content of Na and Ca is preferably 100ppm or less. Carbon black generally contains ash components such as Na, Ca, K, Mg, Al, and Fe mixed from raw oil, fuel oil (or gas), reaction termination water, and granulation water during production, and furnace materials of a reactor. Among them, Na and Ca are usually contained in an amount of several hundred ppm or more, and the decrease in Na and Ca suppresses penetration into the transparent electrode (ITO) and other electrodes, thereby tending to prevent electrical short circuits.
As a method for reducing the content of these ashes containing Na and Ca, a method of strictly selecting materials with extremely low Na and Ca contents as feedstock oil, fuel oil (or gas), and reaction terminating water in the production of carbon black, and a method of extremely reducing the amount of alkali materials for adjusting the structure can be adopted. Other methods include a method of washing carbon black produced from a furnace with water, hydrochloric acid, or the like to dissolve and remove Na and Ca.
Specifically, when the carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide water and then a solvent which is hardly soluble in water is added, the carbon black is transferred to the solvent side, and is completely separated from water, and almost all of Na and Ca present in the carbon black are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100ppm or less, it may be possible to achieve only a carbon black production process in which the raw materials are strictly selected alone or a method in which the raw materials are dissolved in water or acid alone, but it is easier to reduce the total amount of Na and Ca to 100ppm or less by using both methods in combination.
The resin-coated carbon black is preferably so-called acid carbon black having a pH of 6 or less. The dispersion diameter (agglomerate size) in water is preferably small, and the coating under fine cells can be performed. More preferably, carbon black having an average particle diameter of 40nm or less and a dibutyl phthalate (DBP) absorption of 140mL/100g or less is used. When the amount is within the above range, a coating film having good light-shielding properties tends to be obtained. The average particle diameter is an exponential average particle diameter and is an equivalent circle diameter obtained by particle image analysis in which particles are photographed several tens of thousands times by electron microscope observation to obtain photographs of several fields of view, and the particles of about 2000 to 3000 photographs are measured by an image processing apparatus.
The method for producing the resin-coated carbon black is not particularly limited, and for example, after the blending amounts of the carbon black and the resin are appropriately adjusted, the following method can be employed:
1. mixing a resin with a solvent such as cyclohexanone, toluene, xylene, etc., heating and dissolving the mixture to prepare a resin solution, mixing carbon black and water to prepare a suspension, mixing and stirring the resin solution and the suspension to separate the carbon black from the water, removing the water, heating and kneading the mixture to obtain a composition, forming the obtained composition into a sheet, pulverizing the sheet, and drying the sheet;
2. mixing and stirring the resin solution and the suspension prepared in the same manner as described above, granulating the carbon black and the resin, separating the obtained granules, heating, and removing the residual solvent and water;
3. dissolving carboxylic acid such as maleic acid and fumaric acid in the solvent exemplified above, adding carbon black, mixing, drying, removing the solvent to obtain carbon black to which carboxylic acid is attached (added), and adding resin thereto and dry-mixing;
4. stirring the monomer component containing reactive group and water which form the resin to be coated at high speed to prepare suspension, cooling after polymerization, obtaining the resin containing reactive group from the polymer suspension, adding carbon black into the suspension, mixing, reacting the carbon black with the reactive group (grafting the carbon black), cooling and crushing; and so on.
The type of the resin to be coated is not particularly limited, and is usually a synthetic resin, and a resin having a benzene nucleus in its structure is preferable from the viewpoint of dispersibility and dispersion stability because it has a stronger function as an amphoteric surfactant.
Specific examples of the synthetic resin include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphosate resin, epoxy resin, and alkylbenzene resin, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfone, polyphenylsulfone, polyarylate, and polyether ether ketone. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the amount of the coating resin is not less than the lower limit, the carbon black can be sufficiently coated. On the other hand, when the amount of the coating resin is not more than the upper limit, adhesion between the resins tends to be prevented and dispersibility tends to be good.
The carbon black coated with the resin in this manner can be used as a colorant for producing a color separator by a usual method. When such carbon black is used, colored partition walls having a high light-shielding rate and a low surface reflectance tend to be formed at low cost. Further, coating the surface of carbon black with a resin is also expected to have an effect of enclosing ash containing Na and Ca in carbon black.
These organic pigments and inorganic pigments are preferably used after being dispersed so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the average particle diameter is based on the number of pigment particles.
The average particle diameter of the pigment is a value determined from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on the photosensitive resin composition after being sufficiently diluted (usually diluted to a pigment concentration of about 0.005 to 0.2 mass%, but according to the recommended concentration of the pigment by a measuring instrument), and the measurement is performed at 25 ℃.
In addition, dyes other than the organic pigments and inorganic black pigments described above may be used. As dyes that can be used as colorants, there can be mentioned: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
As azo dyes, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black 5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7.
Examples of the anthraquinone-based dye include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60.
Examples of the phthalocyanine dye include c.i. vat blue 5, examples of the quinoneimine dye include c.i. basic blue 3 and c.i. basic blue 9, examples of the quinoline dye include c.i. solvent yellow 33, c.i. acid yellow 3 and c.i. disperse yellow 64, and examples of the nitro dye include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
When the photosensitive resin composition of the present invention contains (E) a colorant, the content of the (E) colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more, and is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 12% by mass or less, and most preferably 10% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount of the organic solvent is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 2 to 20% by mass, further preferably 2 to 15% by mass, further preferably 3 to 12% by mass, and particularly preferably 4 to 10% by mass. When the lower limit value is not less than the above-mentioned lower limit value, light-shielding properties tend to be secured, and when the upper limit value is not more than the above-mentioned upper limit value, the alkali-soluble resin and the ethylenically unsaturated compound relatively increase, so that curability and ink repellency of the coating film tend to be improved.
[1-1-6] (F) dispersant
When the photosensitive resin composition of the present invention contains (E) a colorant, (F) a dispersant is preferably contained in order to finely disperse the (E) colorant and stabilize the dispersed state.
The dispersant (F) is preferably a polymer dispersant having a functional group, and preferably has a carboxyl group from the viewpoint of dispersion stability; a phosphate group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a polymer dispersant derived from a functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. Among these, in particular, the pigment having a primary amino group, a secondary amino group or a tertiary amino group is particularly preferable from the viewpoint that the pigment can be dispersed with a small amount of a dispersant when dispersed; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine.
Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising an amino group-containing monomer and a macromonomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
Specific examples of such a dispersant include: the trade names are EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), Disparlon (registered trademark, manufactured by Nanguo Kabushiki Kaisha), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by shin-Etsu chemical Co., Ltd.), Polyflow (manufactured by Kyoho chemical Co., Ltd.), and Ajiser (registered trademark, manufactured by K.K.).
These polymeric dispersants may be used alone or in combination of two or more.
The weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and preferably 100000 or less, more preferably 50000 or less. For example, the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 to 100000, more preferably 1000 to 50000.
Among these, from the viewpoint of pigment dispersibility, the dispersant (F) preferably contains one or both of a urethane-based polymer dispersant having a functional group and an acrylic-based polymer dispersant, and particularly preferably contains an acrylic-based polymer dispersant.
In addition, from the viewpoint of storage stability, a polymer dispersant having a basic functional group and one or both of a polyester bond and a polyether bond is preferable.
Examples of the urethane and acrylic polymer dispersants include: DISPERBYK-160-167, 182 series (all carbamates), DISPERBYK-2000, 2001 and BYK-LPN21116 (all acrylics) (all made by BYK-Chemie).
Specifically, the preferable chemical structure of the urethane polymer dispersant is exemplified by a dispersion resin having a weight average molecular weight of 1000 to 200000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule. The dispersion resin may be treated with a quaternizing agent such as benzyl chloride to convert all or a part of the tertiary amino groups into quaternary ammonium salt groups.
Examples of polyisocyanate compounds include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4,4 '-diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, etc., aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc., alicyclic diisocyanates such as isophorone diisocyanate, 4, 4' -methylenebis (cyclohexyl isocyanate), omega '-diisocyanate dimethylcyclohexane, etc., xylylene diisocyanate, aliphatic diisocyanates having an aromatic ring such as alpha, alpha' -tetramethylxylylene diisocyanate, etc., and mixtures thereof, Triisocyanates such as lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate and triphenylthiophosphate triisocyanate, and trimers, hydrides and polyol adducts thereof. The polyisocyanate is preferably a trimer of an organic diisocyanate, and particularly preferably a trimer of toluene diisocyanate or a trimer of isophorone diisocyanate.
These may be used alone in 1 kind, or two or more kinds may be used in combination.
Examples of the method for producing an isocyanate trimer include the following methods: polyisocyanates are partially trimerized with a suitable trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, the trimerization is terminated by adding a catalyst poison, and unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired polyisocyanate containing trimerized isocyanate groups.
Examples of the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the same molecule, include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and those obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these compounds.
Examples of the polyether diol include polyether diol, polyether ester diol, and a mixture of two or more thereof. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and a mixture of two or more thereof.
Examples of the polyether ester diol include those obtained by reacting a diol having an ether group or a mixture thereof with another diol with a dicarboxylic acid or an acid anhydride thereof, or by reacting an alkylene oxide with a polyester diol, for example, poly (polyoxybutylene) adipate. The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxybutylene glycol or a compound obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.
As the polyester diol, there may be mentioned: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof with glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, 2, 4-trimethyl-1, aliphatic diols such as 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, and 1, 9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, aromatic diols such as benzenedimethanol and bis (hydroxyethoxy) benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine) by polycondensation, for example, polyethylene adipate, polybutylene adipate, 1, 6-hexanediol adipate, and ethylene propylene glycol adipate, or polylactone diols or polylactone monools obtained by using the above diols or monools having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone diol, polycaprolactone monool, and the like, Polymethyl valerolactone and mixtures of two or more thereof. The polyester diol is particularly preferably polycaprolactone diol or polycaprolactone obtained using an alcohol having 1 to 25 carbon atoms as an initiator.
Examples of the polycarbonate diol include: poly (1, 6-hexanediol) carbonate, poly (3-methyl-1, 5-pentanediol) carbonate, etc., and examples of the polyolefin diol include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.
These compounds may be used alone or in combination of two or more.
The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is preferably 300 to 10000, more preferably 500 to 6000, and further preferably 1000 to 4000.
A compound having an active hydrogen and a tertiary amino group in the same molecule will be described.
Examples of the active hydrogen, i.e., the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, include: among the hydroxyl group, amino group, and mercapto group, the hydrogen atom of an amino group, particularly a primary amino group, is preferable.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and more specifically, an imidazole ring and a triazole ring.
Examples of the compound having an active hydrogen and a tertiary amino group in the same molecule include: n, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, N-dipropyl-1, 3-propanediamine, N-dibutyl-1, 3-propanediamine, N-dimethylethylenediamine, N-diethylethylenediamine, N-dipropylethylenediamine, N-dibutylethylenediamine, N-dimethyl-1, 4-butanediamine, N-diethyl-1, 4-butanediamine, N-dipropyl-1, 4-butanediamine, N-dibutyl-1, 4-butanediamine.
Examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocyclic structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring
Figure BDA0003564604270000691
Nitrogen-containing 5-membered heterocycles such as an azole ring, a benzothiazole ring and a benzothiadiazole ring, and nitrogen-containing 6-membered heterocycles such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring and an isoquinoline ring. Among these nitrogen-containing heterocycles, imidazole ring and triazole ring are preferable.
Examples of the compound having an imidazole ring and an amino group include: 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole.
Examples of the compound having a triazole ring and an amino group include: 3-amino-1, 2, 4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1, 2, 4-triazole, 4-amino-4H-1, 2, 4-triazole-3, 5-diol, 3-amino-5-phenyl-1H-1, 3, 4-triazole, 5-amino-1, 4-diphenyl-1, 2, 3-triazole, 3-amino-1-benzyl-1H-2, 4-triazole.
Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1, 2, 4-triazole are preferable.
These compounds may be used alone or in combination of two or more.
The preferable blending ratio of the raw materials for producing the urethane polymer dispersant is as follows: the amount of the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the same molecule, is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, based on 100 parts by mass of the polyisocyanate compound.
The urethane polymer dispersant can be produced by a known method for producing a polyurethane resin. As the solvent for the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, hydrocarbons such as benzene, toluene, xylene and hexane, partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tert-butyl alcohol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, and polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide are generally used.
These may be used alone or in combination of two or more.
In the production of a urethane polymer dispersant, a urethane reaction catalyst is generally used. Examples of the catalyst for the urethanization reaction include: tin-based amines such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octylate, iron-based amines such as iron acetylacetonate and iron chloride, and tertiary amines such as triethylamine and triethylenediamine.
These may be used alone or in combination of two or more.
The amount of the compound having an active hydrogen and a tertiary amino group introduced into the same molecule is preferably controlled to be in the range of preferably 1 to 100mgKOH/g, more preferably 5 to 95mgKOH/g, in terms of the amine value after the reaction. The amine number is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the lower limit value is not less than the above-mentioned lower limit value, the dispersibility tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the developability tends to be improved.
When the isocyanate group remains in the polymer dispersant, it is preferable to deactivate the isocyanate group with an alcohol or an amino compound because the product has high stability with time.
The weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1000 to 200000, more preferably 2000 to 100000, and further preferably 3000 to 50000. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility and dispersion stability tend to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, solubility tends to be improved and dispersibility tends to be improved.
As the acrylic polymer dispersant, a random copolymer, a graft copolymer, or a block copolymer of a monomer having a functional group (the functional group referred to herein is the functional group described above as the functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group and containing an unsaturated group is preferably used. These copolymers can be produced by a known method.
Examples of the monomer having a functional group and containing an unsaturated group include: unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or a quaternary ammonium group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternary products thereof.
These may be used alone or in combination of two or more.
Examples of the monomer having no functional group and containing an unsaturated group include: n-substituted maleimides such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, alpha-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide, and the like, Acrylonitrile, vinyl acetate, polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly (meth) acrylic acid 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer and the like macromonomer.
These may be used alone or in combination of two or more.
The acrylic polymer dispersant is particularly preferably an a-B or B-a-B block copolymer composed of an a block having a functional group and a B block having no functional group, and in this case, the a block may contain a partial structure derived from the monomer not having a functional group but having an unsaturated group in addition to the partial structure derived from the monomer having a functional group and having an unsaturated group, and these structures may be contained in the a block in any form of random copolymerization or block copolymerization.
The content of the partial structure containing no functional group in the a block is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less.
The B block includes a partial structure derived from the above-mentioned monomer having no functional group but having an unsaturated group, and 1B block may contain a partial structure derived from two or more monomers, and these structures may be contained in the B block in any form of random copolymerization or block copolymerization.
The A-B or B-A-B block copolymer can be produced by, for example, the living polymerization method shown below.
The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method and a free radical living polymerization method.
For the synthesis of the acrylic polymer dispersant, there may be used, for example, the publicly known methods described in Japanese patent application laid-open No. 9-62002, P.Lutz, P.Masson et al, Polym.Bull.12,79(1984), B.C.Anderson, G.D.Andrews et al, Macromolecules,14,1601(1981), K.Hatada, K.Ute, et al, Polym.J.17,977(1985),18,1037(1986), Right hand Haoyi, Ushui, Polymer processing, 36, 366(1987), Tomura, Zubenyoyan, Polymer literature, 46,189(1989), M.Kuroki, T.Aida, J.Am.Chem.sic,109,4737(1987), Zhang, Shangping, organic Synthesis chemistry, 43,300, Y.1985, Sotlh.W.1983, Hercules, 20.
The acrylic polymer dispersant usable in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block/B block ratio constituting the copolymer is preferably 1/99 to 80/20 (mass ratio), and particularly preferably 5/95 to 60/40 (mass ratio). When the amount is within the above range, the dispersibility and the storage stability tend to be well balanced.
In 1g of the A-B block copolymer and the B-A-B block copolymer which can be used in the present invention, the amount of the quaternary ammonium salt group is preferably 0.1 to 10 mmol. When the amount is within the above range, good dispersibility tends to be ensured.
When the block copolymer contains an amino group generated in the production process, the amine value is preferably 1 to 100mgKOH/g, and from the viewpoint of dispersibility, the amine value is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and further preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less. For example, it is preferably 1 to 100mgKOH/g, more preferably 10 to 90mgKOH/g, further preferably 30 to 80mgKOH/g, particularly preferably 50 to 75 mgKOH/g.
The amine value of a dispersant such as a block copolymer is represented by the mass of KOH corresponding to the amount of base of 1g of solid components other than a solvent in a dispersant sample, and is measured by the following method.
0.5 to 1.5g of a dispersant sample was precisely weighed in a 100mL beaker, dissolved in 50mL of acetic acid, and subjected to a 0.1mol/L HClO solution using an automatic titrator equipped with a pH electrode4The solution was subjected to neutralization titration with acetic acid solution, and the amine value was determined by the following equation, with the inflection point of the titration pH curve being set as the titration end point.
Amine value [ mgKOH/g ] (561 XV)/(W X S)
[ wherein, W: the weighed amounts [ g ] of the dispersant samples, V: the titration amount [ mL ] at the end of titration, S: the solid content concentration [ mass% ] of the dispersant sample is shown. ]
The acid value of the block copolymer depends on the presence or absence of an acid group as a base of the acid value and the kind thereof, and is preferably a low acid value, and preferably 10mgKOH/g or less.
The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1000 to 100000. By setting the content within the above range, good dispersibility tends to be ensured.
When the functional group is a quaternary ammonium salt group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the functional group preferably has a repeating unit represented by the following formula (r-i) (hereinafter, may be referred to as "repeating unit (r-i)").
[ chemical formula 45]
Figure BDA0003564604270000731
(in the formula (R-i), R31～R33Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent;
R31～R 332 or more of them may be bonded to each other to form a ring structure;
R34is a hydrogen atom or a methyl group;
x is a linking group having a valence of 2;
Y-are counter anions. )
R of formula (R-i)31～R33The number of carbon atoms of the optionally substituted alkyl group in (1) is not particularly limited, but is 1 or more, preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include: among these, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl are preferable, and methyl, ethyl, propyl, butyl, pentyl, and hexyl are more preferable. The polymer may be in any form of straight chain or branched chain. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
R of the formula (R-i)31～R33The number of carbon atoms of the aryl group optionally having a substituent(s) in (2) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, more preferably 12 or less. Specific examples of the aryl group include: phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl and anthracenyl, of these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl and diethylphenyl are preferred, and phenyl, methylphenyl and ethylphenyl are more preferred.
R of the formula (R-i)31～R33The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is preferably 7 or more, and is preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include: among them, phenylmethyl (benzyl), phenylethyl (phenylethyl), phenylpropyl, phenylbutyl and phenylisopropyl are preferable, and phenylmethyl, phenylethyl, phenylpropyl and phenylbutyl are more preferable, and phenylmethyl and phenylethyl are still more preferable.
Of these, R is preferable from the viewpoint of dispersibility31～R33Each independently is alkyl or aralkyl, specifically, R is preferred31And R33Each independently being methyl or ethyl, and R 32Is phenylmethyl or phenylethyl, more preferably R31And R33Is methyl and R32Is a phenylmethyl group.
When the polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following formula (r-ii) (hereinafter, may be referred to as "repeating unit (r-ii)") from the viewpoint of dispersibility.
[ chemical formula 46]
Figure BDA0003564604270000741
(in the formula (R-ii), R35And R36Each independently is a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent;
R35and R36May be bonded to each other to form a ring structure;
R37is a hydrogen atom or a methyl group;
z is a linking group having a valence of 2. )
R as formula (R-ii)35And R36As the alkyl group optionally having a substituent(s) in (1), R of the formula (R-i)31～R33Those illustrated.
R as formula (R-ii)35And R36As the optionally substituted aryl group in (1), R of the formula (R-i)31～R33Those illustrated.
R as formula (R-ii)35And R36As the aralkyl group optionally having a substituent(s) in (1), R of the formula (R-i)31～R33Those illustrated.
Of these, R35And R36Preferably each independently an optionally substituted alkyl group, more preferably a methyl or ethyl group.
R as formula (R-i)31～R33And R of formula (R-ii)35And R36The alkyl group, aralkyl group or aryl group in (1) may have a substituent such as: halogen atom, alkoxy, benzoyl, hydroxyl.
In the formulae (r-i) and (r-ii), examples of the 2-valent linking groups X and Z include: alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R43-radical, -COOR44A group [ wherein, R43And R44A single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (an alkyloxyalkyl group) having 2 to 10 carbon atoms]Etc., preferably-COO-R44-a radical.
In the formula (r-i), Y as a counter anion-Examples thereof include: cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -。
The content ratio of the repeating unit represented by the formula (r-i) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, particularly preferably 35 mol% or less, and further preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more, relative to the total of the content ratio of the repeating unit represented by the formula (r-i) and the content ratio of the repeating unit represented by the formula (r-ii). For example, the amount is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.
The content of the repeating unit represented by the formula (r-i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and further preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less from the viewpoint of dispersibility. For example, the amount is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, further preferably 5 to 20 mol%, and particularly preferably 10 to 15 mol%.
The content of the repeating unit represented by the formula (r-ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and further preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less, from the viewpoint of dispersibility. For example, the amount is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, further preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.
From the viewpoint of improving the compatibility of a solvent or the like with a binder component and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (r-iii) (hereinafter, may be referred to as "repeating unit (r-iii)").
[ chemical formula 47]
Figure BDA0003564604270000751
(in the formula (R-iii), R40Is ethylene or propylene;
R41is an alkyl group optionally having a substituent;
R42is a hydrogen atom or a methyl group;
n is an integer of 1 to 20. )
R of formula (R-iii)41The number of carbon atoms of the optionally substituted alkyl group in (2) is not particularly limited, but is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include: among these, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl are preferable, and methyl, ethyl, propyl, butyl, pentyl, or hexyl is more preferable, and methyl, ethyl, propyl, or butyl is more preferable. The polymer may be in any form of straight chain or branched chain. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 2 to 6.
From the viewpoint of compatibility with a solvent or a binder component and dispersibility, n in the formula (r-iii) is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. For example, the amount of the surfactant is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
The content of the repeating unit represented by the formula (r-iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. When the amount is within the above range, compatibility with a solvent or a binder component and dispersion stability tend to be compatible with each other. For example, the content ratio of the repeating unit represented by the formula (r-iii) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%.
In addition, from the viewpoint of improving the compatibility of the dispersant with respect to the solvent and the binder component and improving the dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (r-iv) (hereinafter, may be referred to as "repeating unit (r-iv)").
[ chemical formula 48]
Figure BDA0003564604270000761
(in the formula (R-iv), R38Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent;
R39Is a hydrogen atom or a methyl group. )
R of formula (R-iv)38The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((b) is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 4 or more, and further preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include: among these, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl are preferable, and methyl, ethyl, propyl, butyl, pentyl, and hexyl are more preferable. The polymer may be in any form of straight chain or branched chain. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 2 to 8, and further preferably 4 to 8.
R of formula (R-iv)38The number of carbon atoms of the aryl group optionally having a substituent(s) in ((b) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less. Specific examples of the aryl group include: phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl and anthracenyl groups, of these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl and diethylphenyl groups are preferred, and phenyl, methylphenyl, naphthyl and anthryl groups are more preferred, An ethyl phenyl group. For example, the number of carbon atoms of the aryl group is preferably 6 to 16, more preferably 6 to 12, and still more preferably 8 to 12
R of the formula (R-iv)38The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is preferably 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. Specific examples of the aralkyl group include: among them, phenylmethyl (benzyl), phenylethyl (phenylethyl), phenylpropyl, phenylbutyl and phenylisopropyl are preferable, and phenylmethyl, phenylethyl, phenylpropyl and phenylbutyl are more preferable, and phenylmethyl and phenylethyl are still more preferable. For example, the number of carbon atoms of the aralkyl group is preferably 7 to 16, more preferably 7 to 12, and still more preferably 7 to 10.
Among these, from the viewpoint of solvent compatibility and dispersion stability, R is38Alkyl or aralkyl is preferred, and methyl, ethyl, phenylmethyl are more preferred.
As R38Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. As R38The aryl group or aralkyl group in (1) may have a substituent such as: a chain alkyl group, a halogen atom, or an alkoxy group. R 38The chain alkyl group includes any of straight chain and branched chain.
From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (r-iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less. For example, the amount is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol%.
The polymer dispersant may have a repeating unit other than the repeating unit (r-i), the repeating unit (r-ii), the repeating unit (r-iii) and the repeating unit (r-iv). Examples of such repeating units include: styrene monomers such as styrene and alpha-methylstyrene; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of N-methacryloylmorpholine.
From the viewpoint of further improving the dispersibility, the polymeric dispersant is preferably a block copolymer having an a block having a repeating unit (r-i) and a repeating unit (r-ii) and a B block having no repeating unit (r-i) and no repeating unit (r-ii). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing a quaternary ammonium salt group and a tertiary amino group into the a block, the dispersing ability of the dispersant tends to be remarkably improved. The B block preferably has a repeating unit (r-iii), and more preferably has a repeating unit (r-iv).
The A block may contain the repeating unit (r-i) and the repeating unit (r-ii) in any form of random copolymerization or block copolymerization. In this case, the respective repeating units may be contained in the a block in any form of random copolymerization or block copolymerization.
The A block may contain a repeating unit other than the repeating unit (r-i) and the repeating unit (r-ii), and examples of such a repeating unit include the repeating unit derived from the (meth) acrylate monomer described above. The content of the repeating unit other than the repeating unit (r-i) and the repeating unit (r-ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 mol%.
The B block may contain a repeating unit other than the repeating units (r-iii) and (r-iv), and examples of such a repeating unit include styrene-based monomers derived from styrene, alpha-methylstyrene, etc.; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (r-iii) and the repeating unit (r-iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 mol%.
When the photosensitive resin composition of the present invention contains the dispersant (F), the content thereof is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.1 to 8% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and particularly preferably 0.5 to 2% by mass. When the lower limit is not less than the above-mentioned lower limit, generation of residue due to aggregates tends to be suppressed, and when the upper limit is not more than the above-mentioned upper limit, ink repellency and developability tend to be improved.
[1-1-7] ultraviolet absorber
The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the following purpose: the photocuring profile is controlled by absorbing a specific wavelength of a light source for exposure with an ultraviolet absorber. By adding the ultraviolet absorber, effects such as formation of high-definition barrier ribs with a narrow line width and removal of residue remaining in unexposed portions after development can be obtained. As the ultraviolet absorber, a compound having a maximum absorption at a wavelength of 250nm to 400nm, for example, can be used from the viewpoint of inhibiting the light absorption of the photopolymerization initiator (B).
The ultraviolet absorber preferably contains either or both of a benzotriazole compound and a triazine compound. It is considered that by containing either one or both of the benzotriazole-based compound and the triazine-based compound, the light absorption rate of the initiator at the bottom of the film is reduced, and the line width at the lower portion of the coating film is reduced, whereby a highly fine partition wall having a fine line width can be formed.
Examples of the benzotriazole compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl 3- [ 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate, ethylhexyl 3- [ 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, ester compounds of 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 3- [ 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionic acid and C7-9 straight and branched chain alkyl alcohols.
Examples of commercially available benzotriazole compounds include: sumisorb (registered trademark, same hereinafter) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by North City chemical industry), TINUVIN (registered trademark, same hereinafter) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVSORB 78, EVERSORB80, SORB81 (manufactured by SORB 81), ORSORB 701, OSERSORB 702 (manufactured by Shinshui chemical Co., TomiRB), ORESRB 702, Shinshui chemical industry OSUB, Shinshui (manufactured by Tomsab), SERB 706, Shinshui chemical industries (manufactured by Tornab), SERB) 100, Torsorb, Shinshui, SERB (manufactured by Torsorb), SERB 702, SERB 706, SEESRB 702, SERB 706, SERB 702, SEESRB 702, SERB 702, and SERB 702, SEESRB 702, SERB and the same below.
Examples of the triazine compound include: 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5-octyloxyphenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with 2-ethylhexylglycidyl ether, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1, 3-5-triazine. Among these, from the viewpoint of forming a high-definition partition wall having ink repellency and a narrow line width, a hydroxyphenyltriazine compound is preferable.
Examples of commercially available triazine compounds include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).
Examples of the other ultraviolet absorbers include: benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, binaphthalene compounds, phenanthroline compounds, dyes.
More specifically, for example: benzophenone compounds such as Sumisorb 130 (manufactured by Sumitomo chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongshioto chemical industry Co., Ltd.), Tomisorb 800 (manufactured by API Co., Ltd.), SEESORB100, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107 and SEESORB151 (manufactured by Shipro Kasei); benzoic acid ester compounds such as Sumisorb 400 (manufactured by Sumitomo chemical Co., Ltd.) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as α -naphthol, β -naphthol, α -naphthol methyl ether, α -naphthol ethyl ether, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and 2, 7-dihydroxynaphthalene; anthracene such as anthracene and 9, 10-dihydroxyanthracene, and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like. Among these, cinnamic acid derivatives and naphthalene derivatives are preferably used from the viewpoint of ink repellency, and cinnamic acid derivatives are particularly preferably used.
Among these, from the viewpoint of the tapered shape, either one or both of the benzotriazole-based compound and the hydroxyphenyltriazine-based compound are preferable, and the benzotriazole-based compound is particularly preferable.
One kind of the ultraviolet absorber may be used alone, or two or more kinds may be used in combination.
When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content thereof is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, and further preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.01 to 15% by mass, more preferably 0.05 to 15% by mass, still more preferably 0.1 to 10% by mass, still more preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass. When the lower limit value is not less than the lower limit value, a high-definition partition wall having a narrow line width tends to be formed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be high.
When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio of the ultraviolet absorber to the photopolymerization initiator (B) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and further preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less, in terms of the blending amount of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator (B). For example, the amount of the organic solvent is preferably 1 to 500 parts by mass, more preferably 10 to 500 parts by mass, still more preferably 30 to 300 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 80 to 100 parts by mass. When the lower limit value is not less than the lower limit value, a high-definition partition wall having a narrow line width tends to be formed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be high.
[1-1-8] polymerization inhibitor
The photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since the inclusion of the polymerization inhibitor inhibits radical polymerization, the taper angle of the obtained partition wall tends to be increased.
Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of the polymerization inhibiting ability, hydroquinone, methoxyphenol and methylhydroquinone are preferable, and methylhydroquinone is more preferable.
The polymerization inhibitor may be used alone or in combination of two or more.
According to the method for producing an alkali-soluble resin (C), the produced alkali-soluble resin may contain a polymerization inhibitor. In this case, the alkali-soluble resin may be used in a state in which a polymerization inhibitor is contained therein, or a polymerization inhibitor which may be the same as or different from the polymerization inhibitor contained in the resin may be added thereto in the production of the photosensitive resin composition.
When the photosensitive resin composition contains a polymerization inhibitor, the content thereof is not particularly limited, and is preferably 0.0005 mass% or more, more preferably 0.001 mass% or more, and even more preferably 0.01 mass% or more, and is preferably 0.1 mass% or less, more preferably 0.08 mass% or less, and even more preferably 0.05 mass% or less of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.08% by mass, and still more preferably 0.01 to 0.05% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the taper angle tends to be increased, and when the upper limit value is not more than the above-mentioned upper limit value, the ink repellency tends to be increased.
[1-1-9] thermal polymerization initiator
The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. The inclusion of the thermal polymerization initiator tends to increase the degree of crosslinking of the film. Specific examples of such a thermal polymerization initiator include: azo compounds, organic peroxides and hydrogen peroxide.
These thermal polymerization initiators may be used alone or in combination of two or more.
When a thermal polymerization initiator is used in combination with a photopolymerization initiator in order to improve ink repellency and increase the crosslinking density of a film, the total content ratio of these components is preferably set to the content ratio of the photopolymerization initiator in the photosensitive resin composition described above, and from the viewpoint of ink repellency, the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator is preferably 5 to 300 parts by mass per 100 parts by mass of the photopolymerization initiator.
[1-1-10] amino compounds
The photosensitive resin composition of the present invention may contain an amino compound to promote thermal curing. When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 0.5% by mass or more, more preferably 1% by mass or more of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass. When the upper limit value is equal to or less than the upper limit value, the storage stability tends to be maintained, and when the lower limit value is equal to or more than the lower limit value, sufficient thermosetting properties tend to be secured.
Examples of the amino compound include: an amino compound having at least 2 functional groups selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group obtained by condensation-modifying a hydroxymethyl group with an alcohol having 1 to 8 carbon atoms. Specific examples thereof include: a melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by condensation polymerization of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril with formaldehyde; urea-formaldehyde resin obtained by condensation polymerization of urea and formaldehyde; a resin obtained by copolycondensation of formaldehyde and two or more of melamine, benzoguanamine, glycoluril, urea, or the like; a modified resin obtained by modifying the methylol group of the above resin by alcohol condensation.
These amino compounds may be used alone or in combination of two or more.
Among these amino compounds, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins having a modification ratio of 80% or more are even more preferable.
Specific examples of the amino compound include melamine resins and modified resins thereof, including: "CYMEL" (registered trademark, the same below) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, manufactured by Cytec corporation, and "Nicarac" (registered trademark, the same below) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302, manufactured by Sanko chemical Co., Ltd.
Examples of the benzoguanamine resin and its modified resin include: "CYMEL" 1123, 1125, 1128 by Cytec Inc.
Examples of glycoluril resin and modified resin thereof include: "CYMEL" 1170, 1171, 1174, 1172, manufactured by Cytec corporation, and "Nicarac" MX-270, manufactured by Sanko chemical Co.
As the urea resin and its modified resin, for example: "UFR" (registered trademark) 65, 300 manufactured by Cytec corporation, and "Nicarac" MX-290 manufactured by Sanand chemical Co., Ltd.
[1-1-11] silane coupling agent
The photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve adhesion to a substrate.
As the silane coupling agent, for example, epoxy, methacrylic, amino, and imidazole silane coupling agents can be used, but epoxy and imidazole silane coupling agents are particularly preferable from the viewpoint of improving adhesion.
When the photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof in the entire solid content of the photosensitive resin composition is preferably 20 mass% or less, more preferably 15 mass% or less, from the viewpoint of adhesion.
[1-1-12] inorganic Filler
The photosensitive resin composition of the present invention may further contain an inorganic filler for the purpose of improving strength when a cured product is produced, and improving excellent verticality and taper angle of a coating film due to a proper interaction (formation of a matrix structure) with an alkali-soluble resin.
Examples of the inorganic filler include: talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or a surface-treated product thereof with various silane coupling agents.
The inorganic filler preferably has an average particle diameter of 0.005 to 2 μm, more preferably 0.01 to 1 μm. The average particle diameter is a value measured by a laser diffraction scattering particle size distribution measuring apparatus manufactured by Beckman Coulter, Inc. or the like. Among the inorganic fillers, silica sol and silica sol modified products are particularly preferable because they tend to have excellent dispersion stability and an excellent effect of improving the cone angle.
When the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less of the total solid content of the photosensitive resin composition, from the viewpoint of ink repellency. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
[1-1-13] Adhesivity improver
The photosensitive resin composition of the present invention may contain an adhesion improving agent for the purpose of imparting adhesion to a substrate. Examples of the adhesion improver include an olefinic monomer of phosphoric acid.
The vinyl monomer of the phosphoric acid-based compound is preferably a (meth) acryloyloxy group-containing phosphate ester, and is preferably an adhesion improver represented by the following general formula (g1), (g2) or (g 3).
[ chemical formula 49]
Figure BDA0003564604270000841
(in the above general formulae (g1), (g2) and (g3), R51Represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3. )
These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more.
When the photosensitive resin composition of the present invention contains a phosphoric acid-based ethylenic monomer as an adhesion improver, the content thereof is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, and further preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less, of the total solid content of the photosensitive resin composition. For example, the amount is preferably 0.02 to 4% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, the effect of improving the adhesion to the substrate tends to be sufficient, and when the upper limit value is set to be lower than the lower limit value, the deterioration of the adhesion to the substrate tends to be easily suppressed.
[1-1-14] solvent
The photosensitive resin composition of the present invention usually contains a solvent, and the components contained in the photosensitive resin composition can be used in a state dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the following organic solvents.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; glycol diacetate esters such as ethylene glycol diacetate, propylene glycol diacetate, 1, 3-butanediol diacetate, 1, 4-butanediol diacetate, and 1, 6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate;
Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether;
ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone;
monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
linear or cyclic esters such as amyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;
tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.
Examples of commercially available solvents include: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco triner, Socal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (digle) (all trade names), and the like.
The solvent capable of dissolving or dispersing each component contained in the photosensitive resin composition may be selected according to the method of using the photosensitive resin composition of the present invention, and the boiling point of the solvent at atmospheric pressure is preferably 60 to 280 ℃, more preferably 70 to 260 ℃ or lower from the viewpoint of coatability. Among them, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.
One solvent may be used alone, or two or more solvents may be used in combination.
The solvent is preferably used in the following manner: the content ratio of the total solid content in the photosensitive resin composition solution is preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, and particularly preferably 25 mass% or more, and is preferably 90 mass% or less, more preferably 50 mass% or less, further preferably 40 mass% or less, and particularly preferably 35 mass% or less. For example, the solvent is preferably used so that the content of the total solid content in the photosensitive resin composition solution is preferably 10 to 90% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, the occurrence of coating unevenness tends to be suppressed, and when the upper limit value is set to be equal to or lower than the upper limit value, the occurrence of foreign matter, dents, and the like tends to be suppressed.
[1-2] method for producing photosensitive resin composition
The photosensitive resin composition of the present invention is prepared by mixing the components contained in the photosensitive resin composition with a stirrer.
For example, when a component which does not require a solvent, such as a pigment as the colorant (E), is contained, it is preferable to perform a dispersion treatment in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. By the dispersion treatment, the colorant (E) is micronized, and thus the coating properties of the photosensitive resin composition are improved.
The dispersion treatment is preferably carried out in a system using a combination of (E) a colorant, a solvent and (F) a dispersant, or in a system using a combination of (C) an alkali-soluble resin in part or in whole, as desired (hereinafter, the mixture used for the dispersion treatment and the composition obtained by the dispersion treatment are also referred to as "ink" or "pigment dispersion liquid"). In particular, when a polymer dispersant is used as the dispersant (F), the dispersion stability of the obtained ink and photosensitive resin composition is excellent, and thickening with time is suppressed, which is preferable.
In this way, in the step of producing the photosensitive resin composition, it is preferable to produce a pigment dispersion liquid containing at least (E) the colorant, the solvent and (F) the dispersant.
As the (E) colorant, the organic solvent and the (F) dispersant which can be used in the pigment dispersion liquid, the components described as those which can be used in the photosensitive resin composition can be preferably used. The content ratio of the colorant (E) in the pigment dispersion can be preferably the content ratio described in the photosensitive resin composition.
When the colorant (E) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. For the dispersion treatment conditions, the temperature is generally in the range of 0 ℃ to 100 ℃, preferably room temperature to 80 ℃. The appropriate time for the dispersion time is not the same depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and thus can be appropriately adjusted. The approximate criteria for dispersion are: the gloss of the ink is controlled so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.
The pigment dispersed in the ink has a dispersion particle diameter of usually 0.03 to 0.3 μm, which is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment is mixed with other components contained in the photosensitive resin composition to prepare a uniform solution or dispersion. In the production process of the photosensitive resin composition, since fine dust may be mixed into the liquid, it is preferable to perform a filtration treatment of the obtained photosensitive resin composition with a filter or the like.
[2] Spacer and method for forming the same
The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention can be used for forming partition walls, and can be preferably used for forming the following partition walls, for example: partition walls for partitioning an organic layer of an organic electroluminescent element, and partition walls for partitioning a pixel portion of a color filter containing luminescent nanocrystal particles. The partition wall of the present invention is composed of the cured product of the present invention.
The method for forming the partition walls using the photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be used. Examples of the method for forming the partition wall include: the method comprises a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. Specific examples of such a method for forming the partition wall include an ink jet method and a photolithography method.
In the ink jet method, a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are ejected onto a substrate by the ink jet method along a predetermined pattern of partition walls, whereby the photosensitive resin composition is applied onto the substrate to form a pattern of uncured partition walls. Then, the pattern of the uncured barrier ribs is exposed to light, thereby forming the cured barrier ribs on the substrate. The exposure of the pattern of the uncured partition walls is performed in the same manner as in the exposure step in the photolithography method described later, except that no mask is used.
In the photolithography method, a photosensitive resin composition is applied to the entire surface of a region of a substrate where partition walls are to be formed, thereby forming a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed to light corresponding to a pattern of the partition walls, the exposed photosensitive resin composition layer is developed to form the partition walls on the substrate.
In a coating step of coating a photosensitive resin composition on a substrate in photolithography, a photosensitive resin composition layer is formed on a substrate on which partition walls are to be formed, by coating the photosensitive resin composition using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spin coater (a spin coater) or a curtain flow coater, and drying the coating apparatus if necessary to remove a solvent.
Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer laser light using a negative mask, and the photosensitive resin composition layer is partially exposed in accordance with the pattern of the bank. The exposure may be performed using a light source emitting ultraviolet light, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, 10 to 400mJ/cm2Left and right.
Next, in a developing step, the photosensitive resin composition layer exposed to light in accordance with the pattern of the partition walls is developed with a developing solution to form the partition walls. The developing method is not particularly limited, and a dipping method, a spraying method, and the like can be used. Specific examples of the developer include: organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoaming agent and a surfactant may be added to the developer.
Then, the developed partition wall is subjected to post baking, i.e., heat curing treatment. The post-baking is preferably carried out at 80-250 ℃ for 15-180 minutes.
The substrate for forming the partition walls is not particularly limited, and may be appropriately selected depending on the kind of the organic electroluminescent element manufactured using the substrate with the partition walls formed. Preferable substrate materials include glass and various resin materials. Specific examples of the resin material include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; a polycarbonate; a poly (meth) acrylic resin; polysulfones; and (3) a polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. In addition, a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition walls are to be formed, depending on the type of the organic electroluminescent element to be manufactured.
The thickness of the partition wall of the present invention is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 5 μm or more, and particularly preferably 10 μm or more, and is preferably 1mm or less, more preferably 100 μm or less, further preferably 50 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. When the lower limit value is not less than the lower limit value, the light shielding property tends to be improved, and when the upper limit value is not more than the upper limit value, the adhesion tends to be improved. The film thickness of the partition wall is measured by a height difference/surface roughness/fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
[3] Organic electroluminescent element
The organic electroluminescent element of the present invention comprises the partition wall of the present invention.
Various organic electroluminescent elements can be manufactured using the substrate having the partition wall pattern manufactured by the method described above. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into a region surrounded by the partition walls on the substrate after forming the pattern of the partition walls on the substrate by the above-mentioned method.
Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall.
When the partition walls have a skirt shape, the ink for forming an organic layer is repelled at the skirt portions of the partition walls, and therefore the region surrounded by the partition walls may not be sufficiently covered with the ink for forming an organic layer. In contrast, by forming the partition wall in a good shape without a skirt, the region surrounded by the partition wall can be sufficiently covered with the organic layer forming ink. This can eliminate, for example, the problem of halation in the organic EL display element.
As the solvent used for forming the ink for forming an organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the formed film after the ink is injected. Specific examples of the organic solvent include: toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene, and the like. In addition, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like may be added to the ink.
As a method of injecting ink into the region surrounded by the partition walls, an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined portion. The ink used for forming the organic layer may be appropriately selected depending on the kind of the organic electroluminescent element to be produced. When the ink is injected by the ink jet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the ink jet head, but is preferably 4 to 20mPa · s, more preferably 5 to 10mPa · s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.
The light-emitting layer may be an organic electroluminescent layer as described in japanese patent laid-open nos. 2009-146691 and 5734681. In addition, quantum dots as described in japanese patent No. 5653387 and japanese patent No. 5653101 may be used.
[4] Color filter comprising luminescent nanocrystalline particles
The color filter containing luminescent nanocrystal particles of the present invention is not particularly limited as long as it has the partition walls of the present invention, and examples thereof include a color filter in which pixels are formed in regions defined by the partition walls.
FIG. 1 is a schematic cross-sectional view of an example of a color filter having barrier ribs according to the present invention. As shown in fig. 1, the color filter 100 includes: a substrate 10, a barrier rib 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50. The red pixels 30, the green pixels 40, and the blue pixels 50 are repeatedly arranged in a grid pattern in this order. Barrier ribs 20 are provided between these adjacent pixels. In other words, these adjacent pixels are divided from each other by the partition walls 20.
The red pixel 30 includes red-light-emitting nanocrystal particles 2, and the green pixel 40 includes green-light-emitting nanocrystal particles 1. The blue pixel 50 is a pixel that transmits blue light from the light source.
These luminescent nanocrystal particles are nanosized crystals that absorb excitation light and emit fluorescence or phosphorescence, and are crystals having a maximum particle diameter of 100nm or less as measured by a transmission electron microscope or a scanning electron microscope, for example.
The luminescent nanocrystal particle is a substance capable of absorbing light of a given wavelength and emitting light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength, and for example, the nanocrystal particle 2 emitting red light is a substance emitting light (red light) having an emission peak wavelength in a range of 605 to 665nm, and the nanocrystal particle 1 emitting green light is a substance emitting light (green light) having an emission peak wavelength in a range of 500 to 560 nm.
The wavelength (light emission color) of light emitted from the luminescent nanocrystal particle depends on the size (for example, particle diameter) of the luminescent nanocrystal particle, but also on the energy band of the luminescent nanocrystal particle, depending on the solution of schrodinger wave equation for solving the well potential model. Therefore, the luminescent color can be selected by changing the constituent material and the size of the luminescent nanocrystal particle to be used. Examples of luminescent nanocrystal particles include quantum dots.
The method for producing a color filter containing luminescent nanocrystal particles is not particularly limited, and the following methods may be mentioned: a substrate having partition walls made of a cured product of the present invention is prepared, and a layer containing luminescent nanocrystal particles is formed in a region partitioned by the partition walls. The method for forming the layer containing light-emitting nanocrystalline particles is not particularly limited, and for example, the layer can be produced by the following method: an ink composition containing luminescent nanocrystal particles is selectively attached by an ink jet method, and the ink composition is cured by irradiation with an active energy ray or heating.
[5] Image display device
The image display device of the present invention includes the partition of the present invention.
The image display device of the present invention includes, for example, an image display device including the organic electroluminescent element of the present invention. In the case of an image display device including an organic electroluminescent element, the type and structure of the image display device are not particularly limited, and, for example, an active-drive type organic electroluminescent element can be used and assembled by a conventional method. For example, the image display device of the present invention can be formed by a method described in "organic EL display" (OHM corporation, 16 years, 8 months, 20 days, waiter, andkyush, village english to lucky). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.
The image display device of the present invention includes, for example, an image display device including a color filter containing luminescent nanocrystal particles of the present invention.
Examples of the type of image display device include a liquid crystal display device and an image display device including an organic electroluminescent element. In the case of a liquid crystal display device, the liquid crystal display device includes a light source including a blue LED and a liquid crystal layer including an electrode for controlling blue light emitted from the light source for each pixel.
On the other hand, an example of an image display device including an organic electroluminescent element is an image display device in which an organic electroluminescent element emitting blue light is disposed at a position corresponding to each pixel portion of the color filter. Specifically, the method described in Japanese patent laid-open publication No. 2019-87746 can be mentioned.
Examples
The photosensitive resin composition of the present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples within the scope not exceeding the gist thereof.
The components of the photosensitive resin compositions used in the following examples and comparative examples are as follows.
< alkali-soluble resin-I (alkali-soluble resin (C-1)) >
"ZCR-8024H" (weight average molecular weight Mw 3500 and acid value 57mgKOH/g) manufactured by Nippon chemical Co., Ltd., has a partial structure represented by the following formula (C1).
[ chemical formula 50]
Figure BDA0003564604270000921
< alkali soluble resin-II >
"ZCR-1642H" (weight average molecular weight Mw 6500 and acid value 98mgKOH/g) manufactured by japan chemical corporation, which has a partial structure represented by the following formula (C2) but does not have a partial structure represented by the above formula (C1).
[ chemical formula 51]
Figure BDA0003564604270000931
< alkali-soluble resin-III >
An alkali-soluble acrylic copolymer resin was obtained by subjecting a copolymer resin containing dicyclopentyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.30/0.10/0.60) as a constituent monomer to an equivalent addition reaction of acrylic acid to glycidyl methacrylate and further to an addition reaction of tetrahydrophthalic anhydride to the copolymer resin in an amount of 0.39 mol per 1 mol of the copolymer resin. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the solid acid value was 80 mgKOH/g.
< alkali soluble resin-IV >
An alkali-soluble acrylic copolymer resin was obtained by performing an equivalent addition reaction of acrylic acid to glycidyl methacrylate and further performing an addition reaction so that tetrahydrophthalic anhydride was added to the copolymer resin in an amount of 0.10 mol per 1 mol of the copolymer resin, with respect to a copolymer resin containing dicyclopentyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) as a constituent monomer. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 7700, and the solid acid value was 28.5 mgKOH/g.
< dispersant-I >
BYK-LPN21116 (acrylic A-B block copolymer comprising an A block having a quaternary ammonium salt group and a tertiary amino group and a B block having no quaternary ammonium salt group and no amino group, having an amine value of 70mgKOH/g and an acid value of 1mgKOH/g or less) manufactured by BYK-Chemie K.K.)
< solvent-I >
PGMEA: propylene glycol monomethyl ether acetate
< solvent-II >
MB: 3-methoxy-1-butanol
< photopolymerizable monomer >
DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kabushiki Kaisha
< photopolymerization initiator-I >
A compound having the following chemical structure was used.
[ chemical formula 52]
Figure BDA0003564604270000941
< photopolymerization initiator-II >
A compound having the following chemical structure was used.
[ chemical formula 53]
Figure BDA0003564604270000942
< liquid repellent-I >
Megafac RS-90 (fluorine-based, olefinic double bond-containing liquid repellent) manufactured by DIC
< surfactant-I >
Megafac F-559 (fluorine-based surfactant having no crosslinking group) manufactured by DIC
< additive-I >
Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate))
< additive-II >
KAYAMER PM-21 (methacryloyl group-containing phosphate ester) manufactured by Nippon Kabushiki Kaisha
< organic Black pigment >
Irgaphor Black S0100 CF from BASF corporation
Preparation of pigment Dispersion 1 to 3
The pigment, the dispersant, the alkali-soluble resin, and the solvent were mixed in the mass ratio shown in table 1. The solution was subjected to dispersion treatment for 3 hours at a temperature of 25 to 45 ℃ by means of a paint shaker. The beads used were 0.5mm phi zirconia beads added to 2.5 times the mass of the dispersion. After the dispersion ends, the beads were separated from the dispersion by a filter, and pigment dispersions 1 to 3 were prepared.
[ Table 1]
Figure BDA0003564604270000951
Examples 1 to 9 and comparative examples 1 to 3
Using the pigment dispersions 1 to 3 prepared above, the photosensitive resin compositions 1 to 10 were prepared by adding the respective components so that the ratio of the solid content of each component in the total solid content of the photosensitive resin compositions became the blending ratio in table 2, further adding a solvent so that the content of the total solid content became 31 mass% and the solvent-I/solvent-II in the total solvent became 80/20 (mass ratio), and stirring and dissolving the solvent. The obtained photosensitive resin compositions were evaluated by the methods described below.
The blending ratios of the pigment dispersion, the alkali-soluble resin, and the liquid repellent in table 2 are solid content values.
Figure BDA0003564604270000961
The method of evaluating the performance will be described below.
< measurement of contact Angle of PGMEA >
The photosensitive resin composition was applied onto a glass substrate by a spin coater so as to have a thickness of 10 μm after heat curing. Vacuum drying 1 the coated substrateAfter the lapse of time, the film was further dried by heating at 100 ℃ for 120 seconds on a hot plate. The obtained coating film was measured at 27mJ/cm using a high pressure mercury lamp2The entire surface was exposed. At this time, the light intensity at a wavelength of 365nm was 100mW/cm2. Subsequently, the substrate was subjected to spray development at 24 ℃ for 70 seconds using an aqueous solution in which 0.04 mass% of KOH and 0.07 mass% of Emargen a-60 (manufactured by kao corporation, a surfactant) were dissolved as a developing solution, and then washed with pure water for 27 seconds. Finally, the substrate was heated and cured in an oven at the temperature shown in table 2 for 30 minutes to obtain a substrate for measuring a contact angle.
The contact angle of the substrate for contact angle measurement was measured 1 second after 0.7. mu.L of PGMEA was dropped using Drop Master 500 (contact angle measuring apparatus) manufactured by Kyowa Kagaku K.K., at 23 ℃ and a humidity of 50% RH, and the ink repellency was evaluated according to the following criteria. The results are shown in Table 2, and those with a large contact angle indicate high ink repellency.
(evaluation criteria for ink repellency)
A: the contact angle of PGMEA is above 40.0 DEG
B: the contact angle of PGMEA is less than 40.0 °
< evaluation of minimum seal line width >
The photosensitive resin composition was applied onto a glass substrate by a spin coater so as to have a thickness of 10 μm after heat curing. The coated substrate was vacuum-dried for 1 minute, and further heat-dried on a hot plate at 100 ℃ for 120 seconds. Next, the obtained coated substrate was subjected to ultraviolet exposure using a photomask while blocking a wavelength of 330nm or less with a high-pressure mercury lamp. The exposure amount was 50mJ/cm2The exposure gap was 5 μm. At this time, the light intensity at a wavelength of 365nm was 45mW/cm2. The photomask uses exposure masks having linear openings with various widths, such as opening widths of 5 to 50 μm (5 to 20 μm: 1 μm, 25 to 50 μm: 5 μm) and opening lengths of 2 mm. Then, after development treatment was performed under the same conditions as those used in the production of the substrate for measuring contact angle, the substrate was cleaned with pure water for 10 seconds, and then heated and cured in an oven at the temperature shown in table 2 for 30 minutes to produce a contact angle measuring substrateA line pattern substrate with a plurality of spacers is provided.
The entire line (2mm) on the linear pattern substrate was observed with an optical microscope, and the minimum width of the mask having the smallest opening width among the lines that were not broken or peeled and adhered to the substrate was evaluated according to the following criteria. The smaller the minimum adhesion line width, the higher the adhesion.
(evaluation criteria for minimum adhesion line width)
A: less than 13 μm
B: more than 13 μm
As is clear from comparison of examples 1 to 9 and comparative examples 1 to 2 in Table 2, the inclusion of the alkali-soluble resin (C-1) makes the PGMEA contact angle good even at a low exposure amount, and particularly, the PGMEA contact angle becomes high by increasing the content ratio. It is considered that the alkali-soluble resin (C-1) has a benzene ring in the main chain, and therefore, the hydrophobicity of the film is easily increased, and particularly, the crosslinking density is increased by having 2 or more crosslinking groups in the side chain, and therefore, the liquid repellent easily remains on the film surface after development, and high ink repellency is exhibited.
As is clear from comparison between examples 1 to 9 and comparative example 1 in Table 2, the minimum adhesion line width can be reduced by containing the alkali-soluble resin (C-1). It is considered that the alkali-soluble resin (C-1) has 2 or more crosslinking groups in the side chain, and thereby the crosslinking density is increased, and the peeling of the line formed during exposure at the time of development can be suppressed.
When a fluorine-based surfactant having no crosslinking group was used instead of the liquid repellent as in comparative example 3, the ink repellency was insufficient. This is considered to be because, since the film does not have a crosslinking group, the surfactant is eluted out of the coating film during development, and the remaining amount of the surfactant on the film surface after development is reduced. On the other hand, in the case of using the liquid repellent having an ethylenic double bond as a crosslinking group as in examples 1 to 9, since elution during development is suppressed, it is considered that a favorable PGMEA contact angle is exhibited even at a low exposure amount.
As is clear from examples 8 and 9 in table 2, the photosensitive resin composition of the present invention can have both a good PGMEA contact angle and a small minimum adhesion line width even at a post-baking temperature of 150 ℃. It is considered that these properties can be simultaneously achieved by using both the liquid repellent having a crosslinking group and the alkali-soluble resin (C-1).

Claims (12)

1. A photosensitive resin composition comprising: (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent,
the alkali-soluble resin (C) contains an alkali-soluble resin (C-1) having a partial structure represented by the general formula (C1),
the liquid repellent (D) contains a fluorine atom-containing resin having a crosslinking group,
Figure FDA0003564604260000011
in the formula (c1), Rc11Represents a hydrogen atom or a methyl group,
Rc12represents a 2-valent hydrocarbon group optionally having a substituent,
n represents an integer of 2 or 3,
the benzene ring in formula (c1) is optionally further substituted with an optional substituent,
each represents a bond arm.
2. The photosensitive resin composition according to claim 1, wherein in the general formula (c1), Rc12Is a group represented by the following general formula (c1-1),
Figure FDA0003564604260000012
3. the photosensitive resin composition according to claim 1 or 2, wherein a content ratio of the alkali-soluble resin (C-1) in the alkali-soluble resin (C) is 60% by mass or more.
4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) a colorant.
5. The photosensitive resin composition according to claim 4, wherein the content of the colorant (E) is 50% by mass or less in the entire solid content of the photosensitive resin composition.
6. The photosensitive resin composition according to claim 4 or 5, wherein the colorant (E) contains at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.
7. The photosensitive resin composition according to any one of claims 4 to 6, wherein the colorant (E) contains a violet pigment.
8. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.
9. A partition wall, which is composed of the cured product of claim 8.
10. An organic electroluminescent element comprising the partition wall according to claim 9.
11. A color filter comprising luminescent nanocrystal particles, comprising the partition walls according to claim 9.
12. An image display device comprising the partition wall according to claim 9.
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