JP2009161641A - Ink for inkjet printing, color filter for display, and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink for inkjet printing which attains simplification in a production process of a color filter for display and improvement in production stability, and allows to give a printed material with high color density and improved uniformity in each color layer. <P>SOLUTION: The ink for inkjet printing contains a colorant, a crosslinking compound and a polymerization initiator, wherein the crosslinking compound contains at least one compound selected from a group consisting of ethylene oxide adduct di(meth)acrylate of polyethylene glycol, 1,10-decanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate, and propoxylated ethoxylated bisphenol A di(meth)acrylate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ink for inkjet printing, a color filter for display, and a display device that are used to form a color filter for display.

  Various methods for manufacturing a color filter for display used in a liquid crystal display device, an organic EL (Electro-Luminescence) display device, and an electronic paper display device by an inkjet printing method have been proposed.

  The ink composition described in Patent Document 1 contains at least a binder, a bifunctional or trifunctional polyfunctional monomer, and a colorant. The ink described in Patent Document 2 has a weight average molecular weight of 5000 to 20000, one of the main chain and the graft portion is composed of a styrene polymer chain having a styrene monomer unit, and the other has a methacrylate monomer unit. Contains a graft polymer composed of methacrylate polymer chains.

  The resin composition described in Patent Document 3 includes a curable resin, and has an elastic deformation rate of 40% or more in an indentation test according to ISO-14577 of a cured product including only organic components in the solid content of the composition. It is said. The pigment dispersion composition described in Patent Document 4 contains a pigment, a dispersant, a solvent having two acetate structures, and further contains a polyfunctional monomer, a binder resin, and a photopolymerization initiator. Yes.

  The ink composition described in Patent Document 5 includes a di (meth) acrylate compound having a fluorene skeleton, a monomer having a polymerizable unsaturated bond, a polymerization initiator, a pigment, a polyhydric alcohol solvent, and an imidazolidinone derivative. The imidazolidinone derivative is characterized by having a weight ratio of 80% or less.

  Ink-jet printing inks have restrictions on the concentration of the colorant, so that only one printed operation for printing the ink on the substrate to be printed is a printed matter with a low color density and a thin color display. I can't get it. For this reason, in order to obtain a colored layer having a desired color density on the substrate to be printed, complicated steps such as drying the ink after printing and repeating the printing and drying steps a plurality of times are required. In addition, the colored layer of the display filter is not uniform due to the repetition process, and it is difficult to obtain a colored layer of the same quality repeatedly. There is a problem such as lowering.

JP 2001-272529 A JP 2003-128966 A JP 2006-106503 A JP 2006-299090 A JP 2000-034431 A

  An object of the present invention is for inkjet printing, which can obtain a printed matter with a high color density in which the production process of a color filter for display is simplified and the production stability is improved and the uniformity of each colored layer is improved. To provide ink.

  A further object of the present invention is to provide a color filter that can simplify the production process and improve the production stability by applying the ink for inkjet printing to a color filter. The color filter is applied to a display device. The application is to provide a display device with improved display quality.

The present invention contains a colorant, a crosslinkable compound and a polymerization initiator,
The crosslinkable compound is an ethylene oxide addition di (meth) acrylate of polyethylene glycol, 1,10-decanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated 2-methyl-1,3 -An ink for ink jet printing comprising at least one compound selected from the group consisting of propanediol di (meth) acrylate and propoxylated ethoxylated bisphenol A di (meth) acrylate.

In the invention, it is preferable that the colorant is a pigment.
In addition, the present invention is characterized in that the colorant is a mixture of a pigment and a dye.

  Further, the invention is characterized in that the crosslinkable compound has photocurability that is cured by a photosensitive treatment.

  The present invention is also characterized in that the crosslinkable compound has thermosetting properties that are cured by heat treatment.

  According to another aspect of the present invention, there is provided a color filter for display, wherein a colored layer is formed using the ink for ink jet printing.

  According to another aspect of the present invention, there is provided a display device comprising the display color filter.

  According to the present invention, it contains a colorant, a crosslinkable compound and a polymerization initiator, and the crosslinkable compound is an ethylene oxide addition di (meth) acrylate of polyethylene glycol, 1,10-decanediol di (meth) acrylate, At least one compound selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate, ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate and propoxylated ethoxylated bisphenol A di (meth) acrylate Including species.

  As a result, it is possible to obtain a printed matter having a high color density with improved uniformity with a small number of times of printing (for example, once), thereby suppressing the repetition of the printing process and producing a color filter for display. Simplification of the process and improvement of production stability can be realized.

According to the invention, a pigment can be used as the colorant.
According to the invention, a mixture of a pigment and a dye can be used as the colorant.

Moreover, according to this invention, the said crosslinkable compound has photocurability hardened | cured by a photosensitive process.
Thereby, it can harden easily by performing a photosensitive process after printing.

Moreover, according to this invention, the said crosslinkable compound has thermosetting which hardens | cures by heat processing.
Thereby, it can harden easily by performing heat processing after printing.

  Further, according to the present invention, the display color filter includes the colored layer using the ink jet printing ink.

  As a result, it is possible to obtain a printed matter having a high color density with improved uniformity with a small number of times of printing (for example, once), thereby suppressing the repetition of the printing process and producing a color filter for display. Simplification of the process and improvement of production stability can be realized.

  Further, according to the present invention, it is possible to provide a display device with improved display quality by including a color filter for display with improved color density and improved uniformity.

  The ink for inkjet printing of the present invention contains a colorant, a crosslinkable compound and a polymerization initiator, and the crosslinkable compound is an ethylene oxide addition di (meth) acrylate of polyethylene glycol, 1,10-decanediol di (meta). ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate and propoxylated ethoxylated bisphenol A di (meth) acrylate It is characterized by including at least 1 sort of.

  Hereinafter, these crosslinkable compounds defined in the present invention may be referred to as “first crosslinkable compounds”. These first crosslinkable compounds can be used alone or in admixture of two or more.

  These first crosslinkable compounds can be used as a monomer or oligomer, and may be a crosslinkable monomer alone, an oligomer alone, or a mixture of a monomer and an oligomer.

  These first crosslinkable compounds defined in the present invention are referred to as crosslinkable compounds having at least one known ethylenically unsaturated double bond in the molecule (hereinafter referred to as “second crosslinkable compound”). May be used as a mixture. Such a second crosslinkable compound may be a monomer alone, an oligomer alone, or a mixture of a monomer and an oligomer.

  When the second crosslinkable compound is a monomer, such a monomer is preferably a (meth) acrylate monomer, and when the second crosslinkable compound is an oligomer, it is preferably an oligomer of the above monomer.

  Although the monomer of such a second crosslinkable compound is not particularly limited, the following can be exemplified when classified and exemplified based on the number of ethylenically unsaturated double bonds in one molecule. it can.

  First, as a monomer having one ethylenically unsaturated double bond in the molecule, butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, glycidyl acrylate, phenoxy methacrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl Acrylate, t-butyl acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, Dil acrylate, ethoxyethoxyethyl acrylate, methylphenoxyethyl acrylate, caprolactone acrylate, 2-ethylhexyl acrylate, tridecyl acrylate, isodecyl acrylate, isooctyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2 -Hydroxybutyl acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, neopentyl glycol acrylic acid benzoate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, Methoxy-polyethylene Glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxy-polyethylene glycol acrylate, nonylphenol ethylene oxide adduct acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy Examples include -3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and the like.

  Further, as monomers having two ethylenically unsaturated double bonds in the molecule, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Examples include acrylate, tripropylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

  Furthermore, as a monomer having three or more ethylenically unsaturated double bonds in the molecule, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Examples thereof include (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

  Examples of the oligomer of the second crosslinkable compound include oligomers of the monomers exemplified above.

  In the ink for inkjet printing of the present invention, the total content of the first crosslinkable compound and the second masking compound is preferably 5% by weight to 80% by weight with respect to the total amount of the ink for inkjet printing. More preferably, it is 5 to 70% by weight.

  The solvent used in the present invention may be water, a known organic solvent, or a mixture thereof, but an organic solvent is particularly preferable.

  Such an organic solvent is not particularly limited. For example, ethanol, methanol, butanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether , Tetraethyleneglycol Dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol butyl methyl ether, diethylene glycol Mono-t-butyl ether, diethylene glycol dibutyl ether, diethylene glycol isopropyl methyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tripropylene glycol dimethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol Mono-iso-propyl ether dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethyl sulfoxide, Sorbit, sorbitan, acetin, diace Tin, triacetin, sulfolane, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isobutyl acetate, -n-amyl formate, isoamyl acetate, -n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, propyl pyrbenzoate, Ethyl acetoacetate, ethyl binate, γ-butyrolactone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, dimethyl adipate, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, Succinic acid Ethyl, diethyl carbonate, or, preferably used mixtures thereof.

  In particular, such a solvent is preferably a high-boiling organic solvent having a boiling point of 180 ° C. or higher.

  The colorant used in the present invention is not particularly limited, but an organic pigment having a high color density and transmittance is preferably used.

  Moreover, as a coloring agent, although it does not specifically limit with an organic pigment, It is still more preferable that it is a mixture of dye.

  Although it does not specifically limit as an organic pigment used by this invention, The compound classified into Pigment (Pigment) in the color index (The Society of Dyers and Colorists company publication) can be used, Preferably, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185, C.I. I. Pigment red 1, C.I. I. Pigment 2, C.I. I. Pigment red 3, C.I. I. Pigment red 254, C.I. I. Red pigments such as C.I. Pigment Red 177, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6 and the like, and C.I. I. Pigment violet 23:19, C.I. I. Examples thereof include CI Pigment Green 36 and the like and carbon black.

  If necessary, the organic pigment can be finely divided by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc. Or a cleaning treatment with an organic solvent or water for removing impurities may be performed.

  Although it does not specifically limit as dye used by this invention, For example, the compound classified into dye in the color index can be used, and water-soluble red, blue, green, yellow, orange, purple, brown, and black Examples of acid dyes, metal-containing dyes, basic dyes, cationic dyes, direct dyes, reactive dyes, water-insoluble disperse dyes, sulfur dyes, vat dyes, etc. Are preferably soluble dyes or water-insoluble dyes, and more preferably disperse dyes.

  These organic pigments and dyes may be used alone or in combination of two or more.

  The content of the organic pigment and dye used in the present invention in the ink for inkjet printing is preferably 1% by weight to 80% by weight, more preferably 5% by weight to 60% by weight, based on the total amount of the ink for inkjet printing. More preferably, it is 5 to 40% by weight.

  In the inkjet printing ink of the present invention, as the crosslinkable compound, those having photocurability that is cured by a photosensitive treatment and those having thermosetting that is cured by heat treatment are used.

  In order to impart photocurability and thermosetting to the crosslinkable compound, as a polymerization initiator, as an active radical generator that generates an active radical by light or heat, for example, acetophenone compounds, benzoin compounds, benzophenone compounds Examples include compounds, thioxanthone compounds, triazine compounds, and oxime ester compounds.

  By including the polymerization initiator, it is possible to cure the inkjet ink after printing onto the substrate to be printed.

  The acetophenone-based compound is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2- Examples include dimethylamino-1- (4-morpholinophenyl) butan-1-one and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. The

  The benzoin-based compound is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  The benzophenone-based compound is not particularly limited. For example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′- Examples include tetra (t-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

  The thioxanthone compound is not particularly limited, and examples thereof include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Illustrated.

  The triazine-based compound is not particularly limited, and examples thereof include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl). ) -6- (4-Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (4-diechi Amino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5 -Triazine and the like are exemplified.

  The oxime ester-based compound is not particularly limited. For example, 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) and the like are exemplified.

  In addition, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can also be used as active radical generators. .

  Moreover, although it does not specifically limit as an example of a thermal-polymerization initiator, An azo type compound, a peroxide type compound, etc. can be used.

  The azo compound is not particularly limited, and examples thereof include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methyl-2,4-dimethyl). Valeronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) 2,2′-azobis [N-2 (propenyl) -2-methyl-propionamide], 1-[(cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2) -Methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), polydimethylsiloxane unit-containing polymer azo polymerization initiator, Etc. and polyethylene glycol unit-containing azo polymeric initiator is exemplified.

  The peroxide compound is not particularly limited, and examples thereof include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Examples of peroxyesters include t-butyl-peroxylaurate, t-butyl-peroxy-3,5,5-trimethylhexanoate, t-hexyl-peroxy-isopropyl monocarbonate and the like.

  These polymerization initiators may be used alone or in combination of two or more.

  The content of the polymerization initiator used in the present invention in the ink for ink jet printing is preferably 0.5% by weight to 15% by weight, more preferably 0.5% by weight, based on the total amount of ink for ink jet printing. % To 10% by weight.

  The ink for inkjet printing of the present invention contains a colorant, a crosslinkable compound, and a polymerization initiator. By using the first crosslinkable compound as the crosslinkable compound, the number of times of printing is small (for example, once). Thus, it is possible to obtain a printed matter having a high coloring density, thereby suppressing the repetition of the printing process, and simplifying the production process of the display color filter and improving the production stability.

  In addition, the ink for inkjet printing of the present invention may contain a dispersant in addition to the crosslinkable compound, the colorant and the polymerization initiator as described above.

  The dispersant is not particularly limited, and is a polymeric dispersant, for example, a cationic dispersant, an anionic dispersant, a nonionic dispersant, an amphoteric dispersant, a silicone dispersant, a fluorine dispersant, and the like. These surfactants can be used.

  Examples of the cationic dispersant include cationic resins having primary, secondary, or tertiary amino groups, and examples of the anionic dispersant include resins having groups such as carboxylate, sulfonate, and phosphate, Examples of the compounds include resins having a carboxylate group, such as polyacrylate and polystyrene-acrylate, and compounds having a sulfonate group include polyoxyalkylenesulfonate, sodium N-methyl-N-oleyltaurine. Salts, dodecylbenzene sulfonates, and the like are included, and compounds having a phosphate group include polyoxyalkylene alkyl ether phosphates. Furthermore, examples of nonionic dispersants include polyoxyethylene type and amide type, and polyoxyethylene type dispersants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and acetylene glycol. And polyoxyethylene glycol ester copolymers and the like, and the amide type dispersant includes polyoxyethylene fatty acid amide and the like, but the dispersant is not particularly limited thereto.

  These dispersants may be used alone or in combination of two or more.

  Further, the content of the dispersant used in the present invention in the ink jet printing ink is 0.3 wt% to 50 wt%, preferably 1 wt% to 40 wt% with respect to the total amount of the ink for ink jet printing. More preferably, it is 2 to 25% by weight.

  The ink for inkjet printing of the present invention may contain a binder resin in addition to the crosslinkable compound, the colorant, the polymerization initiator, and the dispersant as described above. The cured ink becomes a stronger cured product.

  The binder resin is polymerized in advance, and examples thereof include a non-polymerizable binder resin that does not have self-polymerizability, or a polymerizable binder resin in which a polymerizable substituent is introduced into the non-polymerizable binder resin. Examples of the non-polymerizable binder resin include (meth) acrylic resin, polyester (meth) acrylic resin, and epoxy (meth) acrylic resin, but the binder resin is not limited thereto.

  These binder resins may be used alone or in combination of two or more.

  The content of the binder resin used in the present invention in the ink for ink jet printing is preferably 50% by weight or less, more preferably 20% by weight or less, with respect to the total amount of ink for ink jet printing.

  The ink for inkjet printing of the present invention may contain known additives such as a filler, a polymer compound other than the binder resin, an adhesion promoter, an aggregation inhibitor, an organic acid, and a curing agent, as necessary. However, the additive is not limited to these.

  Here, as the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are exemplified, but as adhesion promoters This But it is not limited to, et al.

  Moreover, these adhesion promoters may be used alone or in combination of two or more.

  The ink for inkjet printing used in the present invention is provided as a uniform dispersion system by atomizing a colorant in a crosslinkable compound, a dispersant, a binder resin and other additives.

  The method for obtaining such a colorant atomization and a uniform dispersion system is not particularly limited, and may be a known method such as a dispersion atomization method using a batch type dispersion peptizer or a continuous dispersion peptizer, such as a roll mill. The colorant can be uniformly dispersed in the ink for inkjet printing by stirring and mixing using a dispersing machine such as a ball mill, a colloid mill, a jet mill, or a bead mill.

  When the colorant atomizes a water-insoluble organic pigment or dye, it is not particularly limited, but the average particle diameter is preferably in the range of 50 nm to 100 nm.

  The polymerization initiator is preferably added to the composition in which the colorant is uniformly dispersed in this way.

  Such a dispersion composition can be made into an ink for ink jet printing suitable for the ink jet printing method by subsequent filtration.

  In the present invention, ink for inkjet printing can be printed by a known inkjet printing head and printing apparatus or a printing apparatus manufactured using a known inkjet printing head.

  The inkjet print head is not particularly limited, and a known print head such as a piezo method, a baffle jet method, or an electrostatic method is used.

  In the present invention, ink for inkjet printing can be printed on a known substrate to be printed, but the substrate to be printed may be, for example, a known glass substrate, plastic substrate, or plastic film substrate. The substrate is not limited to these.

  The ink for inkjet printing of the present invention can be dried after being printed on a substrate to be printed, and further cured by a photosensitive treatment or heat treatment.

  The method for photocuring the ink for inkjet printing of the present invention is not particularly limited, and known methods can be applied.

  As a photocuring method, for example, after printing ink for inkjet printing on a substrate to be printed, it is dried by a known method, and ultraviolet rays, far ultraviolet rays, g rays, h rays, i rays, KrF having a wavelength of 400 to 200 nm are dried. Examples of the photocuring method include, but are not limited to, a photosensitizing method using active energy rays such as excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, or ion beam.

  In addition, as a method of thermosetting, for example, after printing ink for inkjet pudding on a substrate to be printed, it is dried by a known method and heat-treated in a room at 80 ° C. or higher under atmospheric pressure for 10 minutes or more. Alternatively, it may be heat-treated for 10 minutes or longer by blowing hot air at a temperature of 80 ° C. or higher under atmospheric pressure, or may be placed on a hot plate at a temperature of 80 ° C. or higher under atmospheric pressure and heat-treated for 10 minutes or longer. Although a method is illustrated, as a thermosetting method, it is not limited to these.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples.

[Example 1]
(Formation of black matrix substrate)
A TK-41 negative resin black matrix material manufactured by Sumitomo Chemical Co., Ltd. was applied by a known method onto a Corning Eagle 2000 liquid crystal transparent glass substrate having an outer dimension of 370 mm × 470 mm and a thickness of 0.5 mm. The rotating film thickness was adjusted to 2.3 μm. Then, it heat-processed at 80 degreeC for 120 second, and mask exposure was performed by the well-known method with the exposure amount of 150 mJ / cm < ² >. Next, development was performed using a 0.5% aqueous sodium carbonate solution, followed by washing with water by a known method and drying. Next, the glass substrate was baked at 230 ° C. for 20 minutes to obtain a black matrix substrate having a rectangular opening with a width of 70 μm × 225 μm and a film thickness of 2.0 μm.

(Preparation of red ink for inkjet printing)
As a coloring agent, C.I. I. 12 parts by weight of Pigment Red 254, 4 parts by weight of Disperbyk-168 (manufactured by Big Chemie Japan) as a dispersant, and 63.4 parts by weight of diethylene glycol diethyl ether are mixed, and the pigment is dispersed using a known bead mill. To prepare a red pigment dispersion.

  Separately, 20 parts by weight of 1,10-decanediol diacrylate (first crosslinkable compound) containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor and 1,2-octanedione, 1- [ 4- (Phenylthiophenyl)]-, 2- (O-benzoyloxime) 0.6 part by weight was added with stirring to obtain a mixture.

  This mixed liquid and the prepared red pigment dispersion were mixed while being stirred by a known method, and further filtered through a membrane filter having a pore diameter of 3 μm to obtain a red ink for inkjet printing. When the particle diameter of the pigment in the obtained red ink for inkjet printing was measured with a microtrack particle size distribution analyzer (HRA (X-100) manufactured by Nikkiso Co., Ltd.), the particle size was in the range of 50 to 100 nm. The average particle size was 70 nm.

(Printing of red ink for inkjet printing)
The obtained red ink for ink-jet printing was printed and filled in a predetermined opening of the black matrix substrate using a light rex 120 (manufactured by light rex) ink jet printing apparatus. Thereafter, heating was performed at a temperature of 120 ° C. for 5 minutes, and further heating was performed at a temperature of 230 ° C. for 20 minutes to cure the red ink for inkjet printing, thereby forming a pattern of a red colored layer on the black matrix substrate. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 2]
In Example 1, instead of 20 parts by weight of 1,10-decandiol diacrylate containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor, ethylene oxide addition of polyethylene glycol containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor A red ink for inkjet printing was obtained in the same manner as in Example 1 except that 20 parts by weight of diacrylate (first crosslinkable compound) was used, and red on the black matrix substrate in the same manner as in Example 1. A colored layer pattern was formed. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 3]
In Example 1, instead of 20 parts by weight of 1,10-decanediol diacrylate containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor, tricyclodecane dimethanol dimer containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor A red ink for inkjet printing was obtained in the same manner as in Example 1 except that 20 parts by weight of methacrylate (first crosslinkable compound) was used. Further, red coloring was performed on the black matrix substrate in the same manner as in Example 1. A layer pattern was formed. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 4]
In Example 1, instead of 20 parts by weight of 1,10-decanediol diacrylate containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor, ethoxylated 2-methyl- containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor A red ink for inkjet printing was obtained in the same manner as in Example 1 except that 20 parts by weight of 1,3-propanediol diacrylate (first crosslinkable compound) was used. Further, in the same manner as in Example 1, A red colored layer pattern was formed on the black matrix substrate. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 5]
In Example 1, instead of 20 parts by weight of 1,10-decanediol diacrylate containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor, propoxylated ethoxylated bisphenol A containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor Except for using 20 parts by weight of dimethacrylate (first crosslinkable compound), a red ink for inkjet printing was obtained by the same method as in Example 1, and further red on the black matrix substrate by the same method as in Example 1. A colored layer pattern was formed. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 6]
In Example 1, C.I. I. Instead of 12 parts by weight of CI Pigment Red 254, C.I. I. 6 parts by weight of Pigment Red 254 and C.I. I. Except for using 6 parts by weight of Pigment Red 177, a red ink for inkjet printing was obtained by the same method as in Example 1, and a red colored layer pattern was formed on the black matrix substrate by the same method as in Example 1. did. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 7]
(Preparation and printing of green ink for inkjet printing)
In Example 1, C.I. I. Instead of 12 parts by weight of CI Pigment Red 254, C.I. I. Except for using 12 parts by weight of Pigment Green 36, green ink for inkjet printing was obtained in the same manner as in Example 1, and a green colored layer pattern was formed on the black matrix substrate in the same manner as in Example 1. did. The resulting colored layer was a dark green colored layer that was uniform and free of defects.

[Example 8]
(Preparation and printing of blue ink for inkjet printing)
In Example 1, C.I. I. Instead of 12 parts by weight of CI Pigment Red 254, C.I. I. Except for using 12 parts by weight of Pigment Blue 15: 6, a blue ink for inkjet printing was obtained by the same method as in Example 1, and a blue colored layer pattern was formed on the black matrix substrate by the same method as in Example 1. Formed. The resulting colored layer was a dark blue colored layer that was uniform and free of defects.

[Example 9]
In Example 1, C.I. I. Instead of 12 parts by weight of CI Pigment Red 254, C.I. I. Pigment Blue 15: 6 8 parts by weight and C.I. I. Except for using 4 parts by weight of Disperse Blue 79, a blue ink for inkjet printing was obtained in the same manner as in Example 1, and a blue colored layer pattern was formed on the black matrix substrate in the same manner as in Example 1. Formed. The resulting colored layer was a dark blue colored layer that was uniform and free of defects.

[Example 10]
In Example 1, instead of 20 parts by weight of 1,10-decanediol diacrylate containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor, 1,10-decanediol diester containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor Example except that 15 parts by weight of acrylate (first crosslinkable compound) and 5 parts by weight of tricyclodecane dimethanol diacrylate (first crosslinkable compound) containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor were used. A red ink for ink jet printing was obtained by the same method as in Example 1, and a red colored layer pattern was formed on the black matrix substrate by the same method as in Example 1. The resulting colored layer was a dark red colored layer that was uniform and free of defects.

[Example 11]
C. I. 15 parts by weight of Pigment Red 254 and 5 parts by weight of Disperbyk-168 (manufactured by Big Chemie Japan) as a dispersant and 19 parts by weight of isobornyl acrylate are mixed, and the pigment is mixed using a known bead mill. A red pigment dispersion was prepared by dispersing.

  Separately, 20 parts by weight of 1,10-decanediol diacrylate (first crosslinkable compound) containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor and trimethylolpropane containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O--) as a polymerization initiator in a mixed solution of 40 parts by weight of triacrylate (second crosslinkable compound). 1 part by weight of benzoyloxime was added with stirring to obtain a mixed solution.

  This mixed solution and the red pigment dispersion were mixed while being stirred by a known method, and then filtered through a membrane filter having a pore size of 3 μm to obtain a red ink for inkjet printing. When the particle diameter of the pigment in the obtained red ink for inkjet printing was measured with a microtrack particle size distribution analyzer (HRA (X-100) manufactured by Nikkiso Co., Ltd.), the particle size was in the range of 50 to 100 nm. The average particle size was 70 nm.

  Next, a red colored layer pattern was formed on the black matrix substrate by the same method as in Example 1. The resulting colored layer was a uniform and defect-free red colored layer having a high color density.

[Example 12]
C. I. 9 parts by weight of Pigment Red 254 and 2.8 parts by weight of Disperbyk-168 (manufactured by Big Chemie Japan), 9.1 parts by weight of dipropylene glycol monomethyl ether acetate and 67.5 parts of isobornyl acrylate Part by weight was mixed and the pigment was dispersed using a known bead mill to prepare a red pigment dispersion.

  Separately, 7 parts by weight of 1,10-decanediol diacrylate (first crosslinkable compound) containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor and trimethylolpropane containing 100 ppm of 4-methoxyphenol as a polymerization inhibitor 1,4-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O-benzoyloxime) as a polymerization initiator in a mixed solution of 4 parts by weight of triacrylate (second crosslinkable compound) ) After mixing 0.6 parts by weight with stirring by a known method, the mixture was further filtered through a membrane filter having a pore diameter of 3 μm to obtain a red ink for inkjet printing. When the particle diameter of the pigment in the obtained red ink for inkjet printing was measured with a microtrack particle size distribution analyzer (HRA (X-100) manufactured by Nikkiso Co., Ltd.), the particle size was in the range of 50 to 100 nm. The average particle size was 70 nm. Next, a red colored layer was formed on the black matrix substrate by the same method as in Example 1. The obtained red colored layer was a uniform colored layer having a high color density and no defects.

[Example 13]
The red ink for ink jet printing prepared in Example 1, the green ink for ink jet printing prepared in Example 7, and the blue ink for ink jet printing prepared in Example 8 were prepared in the same manner as in Example 1, using a black matrix. A display color filter in which red, green, and blue colored layers were formed on a black matrix substrate was printed on each predetermined opening of the substrate.

  The obtained display color filter was a color filter that was uniform for each pixel and had no defects.

[Example 14]
The display color filter obtained in Example 13 was panelized for a liquid crystal display device by a known method to produce a liquid crystal display device.

  When the liquid crystal display device was turned on by a known method, a uniform display free from luminance spots and color spots was obtained.

Claims (7)

Containing a colorant, a crosslinkable compound and a polymerization initiator,
The crosslinkable compound is an ethylene oxide addition di (meth) acrylate of polyethylene glycol, 1,10-decanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated 2-methyl-1,3 An ink for ink-jet printing, comprising at least one compound selected from the group consisting of propanediol di (meth) acrylate and propoxylated ethoxylated bisphenol A di (meth) acrylate.   The ink for inkjet printing according to claim 1, wherein the colorant is a pigment.   2. The ink for inkjet printing according to claim 1, wherein the colorant is a mixture of a pigment and a dye.   The ink for inkjet printing according to any one of claims 1 to 3, wherein the crosslinkable compound has photocurability that is cured by a photosensitive treatment.   The ink for inkjet printing according to any one of claims 1 to 3, wherein the crosslinkable compound has thermosetting properties that are cured by heat treatment.   A display color filter, wherein a colored layer is formed using the ink for inkjet printing according to any one of claims 1 to 5.   A display device comprising the display color filter according to claim 6.