CN110244513B - Colored photosensitive composition, black photo spacer and color filter - Google Patents

Colored photosensitive composition, black photo spacer and color filter Download PDF

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Publication number
CN110244513B
CN110244513B CN201910370357.1A CN201910370357A CN110244513B CN 110244513 B CN110244513 B CN 110244513B CN 201910370357 A CN201910370357 A CN 201910370357A CN 110244513 B CN110244513 B CN 110244513B
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pigment
acid
photosensitive composition
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colored photosensitive
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CN110244513A (en
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岩田训志
泽井良尚
裴丽华
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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

Abstract

A colored photosensitive composition contains a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment contains a pigment shown in the following (A) and a pigment shown in the following (B). (A) One selected from the group consisting of c.i. pigment orange 43, c.i. pigment orange 64 and c.i. pigment orange 72; (B) C.I. pigment blue 60.

Description

Colored photosensitive composition, black optical spacer and color filter
The present application is a divisional application of the patent application having an application date of 2013, 1/30, and an application number of 201380007458.3, entitled "colored photosensitive composition, black light spacer, and color filter".
Technical Field
The present invention relates to a colored photosensitive composition and the like. More particularly, the present invention relates to a colored photosensitive composition which is preferably used for forming a black light spacer or the like in a color filter such as a liquid crystal display, a black light spacer formed using the colored photosensitive composition, and a color filter containing the black light spacer.
Background
A Liquid Crystal Display (LCD) utilizes the property of switching the alignment method of liquid crystal molecules by on/off of a voltage applied to the liquid crystal. On the other hand, each member constituting a cell of an LCD is often formed by using a photosensitive composition typified by photolithography. The application range of photosensitive compositions will tend to be further expanded in the future because of the ease of formation of fine structures and the ease of handling of large-screen substrates.
However, in the LCD using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electric characteristics of the photosensitive composition itself or due to the influence of impurities contained in the photosensitive composition, and thus, there is a problem that display unevenness of the display occurs. In particular, a member close to a liquid crystal layer in a color liquid crystal display device, for example, a member for keeping a constant interval between 2 substrates in a liquid crystal panel, that is, a so-called column spacer, a photo spacer, or the like, has a large influence.
Conventionally, when a spacer having no light-shielding property is used in a TFT-type LCD, the TFT as a switching element may be erroneously operated by light transmitted through the spacer. To prevent this, patent document 1, for example, describes that the spacer has light-shielding properties.
However, in order to make the spacer light-shielding property, it is generally considered to add a colorant containing a pigment or the like to the photosensitive composition, but as the colorant is added, curability of the spacer layer decreases due to a decrease in the transparent component, and the properties may be impaired by the influence of impurities or the like derived from the pigment.
In order to control the voltage holding ratio, a method of improving curability, a method of controlling a curable resin, a dispersant, or the like of a photosensitive composition, or the like has been proposed.
On the other hand, in recent years, a method of forming spacers having different heights at once according to a change in panel structure when manufacturing the spacers by photolithography has been proposed. Patent document 2 discloses that the shape and the height difference of spacers having different heights can be achieved by controlling the exposure amount and the residual film ratio.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. H8-234212
Patent document 2: japanese patent laid-open publication No. 2009-31778
Disclosure of Invention
Problems to be solved by the invention
However, patent document 2 relates to a spacer to which no pigment is added, and has found that: when this is applied to the one-time formation of a colored spacer to which a pigment is added, since the pigment absorbs light in an ultraviolet region contributing to photopolymerization, curability is poor for a pattern having a small light transmittance at an opening, and it is difficult to realize characteristics such as a desired spacer shape having a different height, control of a height difference, and adhesion to a substrate.
The present invention has been made in view of the above circumstances. That is, a main object of the present invention is to provide a colored photosensitive composition which can form a black spacer having excellent adhesion to a substrate while ensuring light-shielding properties and a voltage holding ratio of a liquid crystal, and which can control a shape and a height difference in a method of forming black spacers having different heights at a time by photolithography.
Another object of the present invention is to provide a black photo spacer formed from such a colored photosensitive composition.
Another object of the present invention is to provide a color filter including such a black light spacer.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using a specific pigment as a colorant, and have completed the present invention. That is, the gist of the present invention is as follows.
[1] A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment comprises a pigment represented by the following formula (A) and a pigment represented by the following formula (B),
(A) One selected from the group consisting of c.i. pigment orange 43, c.i. pigment orange 64 and c.i. pigment orange 72;
(B) C.i. pigment blue 60.
[2] The colored photosensitive composition according to [1], wherein the pigment comprises c.i. pigment orange 64 and c.i. pigment blue 60.
[3] The colored photosensitive composition according to [1] or [2], wherein the pigment further contains one selected from the group consisting of C.I. pigment Red 254, C.I. pigment Violet 23 and C.I. pigment Violet 29.
[4] The colored photosensitive composition according to [1], wherein the pigment comprises a pigment represented by the following (1) or a pigment represented by the following (2),
(1) C.i. pigment orange 64, c.i. pigment blue 60 and c.i. pigment red 254;
(2) C.i. pigment orange 64, c.i. pigment blue 60 and c.i. pigment violet 29.
[5] A black photo spacer formed by using the colored photosensitive composition according to any one of the above [1] to [4 ].
[6] A color filter comprising the black photo spacer according to [5 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, in the method of forming black spacers having different heights at one time by photolithography, the balance of light absorption in the ultraviolet region and the visible region is ensured by appropriately combining the pigment species having different light absorption characteristics, and thus, the light-shielding property and the voltage holding ratio of the liquid crystal can be maintained, the shape or the height difference can be controlled, and high adhesion to the substrate can be achieved.
Detailed Description
The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as the invention does not exceed the gist thereof.
In the present specification, "(meth) acryl" or the like means "at least one of acryl and methacryl", "meth (acrylate)" or the like means "at least one of acrylate and methacrylate", or the like, and "(meth) acrylic acid" means "at least one of acrylic acid and methacrylic acid". The same applies to "(meth) acryloyl group". The terms "(acid) anhydride", "acid (anhydride)" and "\8230," as used herein, are intended to include both acids and anhydrides thereof.
The "total solid content" refers to all components contained in the colored photosensitive composition or the pigment dispersion liquid except a solvent component described later.
In the present invention, unless otherwise specified, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of standard polystyrene by GPC (gel permeation chromatography). "c.i." means the color index (c.i.).
In the present invention, unless otherwise specified, "amine number" means an amine number converted to an effective solid content, and is a value represented by the amount of base per 1g of the solid content of the dispersant and the equivalent weight of KOH. The measurement method will be described below. On the other hand, unless otherwise specified, "acid value" means an acid value converted into an effective solid content, and is calculated by neutralization titration.
In the present invention, the term "monomer" means a substance having a meaning relative to a so-called polymer substance, and means a substance having a meaning including a dimer, a trimer, an oligomer, and the like, in addition to a monomer having a narrow meaning.
The colored photosensitive composition of the present invention contains a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, and contains the following (a) and (B) as the pigment, and is particularly preferably used as the colored photosensitive composition: the colored photosensitive composition is used for forming black spacers with different heights at one time by utilizing a photoetching method.
(A) One selected from the group consisting of c.i. pigment orange 43, c.i. pigment orange 64 and c.i. pigment orange 72;
(B) C.i. pigment blue 60.
[ method of Forming Black spacers having different heights at one time ]
First, a method of forming black spacers having different heights at a time by photolithography using the colored photosensitive composition of the present invention is described. The method is mainly characterized by an exposure mask in an exposure process.
A method of using, as an exposure mask, an exposure mask having a light-shielding layer for shielding transmission of light and a plurality of openings for transmitting light, wherein an average light transmittance of some of the openings is smaller than an average light transmittance of other openings is known. This method is a method of using an exposure mask having a light-shielding layer (light transmittance 0%) and a plurality of openings, and having openings (average light transmittance more than 0% and less than 100%, preferably more than 5% and less than 50%, hereinafter referred to as "intermediate transmission openings") in which the average light transmittance is smaller than the openings having the highest average light transmittance (normal light transmittance 100%, hereinafter referred to as "full transmission openings"). In this method, for example, in the case of a negative type colored photosensitive composition, a difference in the degree of curing of the formed pattern is caused by a difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in the exposure amount, and thereafter, a black spacer having a different height can be formed through the development and thermal curing processes.
[ colored photosensitive composition ]
The following describes the constituent materials of the colored photosensitive composition of the present invention.
[1] Pigment (I)
The pigment is a substance that colors the colored photosensitive composition of the present invention.
As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, and a black pigment can be used. Further, as the structure, organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perylene-based and the like, or various inorganic pigments and the like can be used.
The colored photosensitive composition of the present invention contains the following (a) and (B) as essential components as pigments.
(A) One selected from the group consisting of c.i. pigment orange 43, c.i. pigment orange 64, and c.i. pigment orange 72;
(B) C.i. pigment blue 60.
In the colored photosensitive composition of the present invention, the pigment used is not particularly limited except that the above-mentioned (a) and (B) are contained as essential components as the pigment, and a black coloring material obtained by mixing respective colors of red, green, blue, and the like can be used. Further, the pigment may be appropriately selected from black pigments, other inorganic or organic pigments, and dyes, and used in combination.
Specific examples of pigments that can be used are shown below by pigment numbers.
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. Among them, preferred are: c.i. pigment red 48, 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and further preferably: c.i. pigment red 177, 179, 209, 224, 254. Among them, c.i. pigment red 254 (R254) is preferably exemplified.
As the blue pigment, there can be mentioned: c.i. pigment blue 1,2, 9, 14, 15. Among them, preferable are: c.i. pigment blue 15, 1, 15.
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, preferable are: c.i. pigment green 7, 36.
As the yellow pigment, there can be mentioned: c.i. pigment yellow 1,2,3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 1, 36: 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, 184, 185, 188, 189, 190, 191, 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferred are: pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and further preferably: c.i. pigment yellow 83, 138, 139, 150, 180.
As orange pigments, mention may be made of: 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, preferable are: c.i. pigment orange 38, 43, 64, 71, 72. Further preferable examples thereof include: c.i. pigment orange 43, 64, 72. Further, c.i. pigment orange 64 (Or 64) can be preferably mentioned.
As violet pigments, mention may be made of: c.i. pigment violet 1,2, 3. Among them, preferable are: c.i. pigment violet 19, 23, 29, which can be further preferably exemplified by: c.i. pigment violet 23 and 29, and c.i. pigment violet 29 (V29) can be more preferably used.
As the black pigment, there can be mentioned: perylene Black (K0084 and K0086 manufactured by BASF), cyanine Black, fast Black HB (c.i. 26150), irgaphor Black S0100 CF (manufactured by BASF), carbon Black, and titanium Black.
Examples of commercially available products of carbon black include the following products.
Mitsubishi chemical corporation: MA7, MA8, MA11, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, # 0, #3750, #3950, #4000, #4010, # 7B, OIL9B, OIL11B, OIL30B, OIL31
Manufactured by Degussa: printex3, printex3OP, printex30OP, printex40, printex45, printex55, printex60, printex75, printex80, printex85, printex90, printex A, printex L, printex G, printex P, printex U, printex V, printex G, special Black550, special Black350, special Black250, special Black100, special Black6, special Black5, special Black4, color Black FW1, color Black FW2V, color Black FW18, color FW200, color Black S160, color S170
Manufactured by Cabot corporation: monarch120, monarch280, monarch460, monarch800, monarch880, monarch900, monarch1000, monarch1100, monarch1300, monarch1400, monarch4630, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, blak PEARLS480, PEARLS130, VULCAN 72R, elftxc-8
Manufactured by Columbian Carbon corporation: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, RAVEN1100URAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As examples of commercially available products of titanium black, the following products can be cited.
Mitsubishi material corporation: 10S, 12S, 13R, 13M-C, 14M, 15M, L-15M, etc.;
kokui Kabushiki Kaisha: tilackD M, M-50A, M-AM, V, UV-3, UV-6, F, S, C, X, etc.
The colored photosensitive composition of the present invention preferably contains c.i. pigment orange 64 and c.i. pigment blue 60 as pigments from the viewpoints of light-shielding properties, control of voltage holding ratio, shape, and level difference of liquid crystal, and adhesion to a substrate.
The colored photosensitive composition of the present invention preferably contains, as a pigment, one selected from the group consisting of c.i. pigment red 254, c.i. pigment violet 23 and c.i. pigment violet 29 in addition to the above (a) and (B).
In order to improve light-shielding properties, control of voltage holding ratio, shape, and level difference of liquid crystal, and adhesion to a substrate, the colored photosensitive composition of the present invention preferably contains 3 pigments represented by any one of the following (1) to (3) as pigments, and particularly preferably contains 3 pigments represented by (1) or (2) from the viewpoint of voltage holding ratio of liquid crystal.
(1) C.i. pigment orange 64, c.i. pigment blue 60, c.i. pigment red 254
(2) C.i. pigment orange 64, c.i. pigment blue 60, c.i. pigment violet 29
(3) C.i. pigment orange 64, c.i. pigment blue 60, c.i. pigment violet 23
The proportion of the pigment in the colored photosensitive composition of the invention is usually 5 to 50% by weight, preferably 10 to 45% by weight, and more preferably 20 to 42% by weight, based on the total solid content. When the amount of the pigment is more than this range, the shape and height difference of the spacer and the adhesion to the substrate may be deteriorated, or the curable component may be reduced, and the pigment or the like may be eluted into the liquid crystal layer to lower the voltage holding ratio. On the other hand, if it is less than this range, sufficient light-shielding properties as a black light spacer may not be secured.
In the present invention, the effects of improving the light-shielding property, the voltage holding ratio, the shape, and the level difference of the liquid crystal, and the adhesion to the substrate cannot be sufficiently obtained by using the pigments in combination with either too much or too little, and therefore, it is preferable to use (a) at 25 to 70% by weight, particularly preferably at 30 to 60% by weight, and particularly preferably at 35 to 60% by weight, based on 100% by weight of the total of (a) and (B).
That is, (A) has a relatively small absorption of light having a wavelength of about 330 to 380nm and a large absorption of light having a wavelength of about 400 to 550 nm. On the other hand, (B) similarly has a small absorption of light having a wavelength of about 330 to 380nm and a large absorption of light having a wavelength of about 550 to 700 nm. Therefore, by using the 2 pigments in combination with a good balance, the light absorption in the ultraviolet region and the light absorption in the visible region can be well balanced, and the light shielding property, the voltage holding ratio of the liquid crystal, the control of the shape and the height difference, and the adhesion to the substrate can be improved.
The pigment used in the present invention may contain various pigments other than the pigments (a) and (B), and the above-mentioned effects can be sufficiently obtained by the combined use of the pigments (a) and (B), and the total proportion of the pigments (a) and (B) is preferably 50% by weight or more, particularly preferably 60 to 95% by weight, and particularly preferably 70 to 90% by weight, based on 100% by weight of the total of the pigments contained in the colored photosensitive composition of the present invention.
In addition, in the combination of pigments used in the present invention, by using (a) and (B), and further using c.i. pigment red 254 (R254), the following effects can be achieved: the light absorption in the ultraviolet region is suppressed, the absorption in the visible region is increased, and the light-shielding property, the voltage holding ratio of the liquid crystal, the control of the shape and the height difference, and the adhesion to the substrate are improved. In this case, it is preferable that the total of 100% by weight of (A), (B) and R254 is used in a proportion of 20 to 40% by weight of (A), 45 to 65% by weight of (B) and 5 to 25% by weight of R254, and in particular, the total of 25 to 35% by weight of (A), 50 to 60% by weight of (B) and 10 to 20% by weight of R254. Pigments other than the above (a), (B) and R254 may be used, but the total proportion of the (a), (B) and R254 used is preferably 70% by weight or more, particularly 90 to 100% by weight, in the total pigment in the colored photosensitive composition.
In addition, in the combination of pigments used in the present invention, by using (a), (B), and further using c.i. pigment violet 23 (V23), the following effects can be achieved: the light absorption in the ultraviolet region can be suppressed, the absorption in the visible region can be further increased, and the light-shielding property, the voltage holding ratio of the liquid crystal, the control of the shape and the level difference, and the adhesion to the substrate can be further improved. In this case, it is preferable to use (A) in an amount of 30 to 50 wt%, (B) in an amount of 30 to 50 wt%, and V23 in an amount of 10 to 30 wt%, particularly (A) in an amount of 35 to 45 wt%, and (B) in an amount of 35 to 45 wt%, and V23 in an amount of 15 to 25 wt%, of the total 100 wt% of (A), (B), and V23. Pigments other than those (A), (B) and V23 may be used, but the total proportion of the (A), (B) and V23 used in the entire pigment in the colored photosensitive composition is preferably 70% by weight or more, particularly 90 to 100% by weight.
In addition, in the combination of pigments used in the present invention, by using (a), (B), and further using c.i. pigment violet 29 (V29), the following effects can be achieved: the light absorption in the ultraviolet region can be suppressed, and the absorption in the visible region can be further increased, whereby the light-shielding property, the control of the voltage holding ratio, the shape, and the level difference of the liquid crystal, and the adhesion to the substrate can be further improved. In this case, it is preferable to use (A) in an amount of 30 to 50 wt%, (B) in an amount of 30 to 50 wt%, and V29 in an amount of 10 to 30 wt%, particularly (A) in an amount of 35 to 45 wt%, and (B) in an amount of 35 to 45 wt%, and V29 in an amount of 15 to 25 wt%, of the total 100 wt% of (A), (B), and V29. Pigments other than those (A), (B) and V29 may be used, but the total proportion of the (A), (B) and V29 used is preferably 70% by weight or more, particularly 90 to 100% by weight, of the total pigments in the colored photosensitive composition.
The pigment used in the present invention preferably contains (a) and (B), and further contains c.i. pigment red 272 (R272). Since R272 has a large absorption in the visible region, it is advantageous for increasing OD.
[2] Adhesive resin
The binder resin used in the colored photosensitive composition of the present invention is not particularly limited as long as it is a resin of a member used in a color filter, and examples thereof include: epoxy acrylate resins, novolac resins, polyvinyl phenol resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, and the like are preferably used from the viewpoint of controlling the shape and the height difference and the adhesion to the substrate, and epoxy acrylate resins and acrylic resins having a carboxyl group are more preferably used.
The epoxy acrylate resin is synthesized as follows: an alpha, beta-unsaturated monocarboxylic acid ester having a carboxyl group in the alpha, beta-unsaturated monocarboxylic acid or ester moiety is added to an epoxy resin (or epoxy compound), and then reacted with a polybasic acid or an anhydride thereof. The reaction product is not limited to "acrylate" but is conventionally named as it has substantially no epoxy group in its chemical structure, and since an epoxy resin (or an epoxy compound) is used as a raw material and "acrylate" is a typical example.
As the epoxy resin used as a raw material, there can be mentioned: an (o, m, p) cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a trisphenol methane-type epoxy resin, an epoxy resin (or an epoxy compound) represented by the following general formulae (1-a) to (1-a' "), and the like.
Hereinafter, a particularly preferred binder resin as the binder resin in the present invention will be described.
< alkali-soluble resin (A '), alkali-soluble resin (A1') >)
As the binder resin in the present invention, an alkali-soluble resin (a ") obtained by reacting a reactant of an epoxy compound (a") represented by the following general formula (1-a ") and an unsaturated group-containing carboxylic acid (b") with at least one of a polybasic acid and an acid anhydride thereof (c ") can be cited as one of particularly preferable binder resins.
[ chemical formula 1]
Figure BDA0002049735360000101
[ in the above general formula (1-a'), X represents a linking group represented by the following general formula (2 a), (2 b) or (3). Wherein the molecular structure contains 1 or more adamantane structures. l represents an integer of 2 or 3.
[ chemical formula 2]
Figure BDA0002049735360000111
(in the above general formulae (2 a) and (2 b), R 1 ～R 4 And R 13 ～R 15 Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent.
In the above general formula (3), R 5 ～R 12 Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Y represents a 2-valent linking group which optionally has a substituent and which comprises an adamantane structure.
In the above general formulae (2 a), (2 b) and (3), the bond to the glycidoxy group in the general formula (1-a') is represented. ) ]
(1) An epoxy compound (a '), represented by the general formula (1-a')
First, the group X in the epoxy compound (a ') (hereinafter, sometimes referred to as "component (a")) represented by the general formula (1-a') will be described.
When the group X is a structure represented by the general formula (2 a) or (2 b), the general formulae (2 a) and (2 b) preferably each have an adamantane structure of 2 or more and 4 or less. If the adamantane structure is 1, the developing solution resistance tends to be lowered and the resolution tends to be poor.
When the group X is a structure represented by the general formula (3), Y in the general formula (3) is not particularly limited as long as it is a "2-valent linking group optionally having a substituent and containing an adamantyl structure", and is preferably a linking group represented by the following general formula (4) or (5).
[ chemical formula 3]
Figure BDA0002049735360000121
[ the general formulae (4) and (5) each optionally have a substituent. Represents a bonding site to the benzene ring in the general formula (3). ]
The epoxy compound (a ") represented by the above general formula (1-a") is particularly preferably represented by the following general formula (6) or (7).
[ chemical formula 4]
Figure BDA0002049735360000122
[ the adamantane ring represented by the general formula (6) and the adamantane group represented by the general formula (7) may have a substituent.
In the general formula (6), R 16 ～R 23 Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group.
In the general formula (7), R 24 And R 25 Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent.]
R in the above general formulae (2 a), (2 b), (3), (6) and (7) 1 ～R 25 The alkyl group having 1 to 12 carbon atoms in (b) may preferably be an alkyl group having 1 to 10 carbon atoms.
Further, as the substituent optionally contained in these alkyl groups, there may be mentioned: halogen atom, hydroxyl group, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group, etc.
R in the above general formulae (2 a), (2 b), (3), (6) and (7) 1 ～R 25 The substituent optionally having the phenyl group in (1) may be exemplified by: halogen atom, hydroxyl group, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group, etc.
R in the general formulae (2 a) and (2 b) is 1 ～R 4 And R 13 ～R 15 Adamantyl group of the formula (3), an adamantane ring contained in Y of the formula (3), an adamantane ring of the formula (6), an adamantyl group of the formula (7), R of the formula (7) 24 、R 25 The adamantyl group (c) and the substituents which the adamantane ring of the general formulae (4) and (5) may have include: halogen atom, hydroxyl group, alkoxy group having 1 to 10 carbon atoms, carbon atomAlkenyl group, phenyl group, carboxyl group, sulfanyl group, phosphino group, amino group, nitro group, etc. having a sub-number of 2 to 10.
In the above general formula (6), R 16 ～R 23 Particularly preferred is an alkyl group, a halogen atom, an alkoxy group, an alkenyl group or a phenyl group.
In the above general formula (7), R 24 And R 25 Particularly preferred is an alkyl group, a halogen atom, an alkoxy group, an alkenyl group or a phenyl group.
The molecular weight of X represented by the general formula (1-a') is preferably 200 or more and 1000 or less. By setting the molecular weight of X to 200 or more, sufficient chemical resistance can be ensured, and by setting X to 1000 or less, good sensitivity can be ensured.
The epoxy equivalent of the epoxy compound (a ") represented by the general formula (1-a") is preferably 210 or more, more preferably 230 or more. The epoxy equivalent is preferably 450 or less, more preferably 400 or less. By setting the epoxy equivalent of the epoxy compound (a ") to 210 or more, sufficient alkali resistance can be ensured, and by setting to 450 or less, good sensitivity of the produced organic binder can be ensured.
The epoxy compounds (a ") may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The epoxy compound (a ") may be a commercially available compound or may be synthesized from a phenol compound as described below by a known method.
[ chemical formula 5]
Figure BDA0002049735360000131
[ R in the above general formulae (9 a), (9 b) and (10) 1 ～R 15 The same meanings as defined in the general formulae (2 a), (2 b) and (3), respectively.]
For example, an epoxy compound (a ") in which X in the general formula (1-a") is a linking group represented by the general formula (2 a) or (2 b) can be obtained by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a dissolved mixture of a compound represented by the general formula (9 a) or (9 b) and an excess amount of an epihalohydrin such as epichlorohydrin or epibromohydrin, or reacting the mixture at a temperature of 20 to 120 ℃ for 1 to 10 hours while adding the hydroxide.
Further, an epoxy compound (a ") in which X in the general formula (1-a") is a linking group represented by the general formula (3) can be obtained by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a dissolved mixture of the compound represented by the general formula (10) and an excess amount of an epihalohydrin such as epichlorohydrin or epibromohydrin in advance or reacting the mixture at 20 to 120 ℃ for 1 to 10 hours while adding the hydroxide.
In the reaction for obtaining the epoxy compound (a ″), an aqueous solution thereof may be used as the alkali metal hydroxide. In this case, the following method is possible: the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and simultaneously water and epihalohydrin are continuously distilled out under reduced pressure or atmospheric pressure, followed by liquid separation to remove water and continuously return epihalohydrin to the reaction system.
Further, the epoxy compound (a ") represented by the general formula (1-a") can also be produced by the following method: adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like as a catalyst to a dissolved mixture of the compound represented by the above general formula (9 a), (9 b) or (10) and an epihalohydrin, reacting at 50 to 150 ℃ for 1 to 5 hours to obtain a halohydrin etherate of the compound represented by the general formula (9 a), (9 b) or (10), adding a solid or aqueous solution of an alkali metal hydroxide to the obtained halohydrin etherate of the compound represented by the general formula (9 a), (9 b) or (10), and reacting at 20 to 120 ℃ for 1 to 10 hours again to dehydrohalogenate (ring closure).
The amount of epihalohydrin used in the above reaction is usually 1 to 20 moles, preferably 2 to 10 moles, per 1 equivalent of hydroxyl group of the compound represented by the general formula (9 a), (9 b) or (10). The amount of the alkali metal hydroxide used is usually 0.8 to 15 mol, preferably 0.9 to 11 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (9 a), (9 b) or (10).
In the above reaction, in order to smoothly proceed the reaction, an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol to perform the reaction. When alcohols are used, the amount thereof is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. When the aprotic polar solvent is used, the amount thereof to be used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of the epihalohydrin.
(2) Unsaturated group-containing carboxylic acid (b')
Examples of the unsaturated group-containing carboxylic acid (b ") (hereinafter, sometimes referred to as a" component (b ")) include unsaturated carboxylic acids having an ethylenically unsaturated group, and specific examples thereof include: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, and (meth) acrylic acid substituted with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group at the α -position; (meth) acryloyloxyethyl alkyl esters of 2-membered acids such as 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrogenated phthalic acid, 2- (meth) acryloyloxybutyl maleic acid, and 2- (meth) acryloyloxybutyl maleic acid; monomers obtained by adding lactones such as e-caprolactone, β -propiolactone, γ -butyrolactone and δ -valerolactone to (meth) acrylic acid; (meth) acrylic acid dimer, and the like.
Further, there may be mentioned compounds obtained by adding an acid anhydride such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or phthalic anhydride to a hydroxyl group-containing unsaturated compound such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, an acrylic acid adduct of glycidyl methacrylate or a methacrylic acid adduct of glycidyl methacrylate.
A particularly preferred substance is (meth) acrylic acid.
These substances may be used alone in 1 kind, or may be mixed in 2 or more kinds.
As a method for reacting the epoxy group in the component (a ') and the component (b'), a known method can be used. For example, a carboxylic acid can be added to an epoxy compound by reacting the above-mentioned component (a ") and component (b") in an organic solvent at a reaction temperature of 50 to 150 ℃ for several hours to several tens of hours using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, triphenylphosphine or the like as a catalyst.
The amount of the catalyst to be used is preferably 0.01 to 10% by weight, and particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the total of the (a ") component and the (b") component). In order to prevent polymerization during the reaction, a polymerization inhibitor (for example, methoxyphenol, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, t-butylcatechol, phenothiazine, etc.) is preferably used in an amount of 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.
The proportion of the component (b ") to the epoxy group of the component (a") is usually 90 to 100 mol%. Since the residual epoxy groups tend to adversely affect the storage stability, the component (b ") is reacted at a ratio of usually 0.8 to 1.5 equivalents, particularly preferably 0.9 to 1.1 equivalents, to 1 equivalent of the epoxy groups in the component (a").
(3) Polybasic acid and anhydride thereof (c')
As at least one of the polybasic acid and the acid anhydride (c) (hereinafter, sometimes referred to as "component (c)") thereof (or the "polybasic acid (anhydride)"), at least one of a 2-membered acid and an acid anhydride thereof (hereinafter, sometimes referred to as "2-membered acid (anhydride)"), at least one of a 3-membered acid and an acid anhydride thereof (hereinafter, sometimes referred to as "3-membered acid (anhydride)"), at least one of a 4-membered acid and an acid anhydride thereof (hereinafter, sometimes referred to as "4-membered acid (anhydride)") and the like can be used.
As the 4-membered acid (anhydride) (at least one of tetracarboxylic acid and dianhydride thereof), known ones can be used, and examples thereof include: tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and dianhydrides thereof. These substances may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among the above exemplified compounds, biphenyltetracarboxylic acid and anhydrides thereof are particularly preferable as the 4-membered acid (anhydride).
By reacting the reactant of the component (a ') and the component (b ') with the 4-membered acid (anhydride) as the component (c '), the molecular weight is increased by the crosslinking reaction. Therefore, it is preferable because the effects of improving the adhesion to the substrate, adjusting the solubility, improving the sensitivity and alkali resistance are obtained.
As the 2-membered acid (anhydride) (at least one of dicarboxylic acid and anhydride thereof), for example: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl endomethylene tetrahydrophthalic acid, hexachloronorbornenedioic acid, methyl tetrahydrophthalic acid, or anhydrides thereof. Among them, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These 2-membered acids (anhydrides) may be used alone in 1 kind, or in combination of 2 or more kinds.
It is preferable to react the reactant of the component (a ") and the component (b") with the 2-membered acid (anhydride) as the component (c ") because the solubility can be easily adjusted and the adhesion to the substrate can be improved.
As the 3-membered acid (anhydride) (at least one of tricarboxylic acid and anhydride thereof), there can be mentioned: trimellitic acid, hexahydrotrimellitic acid, or anhydrides thereof. Trimellitic anhydride and hexahydrotrimellitic anhydride are particularly preferred. These 3-membered acids (anhydrides) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
By using a 3-membered acid (anhydride) as the component (c ″), the molecular weight of the alkali-soluble resin (a ″) can be increased, and a branch can be introduced into the molecule, whereby a balance between the molecular weight and the viscosity can be achieved. Further, the amount of the acid group introduced into the molecule can be increased, and a resin having a balanced sensitivity, adhesion, and the like can be obtained.
As the component (c ″), a 4-membered acid (anhydride) is particularly preferably used. In this case, the addition rate of the 4-membered acid (anhydride) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to 100 mol% based on the hydroxyl group formed when the component (b ") is added to the component (a"). By setting the addition rate of the 4-membered acid (anhydride) as the component (c ") to the lower limit or more, sufficient solubility of the alkali-soluble resin (a") and good adhesion to the substrate can be ensured.
In view of adjusting the viscosity and solubility of the colored photosensitive composition, it is preferable to replace a part of the 4-membered acid (anhydride) with a 2-membered acid (anhydride).
When a 4-membered acid (anhydride) and a 2-membered acid (anhydride) are used in combination as the component (c ″), the molar ratio is preferably 2-membered acid (anhydride): 4-membered acid (anhydride) =99, more preferably 80. When the ratio of the 4-membered acid (anhydride) is not less than the lower limit, the obtained coating film can have high film properties, and when the ratio of the 2-membered acid (anhydride) is not less than the lower limit, the viscosity of the obtained resin solution can be prevented from increasing, and the workability can be improved.
In addition, in order to improve the adhesion to the substrate, easily adjust the solubility, improve the sensitivity or alkali resistance, etc., in order to make the molecular weight and viscosity, sensitivity, adhesion and other various balance, preferably 4-membered acid (anhydride) and 2-membered acid (anhydride) at least one and 3-membered acid (anhydride) combined use.
When at least one of a 4-membered acid (anhydride) and a 2-membered acid (anhydride) is used in combination with a 3-membered acid (anhydride) as the component (c '), since there is a possibility that the effect is small and the alkali resistance is lowered if the amount of the 3-membered acid (anhydride) used is too small, the amount of the 3-membered acid (anhydride) used is usually 5 to 70 mol%, preferably 10 to 40 mol%, based on the hydroxyl group generated when the component (b ') is added to the component (a ').
The total addition rate of the component (c ") is usually 10 to 100 mol%, preferably 20 to 100 mol%, and more preferably 30 to 100 mol% based on the hydroxyl group formed when the component (b") is added to the component (a "). When the addition rate of the component (c ") is not less than the lower limit, the solubility of the alkali-soluble resin (a") and the adhesion to the substrate become better.
The component (c ") may react with a hydroxyl group generated when the component (b") is added to the component (a ") or may react with any hydroxyl group present in the mixture when the component (b") is added to the component (a ") and the polyol (d") described later is mixed therein.
As a method for adding the component (c ") after adding the component (b") to the component (a "), or after mixing the polyol (d") described later therewith, a known method can be used.
The reaction temperature is usually 80 to 130 ℃ and preferably 90 to 125 ℃. When the reaction temperature exceeds 130 ℃, part of the unsaturated groups in the component (b ") is polymerized, which may result in a sharp increase in molecular weight. If the temperature is lower than 80 ℃, the reaction may not proceed smoothly and the component (c') may remain.
(4) Polyol (d')
The binder resin used in the present invention may be an alkali-soluble resin (A1) obtained by further mixing a polyol (d ") (hereinafter, sometimes referred to as a" component (d ")) with a reaction product obtained by adding the component (b") to the component (a ") and by subjecting the component (c") to an addition reaction with respect to any hydroxyl group present in the mixture.
The component (d') is preferably 1 or 2 or more polyols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol, for example.
By using the component (d ″), the molecular weight of the alkali-soluble resin (A1 ″) can be increased, and a branch can be introduced into the molecule, whereby the molecular weight and the viscosity can be balanced. Further, the introduction rate of an acid group into a molecule can be increased, and an organic binder having a balanced sensitivity, adhesion, and the like can be obtained.
When the amount of the component (d ") is too small, the effect may be small, and when it is too large, thickening or gelation may occur, so that the amount is usually 0.01 to 0.5 times by weight, preferably 0.02 to 0.2 times by weight, based on the reaction product of the components (a") and (b ").
(5) Acid value and molecular weight of the alkali-soluble resins (A ') and (A1')
The acid value of the alkali-soluble resins (A ') and (A1') thus obtained is usually not less than 10mg-KOH/g, preferably not less than 50 mg-KOH/g. The acid value is preferably not less than the lower limit in order to ensure good developability, and is preferably not more than 200mg-KOH/g, more preferably not more than 150mg-KOH/g in order to ensure sufficient alkali resistance of the colored photosensitive composition (that is, in order to prevent roughening of the pattern surface and reduction of the film due to an alkali developer).
The weight average molecular weight (Mw) of the alkali-soluble resins (a ") and (A1") in terms of standard polystyrene, as measured by Gel Permeation Chromatography (GPC), is preferably 1,500 or more, more preferably 2,000 or more. Further, it is preferably 20,000 or less, and more preferably 10,000 or less. When the weight average molecular weight is not less than the lower limit, the sensitivity, the coating film strength, the alkali resistance, and the like are further improved. Further, by setting the content to the above upper limit or less, good developability and resolubility can be obtained.
< alkali-soluble resin (A) >)
The alkali-soluble resin (a) is obtained by further reacting at least one of a polybasic acid and an acid anhydride thereof (c) with a reactant of a specific epoxy resin (a) and an unsaturated group-containing carboxylic acid (b).
(1) Epoxy resin (a)
The epoxy resin (a) is represented by the following general formula (1-a).
[ chemical formula 6]
Figure BDA0002049735360000191
[ in the general formula (1-a), n represents an average value and represents a number of 0 to 10. R is 41 Represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Note that 1 molecule existsAt a plurality of R 41 May be the same or different. G represents a glycidyl group.]
R in the formula (1-a) 41 Represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group, and R is R in view of sensitivity and solubility 41 Particularly, a hydrogen atom or a methyl group is preferable. In addition, a plurality of R present in 1 molecule 41 May be the same or different.
The epoxy resin (a) represented by the above general formula (1-a) can be obtained, for example, by reacting a compound represented by the following general formula (1-a-1) with an epihalohydrin in the presence of an alkali metal hydroxide.
[ chemical formula 7]
Figure BDA0002049735360000192
[ wherein n and R 41 Represents n and R in the general formula (1-a) 41 The same meaning is used.]
The compound represented by the above general formula (1-a-1) can be obtained, for example, by subjecting a compound represented by the following general formula (1-a-2) and a phenol to a condensation reaction in the presence of an acid catalyst.
[ chemical formula 8]
Figure BDA0002049735360000193
[ wherein Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R is 41 Represents R in the above general formula (1-a) 41 The same meaning is used.]
In Z of the above general formula (1-a-2), a halogen atom may preferably be a chlorine atom or a bromine atom, and a lower alkoxy group may preferably be a C1-4 alkoxy group such as a methoxy group or an ethoxy group.
On the other hand, the phenol is an aromatic compound having 1 phenolic hydroxyl group in 1 moleculeSpecific examples thereof include: as R in the general formula (1-a), various ortho-, meta-, or para-isomers of alkylphenols such as phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, tert-butylphenol, octylphenol, xylenol, methylbutylphenol, and di-tert-butylphenol, cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, and cyclohexylcresol, and phenylphenol 41 Substituted phenols substituted with the listed groups. These phenols may be used alone in 1 kind, or in combination of 2 or more kinds.
When the condensation reaction is carried out, the amount of the phenol to be used is preferably 0.5 to 20 mol, and particularly preferably 2 to 15 mol, based on 1 mol of the compound represented by the general formula (1-a-2).
An acid catalyst is preferably used in the condensation reaction, and various kinds of acid catalysts can be used, but hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, and the like are preferable, and p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are particularly preferable. The amount of the acid catalyst used is not particularly limited, but is preferably 0.1 to 30% by weight based on the compound represented by the general formula (1-a-2).
The above condensation reaction may be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the case of using an organic solvent include: toluene, xylene, methyl isobutyl ketone, and the like. The amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the raw materials added. The reaction temperature is preferably in the range of 40 to 180 ℃ and the reaction time is preferably 1 to 8 hours.
After the reaction is completed, neutralization treatment or washing treatment is performed to adjust the pH of the product to 3 to 7, preferably 5 to 7. In the case of the washing treatment with water, the treatment may be carried out using, as a neutralizing agent, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, ammonia, sodium dihydrogen phosphate, and various alkaline substances such as diethylene triamine, triethylene tetramine, aniline, and organic amines such as phenylenediamine. The washing treatment may be carried out by a conventional method. For example, a method of adding water in which the neutralizing agent is dissolved to the reaction mixture and repeating the separation and extraction operations can be employed.
After the neutralization treatment or the water washing treatment, the product is concentrated by distilling the unreacted dihydroxybenzenes and the solvent under reduced pressure and heating, whereby the compound represented by the general formula (1-a-1) can be obtained.
As a method for obtaining the epoxy resin (a) of the present invention represented by the above general formula (1-a) from the compound represented by the above general formula (1-a-1), a known method can be employed. For example, the epoxy resin (a) represented by the general formula (1-a) can be obtained by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a dissolved mixture of the compound represented by the general formula (1-a-1) and an excess amount of an epihalohydrin such as epichlorohydrin or epibromohydrin in advance or reacting the mixture at a temperature of 20 to 120 ℃ for 1 to 10 hours while adding the hydroxide.
In the reaction for obtaining the epoxy resin (a), an aqueous solution of the alkali metal hydroxide may be used, and in this case, the following method may be used: a method in which the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and then liquid separation is performed to remove water and continuously return epihalohydrin to the reaction system.
Further, the following method may be used: adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like as a catalyst to a dissolved mixture of the compound represented by the above general formula (1-a-1) and an epihalohydrin, reacting at 50 to 150 ℃ for 1 to 5 hours to obtain a halohydrin etherate of the compound represented by the general formula (1-a-1), adding a solid or aqueous solution of an alkali metal hydroxide to the obtained halohydrin etherate of the compound represented by the general formula (1-a-1), and reacting at 20 to 120 ℃ for 1 to 10 hours again to dehydrohalogenate (ring closure).
The amount of epihalohydrin used in the above reaction is usually 1 to 20 moles, preferably 2 to 10 moles, based on 1 equivalent of hydroxyl group of the compound represented by the general formula (1-a-1). The amount of the alkali metal hydroxide used is usually 0.8 to 15 mol, preferably 0.9 to 11 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1).
In addition, in order to smoothly progress the reaction, an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol to perform the reaction. When alcohols are used, the amount thereof is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. When the aprotic polar solvent is used, the amount thereof to be used is 5 to 100% by weight, preferably 10 to 90% by weight, based on the amount of the epihalohydrin.
The reaction product of such epoxidation reaction is washed with water or not, and epihalohydrin or other additive solvent and the like are removed under reduced pressure and heat, for example, under conditions of 110 to 250 ℃ and a pressure of 1.3kPa (10 mmHg) or less, whereby the intended epoxy resin (a) is obtained.
In order to further produce an epoxy resin having a small amount of hydrolyzable halogen, the epoxy resin obtained may be dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to the solvent to carry out a reaction, thereby enabling the ring closure to be reliably carried out. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, and particularly preferably 0.05 to 0.2 mol, based on 1 equivalent of the hydroxyl group of the compound represented by the general formula (1-a-1) used for epoxidation. The reaction temperature is 50 to 120 ℃ and the reaction time is usually 0.5 to 2 hours.
After the reaction is completed, the formed salt is removed by filtration, washing with water, or the like, and the solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure, whereby the epoxy resin (a) represented by the above general formula (1-a) can be obtained.
(2) Unsaturated group-containing carboxylic acid (b)
Examples of the unsaturated group-containing carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples thereof include: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, alpha-haloalkyl of (meth) acrylic acid, alkoxy, halogen, nitro, cyano-substituted compounds, 2- (meth) acryloyloxyethylsuccinic acid, 2-acryloyloxyethyladipic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhexanoic adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylhutylphthalic acid, 2- (meth) acryloyloxybutylhutylhydrophthalic acid, 2- (meth) acryloyloxybutylhutylhydrolactone, butyrolactone, beta-caprolactone, pentaerythritol, delta- α -hydroxy-butyrolactone, pentaerythritol, and the like, monomers formed from acids (anhydrides) such as phthalic acid (anhydride) and maleic acid (anhydride), and (meth) acrylic acid dimers.
Among them, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity. These substances may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
(3) Reaction of epoxy resin (a) and unsaturated group-containing carboxylic acid (b)
As a method for reacting the epoxy group in the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), a known method can be used. For example, the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) are reacted in an organic solvent at a reaction temperature of 50 to 150 ℃ for several hours to several tens of hours using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine, triphenylphosphine or the like as a catalyst, whereby the carboxylic acid can be added to the epoxy resin.
The amount of the catalyst to be used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (total of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b)).
In order to prevent polymerization during the reaction, a polymerization inhibitor (for example, methoxyphenol, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, t-butylcatechol, phenothiazine, etc.) is preferably used in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the reaction raw material mixture.
The proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. Since the residual epoxy group adversely affects the storage stability, the reaction is usually carried out in a proportion of 0.8 to 1.5 equivalents, particularly preferably 0.9 to 1.1 equivalents, of the unsaturated group-containing carboxylic acid (b) to 1 equivalent of the epoxy group in the epoxy resin (a).
(4) Polybasic acid and anhydride thereof (c)
As the polybasic acid and the acid anhydride (c) thereof to be added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), known ones can be used, and examples thereof include: dibasic carboxylic acids or anhydrides thereof such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl endomethylenetetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, 5-norbornene-2, 3-dicarboxylic acid, and methyl-5-norbornene-2, 3-dicarboxylic acid; and polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and biphenyl tetracarboxylic acid, and anhydrides thereof. Among them, preferred are: tetrahydrophthalic anhydride or succinic anhydride. These substances can be used alone in 1, also can be combined with more than 2.
The addition rate of at least one of the polybasic acid and the anhydride thereof (c) is usually 10 to 100 mol%, preferably 20 to 100 mol%, and more preferably 30 to 100 mol% of the hydroxyl group generated when the unsaturated group-containing carboxylic acid (b) is added to the epoxy resin (a). When the addition rate is too high, the residual film rate during development may be lowered, and when it is too low, the solubility may be insufficient or the adhesion to the substrate may be insufficient. When a polybasic acid and an anhydride thereof are used in combination, the above addition ratio indicates the total addition ratio of the polybasic acid and the anhydride thereof.
As a method of adding the unsaturated group-containing carboxylic acid (b) to the epoxy resin (a) and then adding at least one of the polybasic acid and the anhydride thereof (c), a known method can be used.
In the present invention, after at least one of the polybasic acid and the acid anhydride (c) thereof is added as described above, the epoxy group-containing compound (d) may be added to a part of the generated carboxyl groups. In this case, as the epoxy group-containing compound (d), an epoxy group-containing unsaturated compound such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, or a glycidyl ether compound having a polymerizable unsaturated group may be added for the purpose of improving photosensitivity, and a glycidyl ether compound having no polymerizable unsaturated group may be added for the purpose of improving developability, or both of them may be used in combination. Specific examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group (trade names: denacol EX-111, denacol EX-121, denacol EX-141, denacol EX-145, denacol EX-146, denacol EX-171, and Denacol EX-192, manufactured by Nagase chemical industry Co., ltd.), and the like.
The alkali-soluble resin (a) of the present invention may be a resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group of a resin obtained by further reacting the above-mentioned reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with at least one of a polybasic acid and an acid anhydride (c) thereof.
(5) Physical Properties of the alkali-soluble resin (A)
The weight average molecular weight (Mw) of the alkali-soluble resin (a) used in the present invention, as measured by Gel Permeation Chromatography (GPC), in terms of polystyrene is usually 1500 or more, preferably 2000 or more, and usually 50000 or less, preferably 30000 or less, more preferably 10000 or less. When the weight average molecular weight of the alkali-soluble resin (a) is too small, the sensitivity is deteriorated, and when it is too large, the solubility in the developer is insufficient, which is not preferable.
The acid value (mgKOH/g) of the alkali-soluble resin (a) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. When the acid value of the alkali-soluble resin (a) is too low, sufficient solubility may not be obtained, and when the acid value is too high, curability tends to be insufficient, and surface properties of the coating film tend to be deteriorated.
The synthesis reaction of the alkali-soluble resin (a), such as the condensation reaction of the compound represented by the above general formula (1-a-2) and the phenolic compound, the reaction of the compound represented by the above general formula (1-a-1) obtained by the condensation reaction with the epihalohydrin, and the addition reaction of at least one of the unsaturated group-containing carboxylic acid (b) and the polybasic acid and the acid anhydride thereof (c), can be carried out by a known method, for example, the method described in jp 2005-55814 a.
< alkali-soluble resin (A') >)
As another example of the binder resin in the present invention, a particularly preferable one is an alkali-soluble resin (a ') obtained by reacting a reactant of an epoxy compound (a ') represented by the following general formula (1-a ') and an unsaturated group-containing carboxylic acid (b ') with at least one of a polybasic acid and an acid anhydride thereof (c ').
[ chemical formula 9]
Figure BDA0002049735360000251
In the above general formula (1-a'), p and q each independently represent an integer of 0 to 4, R 31 And R 32 Each independently represents an alkyl group or a halogen atom. R 33 And R 34 Each independently represents an alkylene group. x and y each independently represent an integer of 0 or more.]
(1) An epoxy compound (a ') represented by the general formula (1-a')
First, an epoxy compound (a ') represented by the above general formula (1-a ') (hereinafter, may be referred to as a "component (a ')") will be described.
In the above general formula (1-a'), as R 31 And R 32 The alkyl group of (3) is preferably an alkyl group having 1 to 10 carbon atoms as a halogenExamples of the atoms include: cl, br, F, etc. As R 31 And R 32 Particularly, each independently is an alkyl group having 1 to 5 carbon atoms.
R 31 And R 32 The mechanism of action of the alkyl group or the halogen atom(s) is not specifically defined, but it is presumed that the mechanism affects the three-dimensional structure of the molecule and controls the degree of solubility in the developer.
Therefore, from the above viewpoint, p and q in the general formula (1-a') each independently represent an integer of 0 to 4, preferably 1 or 2.
R 31 And R 32 The position of bonding to the benzene ring is not particularly limited, but is preferably relative to
[ chemical formula 10]
Figure BDA0002049735360000252
Or
[ chemical formula 11]
Figure BDA0002049735360000253
Are in the ortho position.
In addition, R is 31 And R 32 The same group or different groups may be used, but the same group is preferable from the viewpoint of production cost.
As R 33 And R 34 The alkylene group of (b) may be an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group or an alkylene group independently of each other.
x and y each independently represent an integer of 0 or more, and are usually 0 to 6, preferably 0 to 3. In general, the larger x and y, the higher the solubility, but if it is too large, the sensitivity may be lowered.
In addition, R is 33 And R 34 The same group or different groups may be used, but the same group is preferable from the viewpoint of production cost.
The molecular weight of the component (a') is usually in the range of 200 to 200,000, preferably 300 to 100,000, in terms of weight average molecular weight (Mw) of standard polystyrene measured by Gel Permeation Chromatography (GPC). When the molecular weight is not less than the lower limit, the film formability is improved, and when the molecular weight is not more than the upper limit, gelation at the addition reaction of the unsaturated group-containing carboxylic acid (b') described later is suppressed.
(2) Unsaturated group-containing carboxylic acid (b')
As the unsaturated group-containing carboxylic acid (b ') (hereinafter, sometimes referred to as "component (b')"), the same compounds as those listed as the unsaturated group-containing carboxylic acid (b ") in the < alkali-soluble resin (A"), alkali-soluble resin (A1 ") > can be used. Among these, the α, β -unsaturated carboxylic acids are preferred to be (meth) acrylic acid, and particularly acrylic acid is preferred because it is rich in reactivity. In the case of an α, β -unsaturated carboxylic acid ester having a carboxyl group in the ester moiety, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylmaleic acid are preferable.
The amount of the component (b ') used is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the component (a').
When the amount of the component (b ') is not less than the lower limit, a sufficient amount of unsaturated groups can be introduced, and the subsequent reaction with at least one of the polybasic acid and the anhydride (c') thereof becomes sufficient. Further, it is also preferable that a large amount of epoxy groups never remain. When the amount of the component (b ') used is not more than the upper limit, it is preferable in that the component (b') does not remain as an unreacted product. By satisfying the above range, high photocurability can be obtained.
(3) Polybasic acid and anhydride (c')
The polybasic acid and its anhydride (c ') may be the same compounds as those listed as the polybasic acid and its anhydride (c ') in the < alkali-soluble resin (A "), alkali-soluble resin (A1 ') > and, among them, tetrahydrophthalic acid, biphenyltetracarboxylic acid and their anhydrides are preferred.
The addition ratio of at least one of the polybasic acid and the anhydride (c ') thereof is preferably such that the acid value of the finally obtained alkali-soluble resin (A') becomes 10 to 150mg-KOH/g, more preferably 20 to 140mg-KOH/g. When the acid value is not less than the lower limit, the alkali developability is good, and when the acid value is not more than the upper limit, sufficient photocurability can be obtained.
In addition reaction of the component (c '), a polyfunctional alcohol (d') such as trimethylolpropane, pentaerythritol, dipentaerythritol, or the like may be added to produce a substance having a multi-branched structure introduced therein. Examples of the polyol (d ') include the same compounds as those described above as the polyol (d ") in the < alkali-soluble resin (a"), alkali-soluble resin (A1') > and the like, and preferred compounds and preferred amounts thereof are also the same.
The synthesis reaction of the alkali-soluble resin (a ') such as the addition reaction of the unsaturated group-containing carboxylic acid (b') and at least one of the polybasic acid and the anhydride thereof (c ') to the epoxy compound (a') can be carried out by a known method, and can be carried out, for example, by the methods described in japanese patent application laid-open nos. 2005-126685, 2005-325331, and 2006-241224.
The weight average molecular weight (Mw) of the alkali-soluble resin (a') measured by Gel Permeation Chromatography (GPC) in terms of standard polystyrene is usually 1,000 or more, preferably 1,500 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 8,000 or less. When the weight average molecular weight is equal to or less than the upper limit, the developability is good, and when the weight average molecular weight is equal to or more than the lower limit, the alkali resistance is good.
< alkali soluble resin (A' ") >)
As another example of the binder resin in the present invention, a particularly preferable example is an alkali-soluble resin (a ' ") obtained by reacting at least one of a polybasic acid and an acid anhydride thereof (c '") with a reactant of an epoxy resin (a ' ") represented by the following general formula (1-a '") and an unsaturated group-containing carboxylic acid (b ' ").
[ chemical formula 12]
Figure BDA0002049735360000271
[ in the above general formula (1-a'), R 51 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 52 Represents a 2-valent polycyclic hydrocarbon group having 5 to 16 carbon atoms, R 53 And R 54 Each independently represents a hydrogen atom or a glycidyl group. s represents 1 or 2.t and z represent the ratio of each repeating unit, and t.gtoreq.z.gtoreq.0.5 t.]
In the general formula (1-a'), R 51 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and among them, a hydrogen atom or a methyl group is preferable from the viewpoint of photocurability. In addition, s represents 1 or 2, preferably 1.
R 52 Represents a 2-valent polycyclic hydrocarbon group having 5 to 16 carbon atoms. Such a group can be formed by performing a reaction described later using, as a raw material, an unsaturated polycyclic hydrocarbon ring compound having at least 2 carbon-carbon double bonds in the same skeleton (hereinafter, may be simply referred to as "unsaturated polycyclic hydrocarbon compound").
Examples of the unsaturated polycyclic hydrocarbon ring compound used as a raw material include the following compounds, but are not limited thereto.
[ chemical formula 13]
Figure BDA0002049735360000281
Of these compounds, a crosslinked carbocyclic ring is more preferable, and dicyclopentadiene is particularly preferable.
The epoxy resin (a '") represented by the general formula (1-a'") can be obtained by glycidylating a hydroxyl group of an addition polymerization reaction product of the unsaturated polycyclic hydrocarbon compound and a phenol compound represented by the general formula.
[ chemical formula 14]
Figure BDA0002049735360000282
[ in the above formula, R 51 And s has the same meaning as defined in the above general formula (1-a').]
The epoxy resin (a '") is particularly preferably a compound represented by the following general formula (1-a'" -1) obtained by glycidylating an addition polymerization reaction product of dicyclopentadiene and the above phenol compound.
[ chemical formula 15]
Figure BDA0002049735360000291
[ in the above general formula (1-a' -1), R 53 、R 54 T and z are as defined in the above formula (1-a').]
The ratio of glycidyl groups introduced into the phenolic resin of the general formulae (1-a ') and (1-a' -1) is preferably 50 to 100 mol% based on the phenolic hydroxyl groups in the phenolic resin before glycidylation that is, t and z in the above general formula (1-a ') and general formula (1-a' -1) need to have a relationship of t.gtoreq.z.gtoreq.0.5 t, preferably 70 to 100 mol% are substituted by glycidyl groups.
The alkali-soluble resin (a ' ") is obtained by reacting a reactant of the epoxy resin (a '") represented by the general formula (1-a ' ") and the unsaturated group-containing carboxylic acid (b '") with at least one of a polybasic acid and an acid anhydride (c ' ") thereof.
As the unsaturated group-containing carboxylic acid (b' "), the same compounds as exemplified as the unsaturated group-containing carboxylic acid (b") in the < alkali-soluble resin (a "), alkali-soluble resin (A1") > can be used, and preferred compounds and the reason therefor are also the same as described above.
The proportion of the unsaturated group-containing carboxylic acid (b '") added to the epoxy group of the epoxy resin (a'") is usually 90 to 100 mol%. Since the residual epoxy group adversely affects the storage stability, the unsaturated group-containing carboxylic acid (b '") is reacted usually at a ratio of 0.8 to 1.5 equivalents, particularly preferably at a ratio of 0.9 to 1.1 equivalents, based on 1 equivalent of the epoxy group in the epoxy resin (a'").
The polybasic acid and its acid anhydride (c' ") may be the same compounds as those listed as the polybasic acid and its acid anhydride (c") in the < alkali-soluble resin (a "), alkali-soluble resin (A1") > and the preferred compounds and the reasons therefor are the same as those described above.
The addition rate of at least one of the polybasic acid and the anhydride thereof (c '") is usually 15 to 100 mol% based on the hydroxyl group formed when the unsaturated group-containing carboxylic acid (b'") is added to the epoxy resin (a '"), preferably 20 to 90 mol%, and the acid value of the finally obtained alkali-soluble resin (A') is preferably 45 to 160mg-KOH/g. By setting the addition ratio to the upper limit or less, a reduction in the residual film ratio during development can be prevented, and by setting the addition ratio to the lower limit or more, good solubility and adhesion to the substrate can be obtained. In addition, in the case of using a polybasic acid and an anhydride thereof in combination, the above addition rate represents the total addition rate of the polybasic acid and the anhydride thereof.
The synthesis reaction of the alkali-soluble resin (a ' ") such as the reaction between the unsaturated polycyclic hydrocarbon compound and the phenol compound, the glycidylation reaction of hydroxyl groups in the phenolic resin obtained by the reaction, and the addition reaction of at least one of the unsaturated group-containing carboxylic acid (b '") and the polybasic acid and the acid anhydride thereof (c ' ") can be carried out by a known method, and can be carried out, for example, by the method described in japanese unexamined patent application publication No. 5-214048.
The weight average molecular weight of the alkali-soluble resin (A' ") is usually 1,500 to 4,000, preferably 2,000 to 3,500, and more preferably 2,500 to 3,000. When the weight average molecular weight is too small, the developing solubility may be too high, and when it is too large, the developing solubility may be too low.
In the present invention, these binder resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The binder resins in the colored photosensitive composition of the invention are preferably the alkali-soluble resins (a) and (a ' ") in view of the balance between the shape and height difference control and the adhesion to the substrate among the alkali-soluble resins (a), (a '), (a"), (a ' "), (A1") described above.
The content of the binder resin is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less, based on the total solid content of the colored photosensitive composition of the present invention. By setting the content of the binder resin to the lower limit value or more, the shape and the level difference can be controlled, and the solubility of the developer in the unexposed portion can be secured. By setting the upper limit value to the lower limit value, the occurrence of wrinkles due to excessive shrinkage during heat curing can be suppressed.
[3] Photopolymerizable monomer
In the present invention, the photopolymerization initiator may be used together with a photopolymerizable monomer such as an ethylenically unsaturated compound.
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 possibility of expanding the difference in developer solubility between an exposed portion and a non-exposed portion accompanying the same, and further preferably a (meth) acrylate compound derived from a (meth) acryloyloxy group.
Further, from the viewpoint of voltage holding ratio, it is preferable to use a compound having 3 or more ethylenically unsaturated bonds in the molecule.
Examples of the compound having 1 or more ethylenically unsaturated bonds in the molecule include: unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, and styrene.
As the compound having 2 or more ethylenically unsaturated bonds in the molecule, there are typically mentioned: esters of unsaturated carboxylic acids and polyhydric compounds, phosphoric acid esters containing (meth) acryloyloxy groups, urethane (meth) acrylic acids formed from hydroxy (meth) acrylate compounds and polyisocyanate compounds, and epoxy (meth) acrylates formed from (meth) acrylic acids or hydroxy (meth) acrylate compounds and polyepoxides, and the like.
Specific examples of the esters of the unsaturated carboxylic acid and the polyhydric compound include the following compounds.
Reactants of unsaturated carboxylic acids and sugar alcohols; specific examples of sugar alcohols include: ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and the like.
A reactant of an epoxide adduct of an unsaturated carboxylic acid and a sugar alcohol; the sugar alcohol is the same as described above. Specific examples of the epoxide adduct include: ethylene oxide adducts and propylene oxide adducts.
A reactant of an unsaturated carboxylic acid and an alcohol amine; specific examples of the alkanolamines include: diethanolamine, triethanolamine, and the like.
Specific esters of unsaturated carboxylic acids and polyols are described below.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and also butyrate, isobutyrate, maleate, itaconate, citraconate, and the like.
As other esters of unsaturated carboxylic acids and polyhydroxy compounds, mention may be made of: unsaturated carboxylic acid and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, etc., or their ethylene oxide adducts. Specific examples thereof include: bisphenol a di (meth) acrylate, bisphenol a bis [ oxyethylene (meth) acrylate ], bisphenol a bis [ glycidyl ether (meth) acrylate ], and the like, and further, there can be mentioned: the reactant of the above-mentioned unsaturated carboxylic acid and a heterocyclic polyol such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, and the like, include: the reactant of the unsaturated carboxylic acid and the polycarboxylic acid with the polyhydroxy compound, for example, a condensate of (meth) acrylic acid and phthalic acid with ethylene glycol, a condensate of (meth) acrylic acid and maleic acid with diethylene glycol, a condensate of (meth) acrylic acid and terephthalic acid with pentaerythritol, a condensate of (meth) acrylic acid and adipic acid with butanediol and glycerin, and the like.
The (meth) acryloyloxy phosphate-containing compounds are preferably represented by the following general formulae (6), (7) and (8).
[ chemical formula 16]
Figure BDA0002049735360000321
(in formulae (6), (7) and (8), R A Represents a hydrogen atom or a methyl group, e and g are integers of 1 to 25, and f is 1,2 or 3. )
Among them, e and g are preferably 1 to 10, particularly preferably 1 to 4, and specific examples thereof include: (meth) acryloyloxyethyl phosphate, bis [ (meth) acryloyloxyethyl ] phosphate, and (meth) acryloyloxyethyl glycol phosphate, and these may be used alone or as a mixture.
Examples of the urethane (meth) acrylates formed from the hydroxyl (meth) acrylate compound and the polyisocyanate compound include: and a reaction product of a hydroxyl (meth) acrylate compound such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, or tetramethylolethane tri (meth) acrylate, and a polyisocyanate compound containing: aliphatic polyisocyanates such as hexamethylene diisocyanate and 4-isocyanatomethyl-1, 8-octane diisocyanate, alicyclic polyisocyanates such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate and bicycloheptane triisocyanate, aromatic polyisocyanates such as 4, 4-diphenylmethane diisocyanate and tris (isocyanatophenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate.
Examples of the above-mentioned substances include those having the trade names "U-4HA", "UA-306A", "UA-MC340H" and "U6LPA" manufactured by Ninghama chemical Co., ltd.
Among them, a compound having 4 or more urethane bonds [ -NH-CO-O- ] and 4 or more (meth) acryloyloxy groups in 1 molecule is preferable, and the compound can be obtained by reacting a compound having 4 or more, preferably 6 or more isocyanate groups in 1 molecule, such as "Duranate ME20-100" manufactured by Asahi Kasei chemical Co., ltd, with a compound having 1 or more hydroxyl groups and 2 or more, preferably 3 or more (meth) acryloyloxy groups in 1 molecule, such as pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the compound having 4 or more, preferably 6 or more isocyanate groups in 1 molecule, such as pentaerythritol, polyglycerin, and the compound having 4 or more hydroxyl groups in 1 molecule, with a diisocyanate compound, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and toluene diisocyanate; or a compound obtained by reacting a compound having 2 or more hydroxyl groups in 1 molecule such as ethylene glycol with a compound having 3 or more isocyanate groups in 1 molecule such as a biuret type such as "Duranate 24A-100", "Duranate 22A-75PX", "Duranate 21S-75E", "Duranate 18H-70B", or an adduct type such as "Duranate P-301-75E", "Duranate E-402-90T", or "Duranate E-405-80T", manufactured by Asahi Kasei corporation; or a compound obtained by polymerizing or copolymerizing isocyanate (meth) acrylate or the like.
Examples of the epoxy (meth) acrylates formed from the (meth) acrylic acid or hydroxy (meth) acrylate compound and the polyepoxide compound include: a reaction product of (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, with a polyepoxide compound including: aliphatic polyepoxides such as (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, and (poly) sorbitol polyglycidyl ether, aromatic polyepoxides such as phenol novolac polyepoxide, brominated phenol novolac polyepoxide, (o-, m-, p-) cresol novolac polyepoxide, bisphenol a polyepoxide, and bisphenol F polyepoxide, and heterocyclic polyepoxides such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl isocyanurate tri (2-hydroxyethyl) ester.
Examples of other ethylenically unsaturated compounds other than the above-mentioned compounds include: (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate; thioether bond-containing compounds in which the ether bond of an ether bond-containing ethylenically unsaturated compound is vulcanized to a thioether bond by phosphorus sulfide 5 or the like to increase the crosslinking rate; and compounds obtained by bonding a polyfunctional (meth) acrylate compound to a silica sol having a particle diameter of 5 to 30nm [ for example, an isopropyl alcohol-dispersed organic silica sol ("IPA-ST" manufactured by japanese chemical corporation), a methyl ethyl ketone-dispersed organic silica sol ("MEK-ST" manufactured by japanese chemical corporation), a methyl isobutyl ketone-dispersed organic silica sol ("MIBK-ST" manufactured by japanese chemical corporation ], and the like ] using a silane coupling agent containing an isocyanate group or a mercapto group, and the like, and compounds obtained by reacting and bonding an ethylenically unsaturated compound to a silica sol via a silane coupling agent, thereby improving the strength or heat resistance of a cured product.
In the present invention, the ethylenically unsaturated compound is preferably an ester (meth) acrylate or a urethane (meth) acrylate, and particularly preferably a 5-functional or higher functional compound such as dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate.
The above ethylenically unsaturated compounds may be used alone or in combination of 2 or more.
The proportion of the photopolymerizable monomer in the colored photosensitive composition of the invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, and particularly preferably 12 to 30% by weight, based on the total solid content. If the proportion of the photopolymerizable monomer is more than this range, the curing degree tends to be lowered as the proportion of the other component is decreased, and thus the voltage holding ratio tends to be deteriorated. On the other hand, if the proportion of the photopolymerizable monomer is too small, the amount of the alkali resin increases, and thus the developability tends to decrease.
[4] Photopolymerization initiator
The photopolymerization initiator is usually used in the form of a mixture with an accelerator (photopolymerization initiator system), and is used in combination with a sensitizing dye or the like added as needed.
The photopolymerization initiator system is a component having a function of directly absorbing light or sensitizing light to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
As the photopolymerization initiator constituting the photopolymerization initiator system component, various compounds described in, for example, international publication No. 2008/153000 can be used.
The photopolymerization initiator used in the colored photosensitive composition of the invention is particularly preferably an oxime ester compound in view of good generation efficiency of the polymerization active radical, and among them, the compounds exemplified below can be preferably used. [ chemical formula 17]
Figure BDA0002049735360000351
[ chemical formula 18]
Figure BDA0002049735360000361
Examples of the accelerator and the sensitizing dye constituting the photopolymerization initiator system component include various compounds described in, for example, international publication No. 2008/153000, and preferred compounds are also the same as those described in international publication No. 2008/153000.
The content of the photopolymerization initiator system component (mixture of photopolymerization initiator and accelerator) is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content in the colored photosensitive composition of the invention. When the content ratio is significantly low, sensitivity to exposure light may be reduced, and conversely, when the content ratio is significantly high, solubility of an unexposed portion to a developer may be reduced, thereby causing development failure.
The content of the sensitizing dye in the colored photosensitive composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, and more preferably 0 to 10% by weight, based on the total solid content in the colored photosensitive composition.
[5] Dispersing agent and dispersing aid
In order to improve the dispersibility of the pigment and to improve the dispersion stability, the colored photosensitive composition of the present invention is preferably used in combination with at least one of a pigment dispersant and a dispersion aid. Among these, the use of a polymer dispersant as a pigment dispersant is preferable because it is excellent in dispersion stability with time. Here, the polymer dispersant is a polymer having a completely different structure from the pigment for securing dispersion stability of the pigment, and the dispersion aid is a pigment derivative or the like for improving dispersibility of the pigment.
Examples of the polymeric dispersant include: polyurethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. Specific examples of such dispersants include dispersants such as EFKA (BASF), disperbYK (BYK-Chemie), disparlon (manufactured by Nakan Kasei Co., ltd.), SOLSPERSE (manufactured by Zeneca corporation), KP (manufactured by shin-Etsu chemical Co., ltd.), and Polyflow (manufactured by Kyoho chemical Co., ltd.).
These polymeric dispersants may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the pigment derivative include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, bisquinone
Figure BDA0002049735360000371
Azines, anthraquinones, indanthrones, perylenes, perinones, diketopyrrolopyrroles
Figure BDA0002049735360000372
Among the derivatives such as azines, quinophthalones are preferable. As substituents of the pigment derivative, there may be mentioned: sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which are bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, and the like, are preferably sulfonic acid groups. In addition, a plurality of these substituents may be substituted for one pigment skeleton.
Specific examples of the pigment derivative include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, bis
Figure BDA0002049735360000373
Sulfonic acid derivatives of oxazines, and the like.
These pigment derivatives may be used alone in 1 kind, or in combination of 2 or more kinds.
In the colored photosensitive composition of the invention, the content of at least one of the dispersant and the dispersing aid is usually 5% by weight or more and 120% by weight or less, preferably 5% by weight or more and 90% by weight or less, more preferably 5% by weight or more and 60% by weight or less, and particularly preferably 5% by weight or more and 40% by weight or less, relative to the pigment. When the content of the dispersant and the dispersing aid is too small, sufficient dispersibility may not be obtained, and when it is too large, the ratio of other components may be relatively decreased, and the voltage holding ratio may be lowered. In the case where the dispersant and the dispersion aid are used in combination, the above content represents the total content of the dispersant and the dispersion aid.
When the pigment derivative is used, the amount thereof is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight, based on the pigment in the colored photosensitive composition.
[6] Solvent(s)
The colored photosensitive composition of the present invention is usually prepared by dissolving or dispersing the above-mentioned pigment, binder resin, photopolymerizable monomer, photopolymerization initiator, dispersant, dispersion aid, and solid components such as other components described later in a solvent.
In the colored photosensitive composition of the present invention, the solvent has a function of dissolving or dispersing a pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and the like, and adjusting the viscosity.
As the solvent, a solvent having a boiling point in the range of 100 to 300 ℃ is preferably selected. More preferably a solvent having a boiling point of 120 to 280 ℃.
Examples of such solvents include various solvents described in international publication No. 2008/153000.
These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Particularly in the case of forming a spacer of black light by photolithography, it is more preferable to select, as the solvent, a solvent having a boiling point in the range of 100 to 200 ℃ (pressure of 1013.25[ hPa ], hereinafter, with respect to the boiling point, all of the solvents are in the range of pressure of 1013.25[ hPa ]. Particularly preferred is a solvent having a boiling point of 120 to 170 ℃.
Among the solvents described in international publication No. 2008/153000, glycol alkyl ether acetates are preferred in view of a good balance of coatability, surface tension, and the like, and a relatively high solubility of the constituent components in the composition.
In addition, the glycol alkyl ether acetates may be used alone or in combination with other solvents. Particularly preferred as the solvent used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is preferable in view of the solubility of the components in the composition. The diol monoalkyl ethers are preferably contained in the solvent in an amount of 5 to 30 wt%, more preferably 5 to 20 wt%, because the diol monoalkyl ethers have high polarity and when the amount of the diol monoalkyl ethers is too large, the pigment tends to aggregate easily and the storage stability tends to be lowered, for example, the viscosity of the colored photosensitive composition increases with time.
In addition, it is also preferable to use a solvent having a boiling point of 150 ℃ or higher (hereinafter, sometimes referred to as "high-boiling solvent") in combination. By using such a high boiling point solvent in combination, the colored photosensitive composition is not easily dried, and the effect of preventing the uniform dispersion state of the pigment in the composition from being broken by rapid drying is obtained. That is, the effect of preventing the occurrence of impurity defects caused by precipitation and solidification of a coloring material or the like at the tip of the slit nozzle is obtained. From the viewpoint of high effects, among the various solvents described in international publication No. 2008/153000, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol mono-ethyl ether acetate are particularly preferable.
The content of the high-boiling solvent in the solvent is preferably 3 to 50 wt%, more preferably 5 to 40 wt%, and particularly preferably 5 to 30 wt%. By setting the amount of the high boiling point solvent to the lower limit or more, it is possible to prevent the occurrence of impurity defects caused by precipitation and solidification of a pigment or the like at the tip of a slit nozzle, for example, and by setting the amount to the upper limit or less, it is possible to appropriately maintain the drying rate of the composition in the color filter production process described later, and thus the problems of defective production rhythm in the reduced pressure drying process and the trace of air holes in the prebaking are not caused.
The high boiling point solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be separately contained.
Preferred high boiling point solvents include, for example, among the various solvents mentioned above: diethylene glycol mono n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanol diacetate, glyceryl triacetate, and the like.
The content of the solvent in the entire colored photosensitive composition of the invention is not particularly limited, and is usually 99% by weight or less, and usually 50% by weight or more, preferably 55% by weight or more, and more preferably 60% by weight or more. By setting the ratio of the solvent to the above upper limit or less, a desired and sufficient amount of solid components such as a pigment, a binder resin, and a photopolymerizable monomer can be contained in the colored photosensitive composition. Further, by setting the lower limit value or more, thickening is suppressed, and good coatability and film thickness uniformity of the coating film can be obtained.
In view of the above, the colored photosensitive composition of the present invention uses a solvent and is adjusted so that the solid content concentration thereof is usually 5 to 50% by weight, preferably 10 to 30% by weight.
[7] Other ingredients
The colored photosensitive composition of the present invention may contain, in addition to the above components, a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, a storage stabilizer, a surface protecting agent, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor, and the like.
[7-1] photoacid generators
The photoacid generator is a compound that can generate an acid under the action of ultraviolet light, and a crosslinking reaction proceeds by the presence of a crosslinking agent such as a melamine compound under the action of the acid generated during exposure. Among the photoacid generators, those having high solubility in a solvent, particularly in a solvent used in the colored photosensitive composition, are preferred, and examples thereof include: diphenyl iodide
Figure BDA0002049735360000402
Dimethyl phenyl iodide
Figure BDA0002049735360000403
Phenyl (p-anisyl) iodide
Figure BDA0002049735360000404
Bis (m-nitrophenyl) iodide
Figure BDA0002049735360000405
Bis (p-tert-butylphenyl) iodide
Figure BDA0002049735360000406
Bis (p-chlorophenyl) iodide
Figure BDA0002049735360000407
Bis (n-dodecyl) iodide
Figure BDA0002049735360000408
P-isobutylphenyl (p-tolyl) iodide
Figure BDA00020497353600004011
P-isopropylphenyl (p-tolyl) iodide
Figure BDA0002049735360000409
Isodiaryl iodides
Figure BDA00020497353600004010
Or chloride, bromide or fluoroborate of triarylsulfonium such as triphenylsulfonium, hexafluorophosphate, and hexafluoroarsenateSalts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate, and the like; sulfonium organoboron complexes such as diphenylbenzoylmethyl sulfonium (n-butyl) triphenylborate; and triazine compounds such as 2-methyl-4, 6-bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4, 6-bistrichloromethyltriazine, but the present invention is not limited thereto.
These photoacid generators may be used alone in 1 kind, or in combination of 2 or more kinds.
When the photoacid generator is used, the content thereof is preferably 0 to 20% by weight, and particularly preferably 2 to 15% by weight, based on the total solid content of the colored photosensitive composition.
[7-2] crosslinking agent
The colored photosensitive composition of the invention may further contain a crosslinking agent, and for example, melamine or guanamine compounds may be used. Examples of the crosslinking agent include melamine and guanamine compounds represented by the following general formula (XI).
[ chemical formula 19]
Figure BDA0002049735360000401
[ wherein, R 61 represents-NR 66 R 67 Radicals or aryl radicals at R 61 is-NR 66 R 67 In the case of R 62 、R 63 、R 64 、R 65 、R 66 And R 67 represents-CH 2 OR 68 And at R 61 In the case of aryl, R 62 、R 63 、R 64 And R 65 One of them represents-CH 2 OR 68 Radical, R 62 、R 63 、R 64 、R 65 、R 66 And R 67 The remaining groups in (A) independently of one another represent a hydrogen atom or-CH 2 OR 68 Wherein R is 68 Represents a hydrogen atom or an alkyl group.]
Among them, aryl is typically phenyl, 1-naphthyl or 2-naphthyl, to which alkyl, alkoxy, halogen atom or the like may be bondedA substituent group. The alkyl group and the alkoxy group may each have 1 to 6 carbon atoms. R is 68 The alkyl groups represented are generally methyl or ethyl groups of the above, especially methyl groups.
The melamine-based compound corresponding to the general formula (XI), that is, the compound of the following general formula (XI-1), includes hexamethylolmelamine, pentamethylmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, and the like.
[ chemical formula 20]
Figure BDA0002049735360000411
[ wherein, in R 62 、R 63 、R 64 、R 65 、R 66 And R 67 In the case that one of them is an aryl group, R 62 、R 63 、R 64 And R 65 One of them represents-CH 2 OR 68 Radical, R 62 、R 63 、R 64 、R 65 、R 66 And R 67 The remaining groups in (A) independently of one another represent a hydrogen atom or-CH 2 OR 68 Wherein R is 68 Represents a hydrogen atom or an alkyl group.]
In addition, with respect to the guanamine-based compound corresponding to the general formula (XI), that is, R in the general formula (XI) 61 As the compound which is an aryl group, there are included tetramethylolbenzoguanamine, tetramethoxymethylbenzguanamine, trimethoxymethylbenzguanamine, tetraethoxymethylbenzguanamine and the like.
Furthermore, crosslinkers having methylol or methylol alkyl ether groups may also be used. Examples thereof are listed below.
2, 6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2, 6-bis (hydroxymethyl) phenol, 5-ethyl-1, 3-bis (hydroxymethyl) perhydro-1, 3, 5-triazin-2-one (commonly known as N-ethyldimethylol triazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3, 5-bis (hydroxymethyl) perhydro-1, 3,5-
Figure BDA0002049735360000412
Diazin-4-one (known as dimethylol furfural) or its dimethyl ether form, tetramethylol glyoxal dialkyl urea or its tetramethyl ether form.
These crosslinking agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When a crosslinking agent is used, the amount of the crosslinking agent is preferably 0.1 to 15% by weight, and particularly preferably 0.5 to 10% by weight, based on the total solid content of the colored photosensitive composition.
[7-3] adhesion improver
The colored photosensitive composition of the present invention may contain an adhesion improving agent in order to sufficiently adhere fine lines and dots.
The adhesion improver is preferably a nitrogen atom-containing compound, a phosphoric acid group-containing compound, a silane coupling agent, or the like, and the nitrogen atom-containing compound is preferably, for example, a diamine (an adhesion enhancer described in japanese patent application laid-open No. 11-184080, or the like) or an azole. Of these, azoles are preferable, imidazoles (adhesion improving agents described in Japanese patent application laid-open No. 9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improving agents described in Japanese patent application laid-open No. 2000-171968, etc.) are particularly preferable, and imidazoles and benzimidazoles are most preferable. Among them, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable, from the viewpoint of preventing fogging and greatly improving adhesion. As the silane coupling agent, various silane coupling agents such as epoxy, methacrylic, and amino can be used, and epoxy or isocyanate silane coupling agents are particularly preferable.
These silane coupling agents may be used alone in 1 kind, or in combination of 2 or more kinds.
When the adhesion improver is blended, the blending ratio thereof varies depending on the type of the adhesion improver to be used, and is preferably 0.01 to 5% by weight, and particularly preferably 0.05 to 3% by weight, based on the total solid content of the colored photosensitive composition. If the amount is less than the above range, a sufficient adhesion improving effect may not be obtained, and if the amount is too large, the developability may be lowered.
[7-4] sensitizing pigment
Examples of the sensitizing dye include: examples of the xanthene dye described in Japanese patent laid-open Nos. 4-221958 and 4-219756, the coumarin dye having a heterocyclic ring described in Japanese patent laid-open Nos. 3-239703 and 5-289335, the 3-oxocoumarin compound described in Japanese patent laid-open Nos. 3-239703 and 5-289335, and the methylenepyrrole dye described in Japanese patent laid-open No. 6-19240 include: and pigments having a dialkylaminobenzene skeleton described in Japanese patent laid-open Nos. Sho 47-2528, sho 54-155292, sho 45-37377, sho 48-84183, sho 52-112681, sho 58-15503, sho 60-88005, sho 59-56403, hei 2-69, sho 57-168088, hei 5-107761, hei 5-210240, and Hei 4-288818.
These sensitizing pigments may be used alone in 1 kind, or in combination in 2 or more kinds.
When the sensitizing dye is blended, the content of the sensitizing dye in the total solid content of the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If the amount is less than the above range, the sensitizing effect may not be exhibited, and if the amount is too large, the developability may be reduced.
[7-5] surfactant
As the surfactant, 1 or 2 or more kinds of various surfactants such as anionic, cationic, nonionic, amphoteric surfactants and the like can be used, but the nonionic surfactant is preferably used in view of low possibility of adversely affecting various properties. Further, fluorine-based and silicon-based surfactants are effective in coatability.
When the surfactant is used, the compounding ratio thereof is usually in the range of 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, and most preferably 0.03 to 0.3% by weight, based on the total solid content in the colored photosensitive composition. When the amount of the surfactant added is less than the above range, smoothness and uniformity of the coating film may not be exhibited, and when the amount of the surfactant added is large, smoothness and uniformity of the coating film may not be exhibited, and other properties may be deteriorated.
[7-6] organic carboxylic acid, organic carboxylic acid anhydride
The colored photosensitive composition of the present invention may contain at least one of an organic carboxylic acid and an organic carboxylic acid anhydride in order to improve developability and improve plate stain.
Examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic carboxylic acids.
Specific examples of the aliphatic carboxylic acid include: monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, heptanoic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as 1,2, 3-propanetricarboxylic acid, aconitic acid, and camphortricarboxylic acid.
Specific examples of the aromatic carboxylic acid include: and carboxylic acids having a carboxyl group directly bonded to a phenyl group such as benzoic acid, toluic acid, cumic acid, 2, 3-dimethylbenzoic acid, 3, 5-dimethylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,3, 5-benzenetetracarboxylic acid, pyromellitic acid, phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyl acetate, coumaric acid, and umbellic acid, and carboxylic acids having a carboxyl group bonded to a phenyl group via a carbon bond.
Among the above organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and among them, malonic acid, glutaric acid and glycolic acid are more preferable, and malonic acid is particularly preferable.
The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. When the molecular weight of the organic carboxylic acid is too large, the plate-stain-improving effect may be insufficient, and when it is too small, sublimation, volatilization, or the like may cause a decrease in the amount of addition or process contamination.
Examples of the organic carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides, and specific examples of the aliphatic carboxylic acid anhydride include: aliphatic carboxylic acid anhydrides such as acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1, 2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Specific examples of the aromatic carboxylic acid anhydride include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like.
Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. When the molecular weight of the organic carboxylic anhydride is too large, the plate-stain-improving effect may be insufficient, and when it is too small, sublimation, volatilization, or the like may cause a decrease in the amount of addition or process contamination.
These organic carboxylic acids and organic carboxylic acid anhydrides may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When these organic carboxylic acids and organic carboxylic acid anhydrides are used, the amount of each of them added is usually 0.01 to 5% by weight, preferably 0.03 to 3% by weight, based on the total solid content of the colored photosensitive composition of the present invention. When the amount of the additive is too small, a sufficient effect of the additive may not be obtained, and when the amount is too large, surface smoothness or sensitivity may be deteriorated, resulting in generation of an undissolved release sheet.
[7-7] thermal polymerization inhibitor
As the thermal polymerization inhibitor, for example, 1 or 2 or more kinds of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2, 6-t-butyl-p-cresol, β -naphthol, etc. can be used.
The compounding ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the colored photosensitive composition, and if the compounding ratio of the thermal polymerization inhibitor is higher than the above range, light-shielding properties and sensitivity of the colored photosensitive composition may be lowered.
[7-8] plasticizer
As the plasticizer, for example: 1 or more than 2 of dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc.
The blending ratio of these plasticizers is preferably in the range of 0 to 5% by weight with respect to the total solid content of the colored photosensitive composition, and if the blending ratio of the plasticizer is higher than the above range, the curing point of the black photo spacer is lowered.
[ method for producing colored photosensitive composition ]
The colored photosensitive composition of the invention is prepared according to a conventional method. The following description will be specifically made by taking examples, but the method for producing the colored photosensitive composition of the present invention is not limited to this method.
From the viewpoint of securing the dispersion stability of the pigment, the colored photosensitive composition of the present invention is preferably a production method in which a pigment dispersion is prepared in advance and other components are mixed therein as described below.
[1] Method for producing pigment dispersion liquid
The pigment, the solvent and the dispersant are weighed in predetermined amounts, and a dispersion aid is used as needed, and the pigment is dispersed in the dispersion treatment step to prepare a liquid pigment dispersion. In the dispersion treatment step, a paint conditioner (paint shaker), a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. Since the pigment is finely pulverized by performing the dispersion treatment, the coating properties and patterning properties such as shape and linearity of the colored photosensitive composition using the pigment dispersion liquid prepared in this way are improved.
In the case of dispersion treatment using a sand mill or a paint shaker, glass beads or zirconia beads having a diameter of 0.1 to 8mm are preferably used. The temperature during the dispersion treatment is usually set to a range of 0 to 100 ℃ and preferably to a range of room temperature to 80 ℃. The dispersion time varies depending on the composition of the pigment dispersion (pigment, solvent, dispersant, etc.) and the size of the apparatus, and therefore, it is necessary to adjust the dispersion time appropriately.
In this case, the standard of dispersion is to control the gloss of the pigment dispersion so that the 20-degree specular gloss in JIS Z8741 (1997) falls within the range of 100 to 200. When the gloss of the pigment dispersion is low, the dispersion treatment is insufficient, coarse pigment particles often remain, and the developability, adhesion, sharpness, and the like are sometimes insufficient. When the gloss value exceeds the above range, the dispersion stability is rather easily impaired by the generation of a large amount of ultrafine particles.
When the pigment is subjected to dispersion treatment, the above-mentioned binder resin, dispersion aid, and the like may be used in appropriate combination. The inclusion of the binder resin can improve dispersion stability in the production of the pigment dispersion liquid.
In this case, the amount of the binder resin added is usually 5 to 100% by weight, preferably 10 to 60% by weight, based on the pigment in the pigment dispersion liquid. When the amount of the binder resin added is equal to or more than the lower limit, higher dispersion stability and patterning property can be obtained, and when the amount is equal to or less than the upper limit, a high pigment concentration can be secured, and higher light-shielding property can be obtained, which is preferable.
The solid content concentration of the pigment dispersion liquid is usually 10 to 40% by weight.
Here, the "total solid content" refers to all components of the pigment dispersion liquid other than the solvent.
[2] Method for producing colored photosensitive composition
The colored photosensitive composition of the invention was prepared as follows: the pigment dispersion obtained in the above-described step is mixed with other components contained in the colored photosensitive composition to prepare a uniform solution. In the dispersion treatment in a liquid in which all the components blended as the colored photosensitive composition are mixed at the same time, the high-reactivity component may be modified due to heat generation during dispersion. In addition, since fine impurities are often mixed into the liquid in the production process, the obtained colored photosensitive composition solution is preferably subjected to a filtration treatment by a filter or the like.
[ Black photo spacer ]
The colored photosensitive composition of the present invention is used in the same applications as known colored photosensitive compositions for color filters, and hereinafter, the case of using the colored photosensitive composition of the present invention as a black light spacer will be described according to specific examples of a method for forming a black light spacer using the colored photosensitive composition of the present invention.
In general, a colored photosensitive composition solution is supplied onto a substrate on which a black photo spacer is to be provided, in a film or pattern form, by a method such as coating, and the solvent is dried. Next, a pattern is formed by a method such as photolithography in which exposure and development are performed. Then, additional exposure or thermal curing treatment is performed as necessary, thereby forming a black photo spacer on the substrate.
[1] Method for supplying substrate
The colored photosensitive composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. The supply method may be performed by a conventionally known method, for example, a spin coating method, a wire bar method, a flow coating method, a dispensing coating method, a roll coating method, a spray coating method, or the like. Further, the ink may be supplied in a pattern by an ink jet method, a printing method, or the like. Among these, the use of the dispensing coating method is preferable from the comprehensive viewpoint that the amount of the coating liquid used can be significantly reduced, the coating liquid is not affected at all by mist and the like adhering during the use of the spin coating method, and the generation of impurities and the like can be suppressed.
The amount of coating varies depending on the application, and in the case of a black optical spacer, the amount is usually in the range of 0.5 to 10 μm, preferably 1 to 9 μm, and particularly preferably 1 to 7 μm in terms of the dry film thickness. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the unevenness is large, a spot defect may occur on the liquid crystal panel.
However, when the colored photosensitive composition of the present invention is used to form black spacers having different heights at a time by photolithography, the black spacers to be finally formed have different heights.
As the substrate, a known substrate such as a glass substrate can be used. In addition, the substrate surface is preferably planar.
[2] Drying method
The drying after the colored photosensitive composition solution is supplied onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Further, a reduced-pressure drying method of drying in a reduced-pressure chamber without increasing the temperature may be combined.
The drying conditions may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within a range of from 15 seconds to 5 minutes at a temperature of from 40 ℃ to 130 ℃, preferably within a range of from 30 seconds to 3 minutes at a temperature of from 50 ℃ to 110 ℃, depending on the kind of the solvent component, the performance of the dryer used, and the like.
[3] Exposure method
The exposure is performed by superimposing a negative mask pattern on the coating film of the colored photosensitive composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to the coating film of the colored photosensitive composition or a method of disposing the exposure mask at a position away from the coating film of the colored photosensitive composition and projecting exposure light through the exposure mask can be used. In addition, a scanning exposure method using a laser without using a mask pattern may be used. In this case, in order to prevent the decrease in sensitivity of the photopolymerizable layer due to oxygen, the exposure may be performed in a deoxygenated atmosphere, or after an oxygen shielding layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer, as necessary.
In a preferred embodiment of the present invention, when the black spacers having different heights are simultaneously formed by photolithography, for example, as described above, an exposure mask having a light-shielding portion (light transmittance of 0%) and an opening (intermediate transmission opening) having an average light transmittance smaller than that of an opening (full transmission opening) having the highest average light transmittance among a plurality of openings is used. In this method, a difference in residual film ratio is caused by a difference in average light transmittance (usually 5% to 40%) between the intermediate transmission opening and the full transmission opening, that is, a difference in exposure amount.
For example, a method of forming an intermediate transmission opening using a matrix-like light-shielding pattern having fine polygonal light-shielding cells is known. Further, a method of controlling light transmittance by using a film of a material such as chromium, molybdenum, tungsten, or silicon as an absorber is known.
The light source used for the exposure is not particularly limited. Examples of the light source include: a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, or a fluorescent lamp, or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium-cadmium laser, a blue-violet semiconductor laser, or a near-infrared semiconductor laser. When the optical filter is used by irradiating light of a specific wavelength, the optical filter may be used.
The optical filter may be of a type capable of controlling light transmittance at an exposure wavelength with a thin film, and examples of materials in this case include: cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), moSi, si, W, al, etc.
The exposure dose is usually 1mJ/cm 2 At least, preferably 5mJ/cm 2 More preferably 10mJ/cm or more 2 Above, and typically 300mJ/cm 2 Below, preferably 200mJ/cm 2 Below, more preferably 150mJ/cm 2 The following.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, and more preferably 75 μm or more, and is usually 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.
[4] Developing method
After the above-mentioned exposure, an image pattern can be formed on the substrate by development using an aqueous solution of a basic compound or an organic solvent. The aqueous solution may also contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; amphoteric surfactants such as alkylbetaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The method of the development treatment is not particularly limited, and the development treatment is usually carried out by a method such as immersion development, spray development, brush development, or ultrasonic development at a development temperature of 10 to 50 ℃, preferably 15 to 45 ℃.
[5] Additional exposure and thermal curing treatment
If necessary, additional exposure may be performed on the substrate after development by the same method as the above-described exposure method, or a thermosetting treatment may be performed. The heat curing conditions in this case may be selected from the range of 100 to 280 ℃, preferably from the range of 150 to 250 ℃, and the time may be selected from the range of 5 to 60 minutes.
The size, shape, etc. of the black photo spacer of the present invention are appropriately adjusted according to the specification, etc. of a color filter to which the black photo spacer is applied, and the colored photosensitive composition of the present invention is particularly useful for simultaneously forming a black photo spacer and an auxiliary spacer having different heights by photolithography, in which case the height of the spacer is usually 2 to 7 μm and the height of the auxiliary spacer is usually 0.2 to 1.5 μm lower than that of the spacer.
[ color filters ]
The color filter of the present invention is provided with the black optical spacer of the present invention as described above, and can be manufactured, for example, as follows: a black matrix, red, green, and blue pixel coloring layers, and a surface protective coating are laminated on a glass substrate as a transparent substrate, and an alignment film is formed after forming a black light spacer.
The color filter of the present invention having the black photo spacer of the present invention is bonded to a liquid crystal driving side substrate to form a liquid crystal cell, and liquid crystal is injected into the liquid crystal cell to manufacture a liquid crystal display device.
Examples
The present embodiment will be described more specifically below with reference to examples and comparative examples, but the present embodiment is not limited to the following examples as long as the gist thereof is not exceeded. In the following, "part" means "part by weight".
The components of the colored photosensitive compositions used in the following examples and comparative examples are as follows.
< adhesive resin-1 >
"ZCR-1569H" (MW = 3000-4000, acid number = about 100 mg-KOH/g) manufactured by Nippon Kagaku Kabushiki Kaisha
The binder resin-1 corresponds to the "alkali-soluble resin (a)" in the present invention.
< adhesive resin-2 >
"ZCR-1642H" (MW =5000 to 6500, acid value = about 100 mg-KOH/g) manufactured by Nippon Kabushiki Kaisha
The binder resin-2 corresponds to the "alkali-soluble resin (a)" in the present invention.
< adhesive resin-3 >
A resin obtained by reacting a reactant of an epoxy compound having the following structure (11) and acrylic acid with Trimethylolpropane (TMP) and biphenyltetracarboxylic dianhydride (BPDA) (MW =3500 to 4500, acid value = about 110 mg-KOH/g)
[ chemical formula 21]
Figure BDA0002049735360000501
The binder resin-3 can be synthesized by the following method.
< Synthesis example 1: synthesis of Binder resin-3 >
50g of the epoxy compound (epoxy equivalent 264) having the structure (11) described above, 13.65g of acrylic acid, 60.5g of methoxybutyl acetate, 0.936g of triphenylphosphine and 0.032g of p-methoxyphenol were put in a flask equipped with a thermometer, a stirrer and a cooling tube, and the reaction was carried out at 90 ℃ while stirring until the acid value reached 5mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by weight of the epoxy acrylate solution, 0.74 parts by weight of Trimethylolpropane (TMP), 3.95 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 parts by weight of tetrahydrophthalic anhydride (THPA) were charged into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ℃ while stirring to effect a reaction.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a binder resin 3 so that the solid content became 50% by weight.
The binder resin-3 corresponds to the "alkali-soluble resin (A1") "in the present invention.
< dispersant >
"DisperbYK-2000" manufactured by BYK-Chemie "
< dispersing aid >
"S12000" manufactured by Lubrizol corporation "
< surfactant >
Megafac F-475 manufactured by Dainippon ink chemical Co., ltd "
< solvent-1 >
PGMEA: propylene glycol monomethyl ether acetate
< solvent-2 >
MB: 3-Methoxybutanol
< photopolymerization initiator >
The following compounds.
[ formula 22 for reducing blood ]
Figure BDA0002049735360000511
< photopolymerizable monomer >
DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kagaku Kogyo
[ preparation of pigment Dispersion 1 to 10]
The pigment, dispersant, dispersion aid, binder resin and solvent shown in table 1 were mixed in the weight ratios shown in table 1. After mixing therein zirconia beads (average particle diameter 0.3 mm) in an amount of 80% of the volume of the dispersion vessel, the mixture was filled in a PICO MILL dispersion vessel and dispersed at a necessary Residence Time (RT) shown in Table 1 to prepare each pigment dispersion.
Figure BDA0002049735360000521
Examples 1 to 5 and comparative examples 1 to 6
The pigment dispersion liquid prepared as described above and the other components shown in table 2 were mixed and stirred at the ratio shown in table 2 to prepare a colored photosensitive composition.
Using the colored photosensitive composition, various evaluations were performed as described below, and the results are shown in table 2.
[ evaluation of height difference (. DELTA.H), adhesion, and Optical Density (OD) ]
< method for one-time formation of cured product having different heights >
Each colored photosensitive composition was applied on a glass substrate ("AN 100" manufactured by AGC company) using a spinner. Subsequently, the film was dried by heating at 110 ℃ for 70 seconds on a hot plate to form a coating film.
The obtained coating film was subjected to exposure treatment using an exposure mask having a full-transmission opening portion of a circular pattern having various diameters of 5 to 50 μm, a middle-transmission opening portion of a circular pattern having various diameters of 5 to 50 μm, and further a solid portion. The intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 10. + -. 2% at a wavelength of 365 nm. The exposure pitch (distance between mask and coated side) was 250 μm. As the irradiation light, 32mW/cm of intensity at a wavelength of 365nm was used 2 The exposure amount of the ultraviolet ray of (4) is 40 to 90mJ/cm 2 6 levels of (a). In addition, the ultraviolet irradiation is performed under air.
Then, a developer prepared from an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant ("a-60" manufactured by kao corporation) was subjected to spray development at 25 ℃ under a water pressure of 0.15MPa, and then the development was stopped with pure water, followed by washing with a water spray. The shower development time was adjusted to 10 to 120 seconds, and was set to 1.5 times the time for dissolving and removing the unexposed coating film.
By the above operation, a pattern from which an unnecessary portion is removed is obtained. The substrate on which the pattern was formed was heated in an oven at 230 ℃ for 20 minutes to cure the pattern, thereby obtaining a substantially columnar spacer pattern.
< evaluation of height Difference >
The difference in height (height difference Δ H) between the completely transmitting opening of the circular pattern having a diameter of 15 μm and the middle transmitting opening of the circular pattern having a diameter of 35 μm was calculated, and the exposure amount was determined to be 40 to 90mJ/cm 2 The value of Δ H was also evaluated according to the following criteria, together with the following maximum values.
(evaluation criteria of height Difference Δ H)
0.5 μm or more: o-
0.3 μm or more and less than 0.5 μm: delta
Less than 0.3 μm: is prepared from
< evaluation of substrate adhesion >
The exposure dose, which maximizes the difference in height (. DELTA.H), is shown in Table 2, with the smallest opening diameter (. Mu.m) remaining with good pattern definition in the completely transmitting opening of the circular pattern of 5 to 50 μm and the same intermediate transmitting opening of 5 to 50 μm as the smallest adhesion. The smaller the value, the more excellent the substrate adhesion. In addition, the remaining with good sharpness means: 24 patterns of the same size were formed, all of which were normally formed.
< evaluation of Optical Density (OD) >
The Optical Density (OD) of the solid portion was measured by a transmission densitometer ("D200-II" manufactured by Gretag macbeth). The film thickness at the measurement site was also measured, and the optical density per unit film thickness (unit OD) was calculated and evaluated according to the following criteria. The OD value is a numerical value indicating light-shielding ability, and the larger the numerical value, the higher the light-shielding property.
(evaluation criteria of Unit OD)
0.8 or more: circle for making
Less than 0.8: is made from
[ evaluation of Voltage Holding Ratio (VHR) ]
< fabrication of liquid Crystal cell >
An electrode substrate a (glass ITO entity for EHC production and evaluation) in which an ITO film was formed on the entire surface of a 5cm square single surface and an electrode substrate B (glass SZ-B111MIN (B) for EHC production and evaluation) in which an extraction electrode (extraction 12426759.
Each colored photosensitive composition was coated on an electrode substrate A, dried in vacuum for 1 minute, and then prebaked on a hot plate at 90 ℃ for 1.5 minutes to obtain a coating film having a dry film thickness of 2.0. Mu.m. Then, the outer peripheral portion was masked by 2mm, and a 3kW high pressure mercury lamp was used at 50mJ/cm 2 The image exposure is performed under the exposure conditions of (1). Next, a developer prepared from an aqueous solution containing about 0.06% by weight of potassium hydroxide and about 0.14% by weight of a nonionic surfactant ("a-60" manufactured by kao corporation) was subjected to spray development at 25 ℃ under a water pressure of 0.15MPa, and then the development was stopped with pure water, followed by washing with a water spray. The shower development time was adjusted to 10 to 120 seconds, and was set to about 1.5 times the time (off time) for dissolving and removing the non-photosensitive layer.
The electrode substrate on which the image was formed was baked at 230 ℃ for 20 minutes, and then a resist-coated electrode substrate (resist substrate) was obtained. Then, the polyimide solution was coated on a resist substrate, and prebaked at 70 ℃ for 2 minutes and postbaked at 220 ℃ for 24 minutes on a hot plate. The resist substrate thus obtained was cut into a 2.5cm square substrate, thereby completing an electrode substrate a for evaluation.
On the other hand, the electrode substrate B was also coated with a polyimide solution, and prebaked on a hot plate at 70 ℃ for 2 minutes and after-baked at 220 ℃ for 24 minutes, thereby completing the evaluation of the electrode substrate B.
Then, an epoxy resin-based sealant containing silica beads having a diameter of 5 μm was applied to the outer periphery of the electrode substrate B using a dispenser, and the applied surface of the electrode substrate a for evaluation was attached to the surface side (sealant side) of the electrode substrate B in a pressure-bonded state, thereby completing an empty cell. Heating in a hot air circulating furnace at 180 deg.C for 2 hr.
The empty cell thus obtained was filled with a liquid crystal (MLC-6608 manufactured by Merck Japan) and the peripheral portion was sealed with a UV curable sealant, thereby completing a liquid crystal cell for voltage holding ratio measurement.
< evaluation of Voltage Holding Ratio (VHR) >
After the liquid crystal cell was annealed (heated at 105 ℃ C. For 2.5 hours in a hot air circulating furnace), a voltage of 5V was applied to the electrode substrates A and B for evaluation under conditions of 0.6Hz and a frame time of 1667msec, and the voltage holding ratio was measured by "VHR-6254" manufactured by Toyang Technica.
Figure BDA0002049735360000561
From the results of table 2, it can be seen that: the colored photosensitive composition of the present invention containing Or64 and B60 as essential components as pigments and the colored photosensitive composition of the present invention containing Or72 and B60 as essential components as pigments are useful for simultaneously forming cured products having different heights and maintaining light-shielding properties, adhesiveness and voltage holding ratio with the same material.
The present invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present application is based on japanese patent application (japanese patent application 2012-018337) filed on 31/1/2012, the contents of which are incorporated herein by reference.

Claims (10)

1. A colored photosensitive composition comprising a pigment, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the pigment comprises a pigment represented by the following formula (A) and a pigment represented by the following formula (B), and further comprises C.I. pigment Violet 23,
the content of the pigment in the colored photosensitive composition is 5 to 50% by weight based on the total solid content,
the total ratio of the pigment (A) and the pigment (B) to the C.I. pigment Violet 23 in the total pigment of the colored photosensitive composition is 70% by weight or more,
the content of the pigment (A) is 25 to 70% by weight based on 100% by weight of the total of the pigment (A) and the pigment (B),
(A) One selected from the group consisting of c.i. pigment orange 43, c.i. pigment orange 64 and c.i. pigment orange 72,
(B) C.i. pigment blue 60.
2. The colored photosensitive composition according to claim 1, wherein the pigment contains c.i. pigment orange 64, c.i. pigment blue 60, and c.i. pigment violet 23.
3. The colored photosensitive composition according to claim 1 or 2, wherein the pigment further contains one selected from the group consisting of c.i. pigment red 254 and c.i. pigment violet 29.
4. The colored photosensitive composition according to claim 1 or 2, wherein the photopolymerization initiator is an oxime ester compound.
5. The colored photosensitive composition according to claim 1 or 2, further comprising a pigment dispersant.
6. The colored photosensitive composition according to claim 5, wherein the pigment dispersant is a polymer dispersant.
7. A black photo spacer formed by using the colored photosensitive composition according to any one of claims 1 to 6.
8. The black optical spacer of claim 7, having different heights.
9. A color filter comprising the black photo spacer according to claim 7 or 8.
10. A liquid crystal display device comprising the color filter according to claim 9.
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JP2017033023A (en) 2017-02-09
JP6409936B2 (en) 2018-10-24
CN104081280B (en) 2019-05-31
KR101985564B1 (en) 2019-06-03
WO2013115268A1 (en) 2013-08-08
JP6229210B2 (en) 2017-11-15
KR20140121824A (en) 2014-10-16
JP2018009194A (en) 2018-01-18
KR20190058671A (en) 2019-05-29
KR102078989B1 (en) 2020-02-19
TWI585529B (en) 2017-06-01
JP6036708B2 (en) 2016-11-30
JPWO2013115268A1 (en) 2015-05-11

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