JP4479342B2 - Coloring composition - Google Patents

Description

  The present invention relates to a coloring composition used for forming various fine coloring patterns. In more detail, this invention relates to the coloring composition used for formation of the various fine coloring pattern by printing.

A fine colored pattern formed by various methods using a colored composition is widely used in various fields such as electronics. For example, a coloring pattern used for a liquid crystal color display is applied with an active energy ray-curable coloring composition containing an alkali-soluble resin, a photopolymerizable compound, and a colorant by a spin coater, and then subjected to exposure and alkali development. It is formed by a photolithography method.
However, patterning by the photolithographic method involves many steps because cleaning, coating, exposure, development, and heat treatment are repeated for each pattern such as black, red, green, and blue. There is a problem that it is difficult to perform proper patterning.

In recent years, patterning has been performed by various methods developed from conventional printing techniques by innovative methods for low cost, large size, and high precision. For example, in order to form a pattern of black, red, green, blue, etc., a method of forming a pattern on a substrate using a relief plate, or after forming a pattern on an intaglio plate, a plurality of patterns are formed on the same substrate via a blanket. The method of transferring the images in an overlapping manner is efficient. These methods are different from the photolithographic method in that the process is short, but stringing occurs in the ink transfer process from the printing plate to the substrate, the printing plate to the blanket, or the ink transfer process from the blanket to the substrate. It has been a problem that the pattern shape is lowered, for example, the linearity of the film is lowered. In addition, when transferring multiple inks on the same substrate, there is a waiting time until the transfer process on the blanket, but the ink is completely dried during this waiting time and loses transferability. There was a case.
JP-A-6-238877 JP-A-4-45175

  Then, an object of this invention is to provide the coloring composition which can control the dry state of a coloring composition and can form a precise pattern with a long transferable duration.

The colored composition in the present invention is a colored composition comprising a transparent resin, a dye carrier made of a precursor thereof or a mixture thereof, a dye, a lactic acid ester organic solvent (A), and a diethylene glycol acetate organic solvent (B). The content of the organic solvent (B) is 1 to 20% by weight based on the total amount of the coloring composition.
In the colored composition of the present invention, the organic solvent (A) is preferably ethyl lactate.
The organic solvent (B) is preferably diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate.

  Since the coloring composition of the present invention contains a lactic acid ester organic solvent (A) and a specific amount of a diethylene glycol acetate organic solvent (B), it can be efficiently controlled to optimum properties in each step of coating, patterning and transfer. The transferability is long, and a precise pattern such as black, red, green, and blue can be formed on the substrate.

First, the coloring composition in this invention is demonstrated concretely.
The coloring composition in the present invention contains a transparent resin, a precursor thereof, or a dye carrier made of a mixture thereof, a dye, and an organic solvent. And in order to control the dry state of a coloring composition, an organic solvent consists of a lactic acid ester type | system | group organic solvent (A) and a diethylene glycol acetate type | system | group organic solvent (B).

The lactic acid ester organic solvent (A) is a solvent having a volume expansion coefficient of 20% or less due to the organic solvent of a silicone rubber used for a silicone rubber blanket, which is generally considered to be excellent in releasability. It can be a good solvent for dispersion. Examples of the lactate organic solvent (A) include methyl lactate (boiling point 147 ° C.), ethyl lactate (boiling point 157 ° C.), butyl lactate (boiling point 188 ° C.), and the like. Of these, methyl lactate and ethyl lactate are preferable from the viewpoint of boiling point, in order to obtain a dry film relatively quickly. Further, from the viewpoint of economy, ethyl lactate is more preferable.
The content of the lactic acid ester organic solvent (A) is preferably 50 to 94% by weight based on the total amount of the colored composition.

The diethylene glycol acetate organic solvent (B) is also a solvent having a volume expansion coefficient of 20% or less due to the organic solvent of the silicone rubber used for the silicone rubber blanket which is generally considered to be excellent in releasability, and is dried. It remains in the coating film to maintain transferability. Examples of the diethylene glycol acetate organic solvent (B) include diethylene glycol monoethyl ether acetate (boiling point 218 ° C.) and diethylene glycol monobutyl ether acetate (boiling point 245 ° C.).
The diethylene glycol acetate-based organic solvent (B) preferably has a higher boiling point than the lactic acid ester-based organic solvent (A) because the transferability duration time becomes longer.

The content of the diethylene glycol acetate-based organic solvent (B) is 1 to 20% by weight, preferably 3 to 15% by weight, based on the total amount of the colored composition. If the content of the diethylene glycol acetate organic solvent (B) is less than 1% by weight, sufficient transferability is hardly exhibited, and if it exceeds 20% by weight, the drying speed of the coated film is remarkably slowed. In some cases, it takes a long time to impart transferability to the coating film.
The coloring composition of the present invention may contain other organic solvents as long as the drying property and transferability are not significantly lowered and the blanket rubber material is not significantly swollen.

As the dye contained in the colored composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

  Examples of the red coloring composition include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122. 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240 Red pigments such as 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of yellow coloring compositions include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, It can be used yellow pigments such 73,174,175,176,177,179,180,181,182,185,187,188,193,194,199.

For the orange coloring composition, for example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used.
For the green coloring composition, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 can be used for the blue coloring composition. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.

Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used for the cyan coloring composition.
For the magenta colored composition, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.

  As the black coloring composition, for example, carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. pigment black 1, 6, 7, 12, 20, 31 or the like can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black coloring composition. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black coloring composition.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic Examples thereof include metal oxide powders such as iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good printability, viscosity stability and the like while maintaining a balance between saturation and lightness.
The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

  As described above, the dye carrier is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins and thermosetting resin fats, and precursors thereof include monomers or oligomers that are polymerized by irradiation or heat to produce transparent resins, which are used alone or Two or more kinds can be mixed and used.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, silicone resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
These transparent resins are reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, isocyanate groups, and epoxy groups for imparting dispersibility, compatibility, coating properties, film forming properties, transferability, and thermosetting properties. It is preferable to have

  The coloring composition of the present invention is a three-roll mill, two-roll mill, sand mill, kneader, attritor, etc. in a dye carrier and a lactic acid ester-based organic solvent (A). These can be produced by finely dispersing using various dispersing means. The diethyl glycol acetate organic solvent (B) can be added when the dye is finely dispersed in the dye carrier and the lactic acid ester organic solvent (A) using various dispersing means, or after being finely dispersed. . Moreover, the coloring composition containing 2 or more types of pigment | dyes can also be manufactured by mixing each pigment | dye separately in the pigment | carrier and the lactic acid ester type | system | group organic solvent (A) separately. When the dye is dispersed in the dye carrier and the lactic acid ester-based organic solvent (A), a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a dye derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in a dye carrier and an organic solvent using the dispersion aid is used. If so, a colored pattern having excellent transparency can be obtained.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, dimethylpolysiloxane-polyalkylene oxide copolymers; alkyl quaternary ammonium salts and their addition of ethylene oxide Examples include chaotic surfactants such as products; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye includes a light yellow aromatic polycyclic compound such as a naphthalene-based or anthraquinone-based compound that is not generally called a dye. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time, and an adhesion improver such as a silane coupling agent in order to improve the adhesion to the transparent substrate. It can also be contained. Moreover, a thermal crosslinking agent, a photocuring agent, etc. can also be added to the colored composition of this invention according to a pattern formation system for the purpose of a coating-film performance improvement.
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

The coloring composition can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, flexographic printing ink.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

  When a coloring pattern other than black is formed by a printing method, the coloring matter is preferably contained in the coloring composition in a proportion of 1.5 to 15% by weight. Moreover, when forming a black pattern, for example, a black matrix, by a printing method, it is preferable to contain in the ratio of 3-30 weight% in a coloring composition. Moreover, it is preferable to contain a pigment | dye in the ratio of 20 to 60 weight% in final coloring patterns other than black, and it is contained in the ratio of 30 to 70 weight% in a black pattern, for example, a black matrix. Is preferred. The remainder consists essentially of the resinous binder provided by the dye carrier.

Hereinafter, the present invention will be specifically described based on examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
[Synthesis of acrylic resin solution]
Into a 2000 ml flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube, 500 parts of ethyl lactate is placed and heated to 90 ° C. while injecting nitrogen gas into the container. At the same temperature, 200 parts of ethyl lactate and 75 parts of methyl methacrylate are added. , A mixture of 75 parts of n-butyl methacrylate, 75 parts of styrene, 45 parts of methacrylic acid, 30 parts of 2-hydroxyethyl methacrylate and 6 parts of azobisisobutyronitrile is added dropwise over 2 hours and further at 90 ° C. for 4 hours. An acrylic resin solution was synthesized by reaction. In addition to cooling to room temperature, the nonvolatile content was adjusted to 20%. The weight average molecular weight of the acrylic resin was 30000.

[Preparation of black pigment dispersion]
Zirconia beads are added to a mixture of 14 parts of a black pigment (“Carbon Black # 47” manufactured by Mitsubishi Chemical Corporation), 1 part of a dispersant (“Solspers 20000” manufactured by Zeneca), 26 parts of the acrylic resin solution and 61 parts of ethyl lactate, The mixture was dispersed for 4 hours using a paint shaker (manufactured by Red Devil), and ethyl lactate was added to obtain a black pigment dispersion having a nonvolatile content of 20%.

[Preparation of blue pigment dispersion]
Zirconia beads in a mixture of 14 parts of a blue pigment (“Heliogen Blue L-6700F” manufactured by BASF), 2.2 parts of a dispersant (“Solspers 20000” manufactured by Zeneca), 25 parts of the acrylic resin solution and 61 parts of ethyl lactate And dispersed with a paint shaker (manufactured by Red Devil) for 4 hours, and ethyl lactate was added to obtain a blue pigment dispersion having a nonvolatile content of 20%.

[Preparation of red pigment dispersion]
11.7 parts of red pigment ("Irga Four Red B-CF" manufactured by Ciba-Geigy), 2.0 parts of red pigment ("Chromotal Red A2B" manufactured by Ciba-Geigy), yellow pigment ("Chromoval Yellow" manufactured by Ciba-Geigy Corporation) GT-AD ”) 0.3 parts, a dispersant (“ Solspers 20000 ”manufactured by Zeneca) 0.6 parts, 25 parts of the acrylic resin solution and 61 parts of ethyl lactate are added with zirconia beads, and a paint shaker (Red Devil For 4 hours, and ethyl lactate was added to obtain a red pigment dispersion having a nonvolatile content of 20%.

[Preparation of green pigment dispersion]
Green pigment (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.) 8.1 parts, yellow pigment (“Funchon First Yellow Y-5688” manufactured by Bayer) 5.9 parts Dispersant (“Solspers 20000” manufactured by Zeneca) ) Add zirconia beads to a mixture of 2.1 parts, 25 parts of the above acrylic resin solution and 61 parts of ethyl lactate, and disperse for 4 hours in a paint shaker (manufactured by Red Devil). A green pigment dispersion was obtained.

(Examples 1-11 and Comparative Examples 1-4)
Pigment dispersion, acrylic resin solution, nonionic surfactant (“BYK-307” manufactured by BYK Chemie), proportion of the composition shown in Table 1 (weight ratio with the total amount of the composition being 100), lactate ester organic solvent (A) Then, a mixture of the diethylene glycol acetate organic solvent (B) was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an ink (coloring composition).
In Example 10 and Comparative Examples 3 and 4, butyl lactate (Example 10 ), cyclohexanone (Comparative Example 3) or 2- (1-methoxy) propyl acetate (Comparative Example 4) was used instead of ethyl lactate. An acrylic resin solution and a pigment dispersion were used.

Using the thin film printing apparatus shown in FIG. 1, printing is performed on a glass substrate by appropriately changing the anilox roll so that the dry coating thickness becomes 1 to 2 μm, and ink drying property evaluation and ink transfer are performed by the following methods. The evaluation of the property duration and the precision pattern formation were evaluated. The results are shown in Table 2.
[Ink drying evaluation]
The ink transferred from the anilox roll to the relief plate causes stringing unless it is in a certain dry state on the plate. For this reason, the time required for peeling and transferring from the letterpress to the blanket cylinder was measured without causing stringing.
<Evaluation criteria>
A: Interfacial peeling transfer can be performed in less than 3 minutes.
○: Interfacial peeling transfer can be performed in 3 minutes or more and less than 5 minutes.
Δ: Interfacial peeling transfer can be performed in 5 minutes or more and less than 8 minutes.
X: Interfacial peeling transfer can be performed for 8 minutes or more.

[Evaluation of ink transfer duration]
In the transfer from the blanket cylinder to the substrate, a waiting time is generated on the blanket cylinder when the transfer is performed on the same substrate. For this reason, the transferability duration after the ink was transferred to the blanket cylinder was measured.
<Evaluation criteria>
A: Interfacial peeling transfer can be performed on the substrate for 3 minutes or more.
○: Interfacial peeling transfer to the substrate is possible for 2 minutes or more and less than 3 minutes.
Δ: Interfacial peeling transfer to the substrate is possible for 1 minute or more and less than 2 minutes.
X: Interfacial peeling transfer to the substrate is possible for less than 1 minute.

[Precise pattern formation evaluation]
The anilox roll was appropriately replaced using the thin film printing apparatus shown in FIG. 1 so that the dry coating thickness was 1 to 2 [mu] m, straight line printing with a line width of 50 [mu] m was performed, and the linear shape was observed.
<Evaluation criteria>
○: A good linear pattern can be continuously printed.
X: The linear pattern is distorted in about 30 continuous printings.
XX: The linear pattern is distorted in about 10 continuous printings.

It is explanatory drawing which showed the thin film printing apparatus used in the Example.

Explanation of symbols

1 Dispenser 2 Doctor 3 Anilox Roll 4 Plate Cylinder 5 Letterpress 6 Silicone Rubber Blanket Cylinder 7 Substrate 8 Printing Table 9 Ink

Claims (3)

Resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm in the visible light region, a dye carrier comprising a monomer or oligomer that is polymerized by irradiation or heat, and a mixture thereof, a dye, or a lactate ester A colored composition comprising an organic solvent (A) and a diethylene glycol acetate organic solvent (B), wherein the content of the organic solvent (A) is 50 to 94% by weight based on the total amount of the colored composition, A patterning coloring composition used for a method of pattern transfer through a silicone rubber blanket, wherein the content of B) is 1 to 20% by weight based on the total amount of the coloring composition.   The coloring composition according to claim 1, wherein the organic solvent (A) is ethyl lactate.   The coloring composition according to claim 1 or 2, wherein the organic solvent (B) is diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate.

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