TW201307405A - Resin composition for image formation purposes which can be used in inkjet method, and display element - Google Patents

Abstract

Provided is a resin composition for image formation purposes, which enables the production of a color filter by an inkjet method without requiring the use of any bank or matrix. A resin composition for image formation purposes, which can be printed in a dot-like or stripe-like pattern on a transparent substrate by an inkjet method. The resin composition comprises at least a fluorinated component, a photopolymerizable component and a photopolymerization initiator, additionally contains a component having a boiling point of 200 DEG C or higher in an amount of 90 wt% or more relative to the total amount of the composition, and is characterized in that a cured film produced using the resin composition has a static contact angle (?) of 35 DEG or greater with respect to another ink that comprises at least a photopolymerizable component and a photopolymerization initiator and additionally contains a component having a boiling point of 200 DEG C or higher in an amount of 90 wt% or more.

Description

Resin composition and display element for image formation used in an inkjet method

The present invention relates to a resin composition which can be used for an image forming film which is formed in a dot shape or a stripe shape by an ink jet method on a transparent substrate, and a cured film using the resin composition as a material for image formation.

In the case of electronic media that replaces paper, the development of display devices such as electronic paper is prevailing. For a CRT or a liquid crystal display of a conventional display, a reflective display method using a display medium composed of white particles or black particles or the like is mainly used for electronic paper, etc., and must have a high white reflectance or a high contrast ratio. . Still, it is sought to have a memory effect on a display image, or can be driven at a low voltage, further thin and light, inexpensive, and the like. Further, in recent years, in terms of display characteristics, of course, white reflectance and contrast ratio which are homogenous to paper are sought, and at the same time, full-color display is expected.

For example, in Patent Literatures 1, 2, and 3, a reflective display device in which an applied mode is used to arbitrarily switch between charged particles and a black state in a black state is provided with a color filter and can be displayed in color. technology. However, any of the so-called color filters can be used as a conventional color filter used in a liquid crystal display device or the like, and has a black matrix which is a light-shielding portion or a partition wall of a specific pixel region. The problem of reflected light loss and brightness due to scattering of charged particles.

Further, Patent Document 4 describes that a color filter having no black matrix is applied to a reflective display device. However, this patent document 4 In the middle, a resist material of a certain color is applied to the support substrate on which the color filter is formed, and after drying, the exposure is performed by using an exposure machine, and the image is developed by an alkali developing solution to form a colored region, and then the color points are repeated. The manufacture of color filters, that is, the so-called photo-micro-etching method, is complicated, and the cost is unfavorable, and the problem of wasteful use of the resist material still exists.

In the manufacture of a color filter using an inkjet method which is well known, such as a liquid crystal display device, as in Patent Documents 5, 6 and 7, an ink composition of red, blue, and green is applied to a region constituting a pixel. The substance is hardened to form a colored coating film. In this case, in order to accurately form and accurately form the colored coating film, a spacer or the like is provided in advance by a photo-extrusion etching step, and the ink composition of each color is simultaneously applied to the region formed thereby, Compared with the aforementioned photolithography etching method, the cost can be cut off, and the waste of the ink composition can be eliminated.

Further, in Patent Document 8, a method of forming a color coating film on a plurality of colored regions without providing a partition has been proposed, but this technique forms a black matrix instead of a partition wall on the support substrate. The ink composition is applied to the area to be dispensed.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2003-161964

[Patent Document 2] JP-A-2004-361514

[Patent Document 3] JP-A-2008-83536

[Patent Document 4] JP-A-2006-267831

[Patent Document 5] JP-A-59-75205

[Patent Document 6] JP-A-2001-350012

[Patent Document 7] JP-A-H11-281815

[Patent Document 8] JP-A-2010-54777

[Summary of the Invention]

As described above, when the color filter is manufactured by the ink jet method, many advantages are obtained, but in the conventional method, it is necessary to additionally form a bank or a black matrix. In general, a partition wall or the like is formed by photolithography, and a color filter cannot be produced by a full ink jet method, thereby offsetting the advantage of low cost of ink jet or simple process. Moreover, there arises a problem that the brightness of the partition walls or the matrix is lowered.

Further, the spacer ink or the matrix is not formed, and the colored ink is ejected by the inkjet method directly on the transparent substrate. Generally, the color mixing problem caused by the superposition of the plurality of colored coating films formed is caused, and it is difficult to form the color filter.

The present invention has been made in view of the above-described state of the art, and it is an object of the invention to provide an image forming resin composition which can produce a color filter by an inkjet method without requiring a partition or a matrix. Thereby, for example, a reflective display device for monochrome display such as electronic paper can display color in an inexpensive and simple manner without lowering the brightness.

The present inventors have made various studies to solve the above problems. In the case where a specific gap region is provided on the transparent substrate, the resin composition for image formation of the present invention is printed, and ultraviolet rays are irradiated to obtain a cured film. Then, other ink is discharged to the gap region, and the ink is not impeded. The partition walls or the matrix can also prevent the problem of color mixing or the like due to the overlapping of the obtained coating films, and the present invention is finally completed.

In other words, the resin composition for image formation of the present invention is a resin composition for image formation which can be printed in a dot shape or a stripe shape by an ink jet method on a transparent substrate, and is characterized in that it contains at least a fluorine-containing component and light. The polymerizable component and the photopolymerization initiator contain 90% by weight or more of the component having a boiling point of 200 ° C or more in the entire composition, and the cured film produced by using the resin composition for image formation contains at least photopolymerizability. The component exhibits a static contact angle θ of 35° or more with a photopolymerization initiator and other inks having a boiling point of 200° C. or higher and 90% by weight or more.

The present invention relates to a resin composition for image formation which can be printed in a dot shape or a stripe shape on a transparent substrate, and contains at least a fluorine-containing component, a photopolymerizable component, and a photopolymerization initiator. Here, the fluorine-containing component contained in the resin composition for image formation is preferably a copolymer composed of a structure represented by the following formula (1);

(wherein R ¹ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a chlorine, X represents a divalent organic group having 1 to 6 carbon atoms, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms; Y is a divalent group and has a residue of a monomer capable of copolymerizing an unsaturated group).

The molecular weight of the copolymer having the structure represented by the above formula (1) is preferably from 3,000 to 100,000. When it is less than 3,000, the liquid repellency is not exhibited, and the compatibility with the resin composition for image formation of 100,000 or more is not suitable. In addition, it is preferable to use a fluorine-containing monomer component represented by the following formula (2) in order to form a copolymer having a structure represented by the formula (1) and a monomer having a fluorine-containing component.

CH ₂ =C(R ¹ )COOXR ^f (2)

(wherein R ¹ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a chlorine, X represents a divalent organic group having 1 to 6 carbon atoms, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms).

In other words, the fluorine-containing component in the resin composition for image formation is preferably a (meth) acrylate unit containing a fluorine-containing perfluoroalkyl group R ^f or an α-chloro acrylate unit containing R ^f as a main component. Copolymers of known (meth) acrylate units are used.

Examples of the monomer represented by the above formula (2) include CH ₂ =CH(R ¹ )COOR ² R ^f , CH ₂ =CH(R ¹ )COOR ² NR ³ SO ₂ R ^f , and CH ₂ =. CH(R ¹ )COOR ² NR ³ COR ^f , CH ₂ =CH(R ¹ )COOCH ₂ CH(OH)R ⁴ R ^f and the like. Here, R ² represents an alkylene group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms. Specific examples of R ² include, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH ₂ -, -CH(CH ₂ CH(( CH ₃ ) ₂ )-etc. Further, specific examples of R ³ include, for example, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH _{3 ,} and the like. Further, specific examples of R ⁴ include, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, and the like. The X in the above formula (1) is easy to obtain, and is preferably an alkylene group having 2 to 4 carbon atoms. The single system represented by the above formula (1) may be used singly or in combination of two or more. By R ^f being a linear or branched perfluoroalkyl group having a carbon number of 4 to 6, or [(CF ₃ ) ₂ CF] ₂ C=C(CF ₃ )-, or (CF ₃ ) ₂ C=C(CF ₂ CF ₃ )-, the fluorine-based compound is excellent in compatibility with other components of the resin composition for image formation of the present invention, and a fluorine-based compound is formed when a resin composition for image formation is formed to form a coating film. There is no agglutination between.

A known (meth) acrylate which is copolymerized with a fluorine-containing unit can be used. Specific examples of such (meth) acrylate include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, 3-pentyl (meth)acrylate, hexyl (meth)acrylate, Octyl methacrylate, hexadecyl (meth) acrylate, 2,2-dimethyl propyl (meth) acrylate, 1-ethyl propyl (meth) acrylate, (meth) acrylate ring Hexyl ester, phenyl (meth) acrylate, (methyl Benzyl acrylate, 2-tert-butylphenyl (meth)acrylate, 2-naphthyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-(meth)acrylate Methoxypropyl ester, 3-methoxybutyl (meth)acrylate, 4-methoxyphenyl (meth)acrylate, 2-methoxycarbonylphenyl (meth)acrylate, (methyl) ) 3-ethoxypropyl acrylate, 2-ethoxycarbonylphenyl (meth)acrylate, 2-ethoxymethyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 2-ethoxycarbonylphenyl (meth)acrylate, 4-butoxycarbonylphenyl (meth)acrylate, 2-chlorophenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, 4-cyanoethyl (meth)acrylate, 2-cyanobenzyl (meth)acrylate, 4-cyanophenyl (meth)acrylate, 4-cyano-3-thiabutyl (meth)acrylate , (meth)acrylic acid 6-cyano-3-thiahexyl ester, 3-thiobutyl (meth)acrylate, 4-thylhexyl (meth)acrylate, 3-thiopentyl (meth)acrylate, ( Methyl)p-toluene acrylate, isobornyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, tetrahydrofuran (meth)acrylate Methyl ester, glycidyl (meth)acrylate, methoxytriethylene (meth)acrylate, ethyl carbitol (meth)acrylate, dihydroxycyclopentaethyl (meth)acrylate, (meth)acrylic acid behenate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, tert-butylaminoethyl (meth)acrylate, ( Dicyclopentenyl (meth)acrylate, dicyclopenteneoxyethyl (meth)acrylate, and the like.

The fluorine-containing component contained in the resin composition for image formation of the present invention is preferably used for suppressing overlap with a coating film produced by another ink, and is preferably a solid content component in the resin composition for image formation. The amount of the total solid content in the resin composition for image formation is preferably 0.05 to 2% by weight, preferably 0.05 to 10% by weight. If it exceeds 10% by weight, it may cause contamination of the ink jet nozzle or contamination of the transparent substrate, or the fluorine-containing system may be analyzed. On the other hand, if it is less than 0.05% by weight, the ink repellency of the surface of the cured film obtained after the ultraviolet ray irradiation becomes insufficient, and the overlap of the coating film by the other ink formed by the subsequent printing becomes remarkable, in particular, for formation. It is difficult to make the static contact angle θ _k 35° or more when the cured film is formed by printing with another ink.

Further, the resin composition for image formation of the present invention and the photopolymerizable component contained in the other ink may be a polyfunctional monomer, and preferably, for example, a liquid polyfunctional acrylic monomer. More preferably, the ink jet discharges an easily low-viscosity bifunctional to trifunctional polyfunctional acrylic monomer. The functional group may, for example, be an acryloxy group, a methacryloxy group or an allyl group, but it is of course also possible to use it. Specific examples of the ultraviolet curing component include 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-butanediol diacrylate, and ethylene glycol dimethacrylate. , neopentyl glycol diacrylate, trimethylolpropane triacrylate, 1,3-butylene glycol dimethacrylate, and the like. Further, in addition to these, photocurability can be improved, and a tetrafunctional or higher polyfunctional acrylic monomer or oligomer can be added. For example, a trifunctional or tetrafunctional acrylate having a pentaerythritol as a skeleton, or a methacrylate, a bifunctional or a hexafunctional acrylate having dipentaerythritol as a skeleton may be mentioned. Or methacrylate or the like. Further, the photopolymerizable component may be different from those of other inks, but may be formed on a transparent substrate by using a coating film (cured film) for forming a uniform image. The same.

Further, the content of the photoinitiator component is preferably 1 to 10% by weight based on the total solid content of the resin composition for image formation and the other inks. If it is less than 1% by weight, the hardening becomes insufficient, and if it is more than 10% by weight, the strength after hardening is insufficient, which is not preferable.

Further, the resin composition for image formation of the present invention and the photopolymerization initiator-based binder or polyfunctional monomer contained in the other ink are different in reaction form (for example, radical polymerization or cationic polymerization). It is appropriately selected in consideration of the kind of each material, but for example, 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2 -Methyl-1-propan-1-one, 2,4,6-trimethylbenzimidyldiphenyl-phosphorus oxide, bis-indolylphosphine oxide, benzoin ethyl ether, benzoin isobutylene Ether, benzoin isopropyl ether, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2-(3-dimethylamino-2-hydroxypropoxy -3,4-Dimethyl-9H-thiaxanthone-9-one m-chloro, benzophenone, methyl phthalic acid benzoate, 4-benzylidene-4'-methyl -diphenyl sulfide, 3,3',4,4'-tetra (t-butylperoxycarbonyl), p-di Of ethyl amine group, a - dimethylamino benzoic acid isoamyl ester, 1,3,5-hexahydro-yl Bing Xixi -s- triazine, 2- [2- ( 5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6 a photopolymerization initiator such as bis(trichloromethyl)-s-triazine, methyl benzhydrylcarboxylate or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

The content of the resin composition for image formation and the photopolymerization initiator in the other inks is preferably 2 to 30% by weight, and preferably 5 to 20% by weight, based on the total solid content. When the photopolymerization initiator content is less than 2% by weight based on the total amount of the solid content, and the resin composition for image formation and other inks are applied to the transparent substrate to be cured, the coating film may be obtained ( The properties of the coating film such as coating film hardness and chemical resistance of the cured film are insufficient. On the other hand, when it is more than 30% by weight, when the resin composition for image formation and other inks are applied to a transparent substrate and cured, the coating film (cured film) is inferior in adhesion to the transparent substrate. In addition, the photopolymerization initiator may be different from the photopolymerizable component, and the resin composition for image formation may be different from those of other inks, but a uniform coating film (cured film) may be formed on the transparent substrate. On the same, should use the same.

The resin composition for image formation and other ink-based blending solvents are all excellent in ejecting from inkjet, and it is preferable to use a component having low volatility, and in particular, to obtain good ink jet discharge property. The component having a boiling point of 200 ° C or higher is 90% by weight or more. When the component having a boiling point of 200 ° C or more is less than 90% by weight, the discharge property of the ink jet becomes unstable, and the drawing cannot be performed satisfactorily, and a continuous uniform pattern cannot be obtained.

For the solvent having a boiling point of 200 ° C or more, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate; diethylene glycol monomethyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether; diethylene glycol monoalkyl ether acetates such as diethylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl Propylene glycol monoalkyl ether acetates such as phenyl ether acetate, propylene glycol monoethyl ether acetate, other ethers such as diethylene glycol dimethyl ether, and high boiling point solvents such as γ-butyrolactone Wait.

Further, the resin composition for image formation and the other ink systems are each intended to have a film forming property, and a binder may be added in a viscosity range in which inkjet discharge is possible. In the case of the binder, either a resin having no polymerization property itself or a resin having polymerization reactivity itself may be used, and two or more kinds of binders may be used in combination.

In order to apply a coloring coating film to a coating film (cured film) obtained from a resin composition for image formation and other inks, and to mix a coloring agent, any one of an organic coloring agent and an inorganic coloring agent can be selected. use. Among them, as the organic colorant, for example, a dye, an organic pigment, a natural pigment, or the like can be used. Further, as the inorganic colorant, for example, an inorganic pigment, an extender pigment or the like can be used. Among these, the organic pigment is preferably used because it has high color developability and high heat resistance. The organic pigment may, for example, be a compound which is classified into a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), and is specifically given the following color index (C.I.) number.

That is, CIPIGMENT YELLOW 1, CIPIGMENT YELLOW 3, CIPIGMENT YELLOW 12, CIPIGMENT YELLOW 13, CIPIGMENT YELLOW 14, CIPIGMENT YELLOW 15, CIPIGMENT YELLOW 16, CIPIGMENT YELLOW 17, CIPIGMENT YELLOW 20, CIPIGMENT YELLOW 24, CIPIGMENT YELLOW 31, CIPIGMENT YELLOW 55, CIPIGMENT YELLOW 60, CIPIGMENT YELLOW 61, CIPIGMENT YELLOW 65, CIPIGMENT YELLOW 71, CIPIGMENT YELLOW 73, CIPIGMENT YELLOW 74, CIPIGMENT YELLOW 81, CIPIGMENT YELLOW 83, CIPIGMENT YELLOW 93, CIPIGMENT YELLOW 95, CIPIGMENT YELLOW 97, CIPIGMENT YELLOW 98, CIPIGMENT YELLOW 100, CIPIGMENT YELLOW 101, CIPIGMENT YELLOW 104, CIPIGMENT YELLOW 106, CIPIGMENT YELLOW 108, CIPIGMENT YELLOW 109, CIPIGMENT YELLOW 110, CIPIGMENT YELLOW 113, CIPIGMENT YELLOW 114, CIPIGMENT YELLOW 116, CIPIGMENT YELLOW 117, CIPIGMENT YELLOW 119, CIPIGMENT YELLOW 120, CIPIGMENT YELLOW 126, CIPIGMENT YELLOW 127, CIPIGMENT YELLOW 128, CIPIGMENT YELLOW 129, CIPIGMENT YELLOW 138, CIPIGMENT YELLOW 139, CIPIGMENT YELLOW 150, CIPIGMENT YELLOW 151, CIPIGMENT YELLOW 152, CIPIGMENT YELLOW 153, CIPIGMENT YELLOW 154, CIPIGMENT YELLOW 155, CIPIGMENT YELLOW 156, C. I.PIGMENT YELLOW 166, C.I.PIGMENT YELLOW 168, C.I.PIGMENT YELLOW 175; C.I.PIGMENT ORANGE 1, C.I.PIGMENT ORANGE 5, C.I.PIGMENT ORANGE 13, C.I.PIGMENT ORANGE 14 CIPIGMENT ORANGE 16, CIPIGMENT ORANGE 17, CIPIGMENT ORANGE 24, CIPIGMENT ORANGE 34, CIPIGMENT ORANGE 36, CIPIGMENT ORANGE 38, CIPIGMENT ORANGE 40, CIPIGMENT ORANGE 43, CIPIGMENT ORANGE 46, CIPIGMENT ORANGE 49 , CIPIGMENT ORANGE 51, CIPIGMENT ORANGE 61, CIPIGMENT ORANGE 63, CIPIGMENT ORANGE 64, CIPIGMENT ORANGE 71, CIPIGMENT ORANGE 73; CIPIGMENT VIOLET 1, CIPIGMENT VIOLET 19, CIPIGMENT VIOLET 23, CIPIGMENT VIOLET 29 , CIPIGMENT VIOLET 32, CIPIGMENT VIOLET 36, CIPIGMENT VIOLET 38; CIPIGMENT RED 1, CIPIGMENT RED 2, CIPIGMENT RED 3, CIPIGMENT RED 4, CIPIGMENT RED 5, CIPIGMENT RED 6, CIPIGMENT RED 7 , CIPIGMENT RED 8, CIPIGMENT RED 9, CIPIGMENT RED 10, CIPIGMENT RED 11, CIPIGMENT RED 12, CIPIGMENT RED 14, CIPIGMENT RED 15, CIPIGMENT RED 16, CIPIGMENT RED 17, CIPIGMENT RED 18 , CIPIGMENT RED 19, CIPIGMENT RED 21, CIPIGMENT RED 22, CIPIGMENT RED 23, CIPIGMENT RE D 30, C.I.PIGMENT RED 31, C.I.PIGMENT RED 32, CIPIGMENT RED 37, CIPIGMENT RED 38, CIPIGMENT RED 40, CIPIGMENT RED 41, CIPIGMENT RED 42, CIPIGMENT RED 48:1, CIPIGMENT RED 48:2, CIPIGMENT RED 48:3, CIPIGMENT RED 48 : 4, CIPIGMENT RED 49:1, CIPIGMENT RED 49:2, CIPIGMENT RED 50:1, CIPIGMENT RED 52:1, CIPIGMENT RED 53:1, CIPIGMENT RED 57, CIPIGMENT RED 57:1 CIPIGMENT RED 57:2, CIPIGMENT RED 58:2, CIPIGMENT RED 58:4, CIPIGMENT RED 60:1, CIPIGMENT RED 63:1, CIPIGMENT RED 63:2, CIPIGMENT RED 64:1, CI PIGMENT RED 81:1, CIPIGMENT RED 83, CIPIGMENT RED 88, CIPIGMENT RED 90:1, CIPIGMENT RED 97, CIPIGMENT RED 101, CIPIGMENT RED 102, CIPIGMENT RED 104, CIPIGMENT RED 105, CIPIGMENT RED 106, CIPIGMENT RED 108, CIPIGMENT RED 112, CIPIGMENT RED 113, CIPIGMENT RED 114, CIPIGMENT RED 122, CIPIGMENT RED 123, CIPIGMENT RED 144, CIPIGMENT RED 146, CIPIGMENT RED 149, CIPIGMENT RED 150, CIPI GMENT RED 151, C.I.PIGMENT RED 166, C.I.PIGMENT RED 168, C.I.PIGMENT RED 170, C.I.PIGMENT RED 171, CIPIGMENT RED 172, CIPIGMENT RED 174, CIPIGMENT RED 175, CIPIGMENT RED 176, CIPIGMENT RED 177, CIPIGMENT RED 178, CIPIGMENT RED 179, CIPIGMENT RED 180, CIPIGMENT RED 185, CIPIGMENT RED 187, CIPIGMENT RED 188, CIPIGMENT RED 190, CIPIGMENT RED 193, CIPIGMENT RED 194, CIPIGMENT RED 202, CIPIGMENT RED 206, CIPIGMENT RED 207, CIPIGMENT RED 208, CIPIGMENT RED 209, CIPIGMENT RED 215, CIPIGMENT RED 216, CIPIGMENT RED 220, CIPIGMENT RED 224, CIPIGMENT RED 226, CIPIGMENT RED 242, CIPIGMENT RED 243, CIPIGMENT RED 245, CIPIGMENT RED 254, CIPIGMENT RED 255, CIPIGMENT RED 264, CIPIGMENT RED 265; CIPIGMENT BLUE 15, CIPIGMENT BLUE 15:3, CIPIGMENT BLUE 15:4, CIPIGMENT BLUE 15:6, CIPIGMENT BLUE 60; CIPIGMENT GREEN 7, CIPIGMENT GREEN 36; CIPIGMENT BROWN 23 , CIPIGMENT BROWN 25; CIPIGMENT BLACK 1, PIGMENT BLACK 7, and so on.

Further, specific examples of the inorganic pigment or the extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, and iron oxide. Red (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, and the like. In addition, the coloring agent which is blended in the resin composition for image formation and the other inks may be used alone or in combination of two or more.

The coloring agent is preferably a clogging nozzle or the like by an inkjet method, and is preferably used in a polymer dispersing agent and particles having a particle diameter of 100 nm or less which are micronized and dispersed. That is, the dispersing agent is blended as needed to allow the colorant to be well dispersed. For example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, a polyfluorene-based or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) exemplified below is preferable. That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl Polyoxyethylene alkylphenyl ethers such as ether; polyethylene glycol diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modification A polymeric surfactant such as a polyester or a tertiary amine modified polyurethane.

The content in the case where the coloring agent is blended is generally a coloring agent in an amount of from 1 to 60% by weight, preferably from 5 to 40% by weight, based on the total amount of the solid content of the resin composition for image formation or other inks. When the blending ratio of the coloring agent is less than 1% by weight based on the total amount of the solid content, it is feared that the resin composition for image formation is applied to a specific film thickness (generally about 0.1 to 2.0 μm). . On the other hand, when it is more than 60% by weight, when the resin composition for image formation or the like is applied onto a transparent substrate and is cured, the adhesion of the colored coating film to the transparent substrate is poor, and the coating film of the coating film hardness or the like is feared. Characteristic not full.

In order to obtain a resin composition for image formation or another ink system, the above-mentioned basic components are mixed, and if necessary, a reactive diluent which is a surface tension adjusting agent or a low viscosity is mixed, and is prepared to have a continuous discharge property. The characteristic value is used as an ink for inkjet. The ink jet heads generally used are those obtained by piezoelectric elements. Therefore, the viscosity is 5~30mPa in the nozzle temperature of 20~45°C. Sec, the surface tension is suitably 20 to 40 N/m. In addition, the resin composition for image formation of the present invention is required to contain a fluorine-containing component, a photopolymerizable component, and a photopolymerization initiator, and a cured film comprising an ink having a boiling point of 200 ° C or more and 90% by weight or more. The static contact angle θ _K is 35° or more, preferably 40° or more. In order to make the static contact angle 35 or more, it is possible to surely prevent the color mixture caused by the overlap of the coating films.

In addition, the transparent substrate used for the production of the color filter using the resin composition for image formation of the present invention is not particularly limited as long as it is permeable to light, but is used, for example, in a liquid crystal display or the like. The glass system is basically preferably a transparent plastic sheet or film having a transmittance of 90% or more of acrylic acid, PET, PC, polyolefin, or the like used in electronic paper or the like.

In order to manufacture a color filter having a uniform coating film (cured film) on the surface, the transparent substrate is surface-treated in advance, and the contact angle of the resin composition to the transparent substrate is adjusted. Since the other ink or the image forming resin composition discharged from the transparent substrate by the inkjet method is liquid, the degree of wetting and spreading is changed by the surface tension and the surface tension of the transparent substrate. Therefore, it is preferable to surface-treat a transparent substrate or the like as needed.

In particular, the resin composition for image formation of the present invention applied in a state in which no adjacent cured film is applied is preferably such that the contact angle θ _L with respect to the transparent substrate is 3° or more. If the contact angle is lower than this, the droplets on the transparent substrate are too wetted and spread, and it is impossible to control the formation of a specific coating film (hardened film). Further, when a linear cured film is formed by using the resin composition for image formation of the present invention, the upper limit of the contact angle θ _{L is} suitably 25°. When the contact angle θ _L exceeds 25°, for example, the droplets of the resin composition for image formation discharged from the nozzle are continuously linearly arranged to draw a straight line, and the droplets that are firstly bounced on the transparent substrate are thereafter The discharged droplets are absorbed and the droplets are concentrated at specific locations, which may result in a non-uniform wetting spread of so-called bulge droplets.

In addition, in recent years, small-sized high-illuminance ultraviolet ray irradiators using UV-LED lamps have been commercially available (for example, Omron, Nichia Chemical Co., Ltd.), and have been painted with these, and then irradiated with ultraviolet rays to be formed on a transparent substrate. The shape of the cured film is confirmed to be effective in, for example, embossing or the like.

In addition, in the state in which the cured film composed of the resin composition for image formation of the present invention is formed in an adjacent region, the other ink is ejected onto the transparent substrate, and the contact angle θ _{L of the} transparent substrate is buried. The gap into the hardened film is not limited by its contact angle. When the wetting extension is emphasized, the contact angle θ _L is preferably 25° or less.

The surface treatment method of the transparent substrate depends on the type of the transparent substrate, and a suitable known means can be used. For example, in addition to the atmospheric piezoelectric slurry method, the corona discharge, and the ultraviolet treatment, a fluorine-based ink-repellent agent or a treatment using a decane coupling agent may be applied in advance.

When the resin composition for forming an image formed on a transparent substrate or another ink is cured to form a coating film (cured film), the sensitivity is determined depending on the sensitivity of the resin composition for image formation, etc. It is about 200 mJ/cm ² or more, preferably 500 mJ/cm ² or more. In the ultraviolet irradiation, an inkjet device including a stepped substrate on which a transparent substrate is placed is used, and the discharge of the resin composition for image formation or the like is performed on the same stage as the ultraviolet irradiation, and the movement of the support substrate between the steps is performed. It becomes unnecessary, and color filters can be efficiently manufactured.

Further, after all the coating films (cured films) are formed on the transparent substrate, sufficient ultraviolet rays may be irradiated. The amount of ultraviolet irradiation at this time is preferably 1000 mJ/cm ² or more, but the degree of hardening depends on the type of the resin composition for image formation or the illuminance/output wavelength of the ultraviolet ray irradiator, and therefore it is generally suitable for the amount of exposure. The volume ratio dependence is less than the exposure amount. Further, unlike the ultraviolet curing, heat treatment at a temperature of about 80 ° C to 160 ° C is added, and the durability as a color filter can be further improved.

In order to produce a color filter by the inkjet method using the resin composition for image formation of the present invention, first, the resin composition for image formation of the present invention is used to print dots at specific intervals in the scanning direction of the inkjet head. Alternatively, the lines are printed at a specific interval in parallel with the scanning direction of the inkjet head (primary printing), and the ultraviolet rays are irradiated to form a specific gap region on the transparent substrate to form a cured film. Then, other inks (secondary printing) are printed on the gap regions, and the coating film is cured by irradiation with ultraviolet rays, and there is no problem of color mixing caused by overlapping with the cured film formed previously, so that it is like a conventional method. Color filter can be produced without the formation of partition walls or matrices sheet.

After the cured resin film is formed by using the resin composition for image formation of the present invention, secondly, other ink is discharged from the gap region formed by the cured film, and several types of coating films are formed on the transparent substrate, as in the conventional method. A black matrix or a partition wall which is necessary for the photolithography etching process is not formed, and a color filter can be manufactured by an inkjet method by preventing color mixture due to overlapping of coating films. Therefore, the problem of brightness reduction caused by the partition walls or the matrix can be solved, and at the same time, the advantages of cost reduction or simple process can be obtained.

The color filter obtained in this manner is suitable for a panel of a black matrix which does not require the light shielding purpose of the TFT element, for example, a reflective display device such as an E-ink type electronic paper, which can provide brightness and color purity. Excellent color display components. Further, the resin composition for image formation of the present invention is not limited to the use of a color filter obtained by an inkjet method. In addition to the color filter, it is generally applicable to the case where a plurality of regions of a specific pattern are formed by inkjet printing.

[Formation for implementing the invention]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

[Examples] <Production of Ink Composition A~K>

As shown in Table 1, first, a color filter was used to coexist a polymer dispersant with diethylene glycol monoethyl ether acetate or propylene glycol monomethyl ether acetate as a solvent. Dispersion was carried out in a bead mill to prepare red, green, blue, and white dispersions. The dispersion was mixed according to the composition shown in Table 1, and subjected to pressure filtration by a 1 μm microfilter to prepare colored inkjet inks (ink compositions) of respective colors.

Further, the meaning of the abbreviation in Table 1 is as follows.

[a] Fluorine-containing liquid repellent (manufactured by Dakin Industries, Inc., trade name: Optool DAC)

[b1] 芴-type epoxy acrylate/anhydride polymerization adduct (V259-ME, manufactured by Nippon Steel Chemical Co., Ltd. Boiling point: cannot be confirmed under atmospheric pressure. 3 or more functional groups)

[b2] A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA boiling point manufactured by Nippon Kayaku Co., Ltd.: cannot be confirmed under atmospheric pressure).

[b3] Pentaerythritol triacrylate (PET-30 boiling point manufactured by Nippon Kayaku Co., Ltd.: cannot be confirmed under atmospheric pressure.)

[b4] Trimethylolpropane triacrylate (SR351S boiling point manufactured by Sartomer Co., Ltd.: cannot be confirmed under atmospheric pressure).

[b5] 1,4-butanediol diacrylate (SR213 boiling point manufactured by Sartomer Co., Ltd.: cannot be confirmed under atmospheric pressure).

[b6]2-Hydroxyethyl acrylate (Lightester HOA, Co., Ltd., boiling point: 190 ° C)

[b7]Phenylethyl methacrylate terminal polydivinylbenzene (Nippon Steel Chemical PDV)

[c1] Irgcure 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (manufactured by Ciba Japan Co., Ltd.)

[d1] KBM-5103: 3-propenyloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[d2]BYK-378: Polyether modified polydimethyl siloxane based surfactant (BYK CHEMI)

[EDGAC] Diethylene glycol monoethyl ether acetate (Daicel chemical boiling point 217 ° C)

[PGMEA] Propylene glycol monomethyl ether acetate (Daicel chemical boiling point 146 ° C)

[PR 254]: PIGMENT RED 254

[PY 150]: PIGMENT YELLOW 150

[PG 36/PY 150=50/50]: Co-dispersion of PIGEMNT GREEN 36 and PIGMENT YELLOW 150

[PB 15:6]: PIGMENT BLUE 15:6

[evaluation method] <Evaluation of the interface of the colored coating film (evaluation of the overlap of the colored coating film)>

First, using the ink composition (i) shown in Table 2, a cured film was obtained as follows. In other words, the Konica Minolta inkjet head (KM 512M, 14 pl gauge) was used to drive the voltage of 4.8 kHz and the applied voltage of 14 pl, and the line width was made at a nozzle temperature of 23 ° C. The dot pitch was set to 50 μm at 70 μm, and five lines were paralleled and drawn on the PET substrate for inkjet at a pitch of 60 μm. Then, after drying at 80 ° C for 3 minutes, the exposure amount of Table 2 was irradiated with an ultraviolet ray irradiator.

Then, the ink composition (ii) shown in Table 2 was drawn at a dot pitch of 50 μm between the five lines obtained with the above-described distance of 60 μm in the same manner as the inkjet discharge conditions of the ink composition (i). After drying at 80 ° C for 3 minutes, it was exposed to 1500 mJ/cm ² and heat-treated at 80 ° C for 30 minutes. The interface between the ink composition (i) originally drawn and the ink composition (ii) depicted in the second time was observed under a microscope. When the overlap (mixing color) of the two colored films is less than 5 μm, the ink composition (i) of Table 2 is applicable (○), and the ink colored film (ii) composed of the ink composition (ii) is ink. When the wet coloring film (i) composed of the composition (i) was wetted and expanded to 5 μm or more, it was uncomfortable (×), and the results are shown in Table 2 as ○ or ×.

<Contact angle>

Further, for the purpose of measuring the static contact angle θ (see Fig. 1), each of the ink compositions (i) shown in Table 2 was spin-coated on a 5-inch glass substrate, and irradiated with a single exposure machine (illuminance of 50 mW/cm ² ). A colored coating film substrate was produced at 1500 mJ/cm ² . On the substrate, 0.5 μl of each ink composition (ii) shown in Table 2 was dropped, and the static contact angle was measured (h in the figure indicates the droplet height). The results of the contact angle values are shown in Table 2.

<Inkjet Spitability Evaluation>

An inkjet head (KM 512M, 14 pl gauge) manufactured by Konica Minolta was used to drive the voltage of 4.8 kHz and the applied voltage of 14 pl, and the continuous discharge property or the intermittent discharge property was evaluated as the inkjet discharge property under the conditions of the head temperature of 23 °C. The continuous discharge test system confirmed that the nozzle was clogged after continuous discharge for 10 minutes. The intermittent discharge system confirmed that the nozzle was clogged after stopping the discharge for 10 minutes. In the continuous discharge test or the intermittent discharge test, if the clogging of the nozzle cannot be confirmed, it is good (○), and if the nozzle is clogged in any of the tests, it is uncomfortable (×), and the result in Table 2 is recorded as ○ or ×.

Fig. 1 is an explanatory view showing a state in which the static contact angle θ of the ink composition is measured in the examples.

Claims (5)

A resin composition for image formation, which is a resin composition for image formation which can be printed in a dot shape or a stripe shape by an inkjet method on a transparent substrate, and is characterized in that it contains at least a fluorine-containing component, a photopolymerizable component, and light. In the case of the polymerization initiator, the cured composition of the resin composition having a boiling point of 200 ° C or more is contained in the total composition, and the cured film produced by using the resin composition for image formation is at least contained in the photopolymerizable component and photopolymerization. 35 is shown as a starting agent and other ink containing 90% by weight or more of a component having a boiling point of 200 ° C or higher. The above static contact angle θ. The resin composition for image formation according to the first aspect of the invention, wherein the cured film produced by using the resin composition for image formation is obtained by irradiating ultraviolet rays of 200 mJ/cm ² or more. The resin composition for image formation according to the first or second aspect of the invention, wherein the fluorine-containing component contained in the resin composition for image formation is a copolymer having a structure represented by the following formula (1) ; (wherein R ¹ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a chlorine, X represents a divalent organic group having 1 to 6 carbon atoms, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms; Y is a divalent group having a residue of a monomer having a copolymerizable unsaturated group). The image forming resin composition according to any one of claims 1 to 3, wherein the resin composition for image formation contains a fluorine-containing component with respect to the total solid content in the resin composition for image formation. It is 0.05 to 10% by weight, and the total solid content in the resin composition for image formation contains 2 to 30% by weight of the photopolymerization initiator. A display element which is applied to a transparent substrate by an inkjet method using a resin composition according to any one of claims 1 to 4, and which is cured by at least an ultraviolet irradiation step as an image forming method. material.