KR102035490B1 - Ink composition for roll printing - Google Patents
Ink composition for roll printing Download PDFInfo
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- KR102035490B1 KR102035490B1 KR1020130104888A KR20130104888A KR102035490B1 KR 102035490 B1 KR102035490 B1 KR 102035490B1 KR 1020130104888 A KR1020130104888 A KR 1020130104888A KR 20130104888 A KR20130104888 A KR 20130104888A KR 102035490 B1 KR102035490 B1 KR 102035490B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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Abstract
The present invention relates to an ink composition for roll printing, and more specifically, by containing a binder resin containing a repeating unit represented by the formulas (1) and (2), the heat resistance is significantly improved to minimize the change in color even when exposed to high temperatures. The present invention relates to an ink composition for roll printing which is excellent in printability and can suppress cracking of a pattern.
Description
The present invention relates to an ink composition for roll printing.
Fine patterns used in semiconductor circuit devices and display devices such as LCDs and PDPs are formed by photolithography using photoresist, and photolithography has an advantage of precisely obtaining desired patterns. Nevertheless, there are disadvantages of going through many steps, using many kinds of materials to maximize the effect of the photoresist, and consuming a large amount of photoresist in a coating or the like process.
Therefore, in recent years, as one of the next-generation processes for overcoming the drawbacks of photolithography, a technique for obtaining a micropattern by a roll printing or an inkjet printing method has been proposed.
Various methods such as offset printing, reverse offset printing, and roll-to-roll printing can be applied to the formation of fine patterns by roll printing, and R (Red) and G ( It is widely applicable to green, B (blue) color and BM (black matrix) patterns, as well as electrode formation patterns of thin film transistors (TFTs) and plasma display panels (PDPs), and pattern transfer of partition material.
When the pattern formed of the ink composition for roll printing is applied to a display or the like, it undergoes a high temperature subsequent process, whereby a color change may occur.
This can be a serious problem especially when the pattern is applied to the non-display portion of the image display apparatus.
In FIG. 1, an image display device (mobile phone) including a touch screen panel is illustrated. A display unit refers to a portion where an image is displayed, and a non-display portion refers to an edge portion where an image is not displayed. Since the non-display portion is the top layer shown to the consumer, the ink used at this time is required to exhibit shielding property, high resistance and excellent colorability.
Accordingly, development of an ink composition having heat resistance for suppressing such color change and having other characteristics such as suppressing crack generation of the pattern and printability is required.
Korean Patent Publication No. 2010-39652 discloses a solvent-free ultraviolet curable white ink composition.
It is an object of the present invention to provide an ink composition for roll printing which is excellent in heat resistance and can minimize color change in high temperature conditions.
Moreover, an object of this invention is to provide the ink composition for roll printing which can suppress a crack generation.
Moreover, an object of this invention is to provide the ink composition for roll printing excellent in printability.
1. An ink composition for roll printing containing a binder resin containing a repeating unit represented by the following formulas (1) and (2):
[Formula 1]
[Formula 2]
2. In the above 1, wherein the repeating units represented by Formula 1 and 2 are included in a molar ratio of 1: 5 to 9, the ink composition for printing rolls.
3. In the above 1, wherein the repeating units represented by Formulas 1 and 2 is included in 30 to 100 mol%, roll printing ink composition.
4. according to the above 1, wherein the binder resin further comprises a repeating unit represented by the following formula (3), a roll printing ink composition:
[Formula 3]
5. In the above 4, wherein the monomers represented by Formulas 1, 2 and 3 are included in a molar ratio of 1: 5 to 9: 1 to 3, the ink composition for roll printing.
6. In the above 4, wherein the repeating unit represented by the formula 3 is contained in 5 to 50 mol%, roll printing ink composition.
7. In the above 1, wherein the binder resin further comprises at least one of the repeating units represented by the following formula 4 to 6, roll printing ink composition:
[Formula 4]
[Formula 5]
[Formula 6]
8. according to the above 1, wherein the binder resin is contained in 0.5 to 10% by weight, ink composition for printing rolls.
9. according to the above 1, further comprising a colorant, a thermal polymerization initiator and a solvent, the ink composition for roll printing.
10. In the above 9, the colorant CI pigment white 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25, 26, 27, 28 and 32 in the group consisting of At least one selected, the ink composition for roll printing.
11. In the above 9, the solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, meth Oxypentyl acetate, benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, methanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and at least selected from the group consisting of γ-butyrolactone Nine, roll printing ink composition.
12. In the above 9, 10 to 50% by weight of the colorant, 0.1 to 3% by weight of the thermal polymerization initiator and 40 to 80% by weight of the solvent, the ink composition for printing rolls.
The ink composition for roll printing of the present invention is excellent in heat resistance and can minimize color change even when exposed to high temperature conditions.
The ink composition for roll printing of this invention can suppress a crack of a pattern.
The ink composition for roll printing of the present invention is excellent in printability because the ink coated on the roll is completely transferred to the substrate during printing.
1 illustrates an image display device (mobile phone) including a touch screen panel.
2 is a photograph which can confirm the color of the coating film formed by the ink composition of Example 1.
3 is a photograph which can confirm the color of the coating film formed by the ink composition of Comparative Example 1.
The present invention includes a binder resin containing a repeating unit represented by the formulas (1) and (2), thereby significantly improving heat resistance and minimizing color change even when exposed to high temperatures, and excellent in printability and suppressing cracking of patterns. It relates to an ink composition for roll printing.
Hereinafter, the present invention will be described in detail.
The ink composition for roll printing of this invention contains a binder resin.
The binder resin serves as a pattern support, and the binder resin according to the present invention includes repeating units represented by the following Chemical Formulas 1 and 2:
[Formula 1]
[Formula 2]
Since the repeating units represented by Chemical Formulas 1 and 2 significantly improve heat resistance, when a pattern applied to a display or the like is formed with the ink composition of the present invention, a change in color that may occur when undergoing a subsequent high temperature process may be minimized. Can be. In addition, after the ink has been coated on the roll, the ink has a suitable viscosity, so that the ink coated on the roll can be completely transferred to the substrate to improve printability and to form a pattern having a fine shape and excellent straightness.
In addition, the repeating unit represented by Formula 2 may be used together with the repeating unit of Formula 1 to suppress expansion and contraction of heat, thereby minimizing the occurrence of cracks in the pattern.
The content ratio of the repeating units represented by Chemical Formulas 1 and 2 is not particularly limited, and may be included, for example, in a molar ratio of 1: 5 to 9, and preferably included in a molar ratio of 1: 8 to 9. When the repeating units represented by Formulas 1 and 2 are included in a molar ratio of 1: 5 to 9, the heat resistance improvement and crack suppression effect may be maximized.
In the binder resin according to the present invention, the repeating units represented by Chemical Formulas 1 and 2 may be appropriately mixed according to the specific types of other repeating units that may be included together, and the content thereof is not particularly limited. For example, in the binder resin, Chemical Formula 1 And 30 to 100 mol% of the repeating unit represented by 2 may be included. When the repeating units represented by Formulas 1 and 2 are within the above range, the heat resistance improvement and crack suppression effect may be maximized.
The binder resin according to the present invention may further include a repeating unit represented by Formula 3 below:
[Formula 3]
By including the repeating unit represented by Formula 3, printability may be further improved.
When the binder resin according to the present invention further includes a repeating unit represented by the formula (3), the content ratio of the repeating units represented by the formulas (1) to (3) is not particularly limited, for example, to the formula (1), (2) and (3) The repeating unit to be represented may be included in a molar ratio of 1: 5 to 9: 1 to 3, preferably, may be included in a molar ratio of 1: 8 to 9: 1 to 3. When the repeating units represented by Formula 1, Formula 2, and Formula 3 are included in a molar ratio of 1: 5 to 9: 1 to 3, the effects of improving heat resistance, cracking, and improving printability may be maximized.
In the binder resin according to the present invention, the repeating unit represented by Chemical Formula 3 may be appropriately mixed according to specific types of other repeating units that may be included together, and the content thereof is not particularly limited, for example, represented by Chemical Formula 3 in the binder resin. 5 to 50 mol% of repeating units may be included. When the repeating unit represented by the formula (3) is within the above range, it is possible to maximize the printability improvement effect.
The binder resin according to the present invention may further include at least one of the repeating units represented by the following Chemical Formulas 4 to 6:
[Formula 4]
[Formula 5]
[Formula 6]
In the case of including the repeating unit represented by Formulas 4 to 6, the printability improvement effect may be further increased.
The molecular weight of the binder resin is not particularly limited, and for example, the weight average molecular weight may be 4,000 to 9,000.
The content of the binder resin is not particularly limited within the range capable of its function, for example, may be included in 0.5 to 10% by weight of the total weight of the ink composition, preferably 3 to 8% by weight. . When the content of the binder resin falls within the above range, it is possible to suppress cracks in the pattern and maximize the heat resistance and printability improvement effect.
The ink composition for roll printing of the present invention further includes a colorant, a thermal polymerization initiator and a solvent.
The colorant may be an organic colorant such as a pigment, a dye, a synthetic or natural colorant, or an inorganic colorant such as a metal oxide, a metal complex salt, or barium sulfate (sieve pigment).
As the colorant, compounds classified as pigments and dyes in the Color Index (The Society of Dyers and Colourists) may be used, and these may be used alone or in combination of two or more thereof.
Specific examples of the pigment include C.I. Pigment Yellow No. 1, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Pigment Red No. 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, 265; C.I. Pigment Blue No. 15, 15: 3, 15: 4, 15: 6, 60; C.I. Pigment Purple No. 1, 14, 19, 23, 29, 32, 33, 36, 37, 38; C.I. Pigment Green No. 7, 10, 15, 25, 36, 47; C.I. Pigment brown 23, 25, 28; C.I. Pigment Black No. 1, 7, carbon black, etc. are mentioned.
Specific examples of the dyes include C.I. Solvent yellow 2, 14, 16, 33, 34, 44, 56, 82, 93, 94, 98, 116, 135; C.I. Solvent orange No. 1, No. 3, No. 7, No. 63; C.I. Solvent Red No. 1, 2, 3, 8, 18, 23, 24, 27, 35, 43, 45, 48, 49, 91: 1, 119, 135 No. 140, 196, 197; C.I. Solvent purple 8, 9, 13, 26, 28, 31, 59; C.I. Solvent blue Nos. 4, 5, 25, 35, 36, 38, 70; C.I. Solvent green 3, 5, 7 and the like.
The ink composition for roll printing of the present invention can be used to form a white non-display portion pattern (white matrix) such as an image display device, a touch screen panel, etc. In this case, the colorant may be a white colorant.
The white colorant is not particularly limited as long as it is a white inorganic pigment generally used in the art, for example CI pigment white 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25 , 26, 27, 28, 32, and the like, and preferably CI pigment white 6 or white 22 in terms of reflection efficiency and whiteness. These can be used individually or in mixture of 2 or more types.
TiO 2 included in the CI pigment white 6 is low in cost and high in refractive index, and thus may be used as an effective white colorant because of excellent hiding power and reflectance. Preferably, the TiO 2 preferably has a rutile structure.
If necessary, the white colorant is organic to remove impurities or resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, or an atomization treatment by sulfuric acid atomization or the like. A washing treatment with a solvent, water, or the like, an ionic impurity removing treatment by an ion exchange method, or the like can also be performed.
The colorant may further include other white pigments without departing from the object of the present invention.
The colorant may be adjusted in accordance with the required color properties, for example, may be included in 10 to 50% by weight, preferably 30 to 50% by weight of the total weight of the ink composition. When the colorant is included in an amount of 10 to 50% by weight, it may have excellent colorability and shielding properties without degrading printability.
As the polymerization initiator, a known thermal polymerization initiator may be used. Among the onium, thermal polymerization initiators containing sulfonium cations and anions have better stability over time and better shrinkage ratio characteristics than other types of thermal polymerization initiators. It is preferable at the point which can improve the adhesiveness between an ink composition and a printed object. These polymerization initiators can be used individually or in mixture of 2 or more types.
Specific examples of the sulfonium cation constituting the polymerization initiator include triphenylsulfonium, tris (4-tolyl) sulfonium, tris (4-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (4-cyanophenyl) sulfonium, tris (4-chlorophenyl) sulfonium, diphenyl (4-hydroxyphenyl) sulfonium, methylphenyl (4-hydroxyphenyl) sulfonium, dibenzylphenylsulfonium, di Benzyl (4-hydroxyphenyl) sulfonium, benzylmethyl (4-hydroxyphenyl) sulfonium, benzylmethyl (4-acetoxyphenyl) sulfonium, methyl (4-hydroxyphenyl) (2-methylphenyl) sulfonium , Dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecaneoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, Methyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18-tri Fluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium, and the like, among which triphenylsulfonium and tris ( 4-tolyl) sulfonium, benzylmethyl (4-hydroxyphenyl) sulfonium, benzylmethyl (4-acetoxyphenyl) sulfonium, methyl (4-hydroxyphenyl) (2-methylphenyl) sulfonium are preferable, More preferably, tris (4-tolyl) sulfonium, benzylmethyl (4-acetoxyphenyl) sulfonium and benzylmethyl (4-hydroxyphenyl) sulfonium are preferable.
In addition, the type of the anion constituting the polymerization initiator is not particularly restricted but includes, for example, F -, Cl -, Br - , I - halogen ion and the like; OH -; ClO 4 -; FSO 3 -, ClSO 3 -, CH 3 SO 3 -, C 6 H 5 SO 3 -, CF 3 SO 3 - of a sulfonic acid ion, and the like; HSO 4 -, SO 4 2 - ions such as sulfate; HCO 3 -, CO 3 2 - ions in the acid, and the like; H 2 PO 4 -, HPO 4 2 -, PO 4 3 - phosphate ions and the like; PF 6 -, PF 5 OH - phosphate ions, such as fluoro; BF 4 -, B (C 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - , etc. of borate ions; AlCl 4 -; BiF 6 -; SbF 6 -, SbF 5 OH - antimony acid ion such as fluoro; ASF 6 -, AsF 5 OH -, and the like, such as ion-fluoro lobby dissipation.
The content of the thermal polymerization initiator according to the present invention is not particularly limited within the range capable of functioning, for example, may be included in 0.1 to 3% by weight of the total weight of the ink composition, preferably 0.3 to 1.5% by weight % May be included. When the content of the thermal polymerization initiator is 0.1 to 3% by weight, it is possible to secure an appropriate degree of polymerization and coating property and at the same time effectively improve adhesion to the printed material.
The solvent may be selected from the group consisting of ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether in consideration of solubility, dispersibility of a colorant, coating properties, and the like; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, methanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
The solvent is not particularly limited in its content within the range capable of functioning, for example, may be included in 40 to 80% by weight of the total weight of the ink composition, preferably 40 to 60% by weight. When the solvent content is 40 to 80% by weight, the ink composition maintains proper coloring power and is easy to print.
The ink composition for roll printing of the present invention may be used in combination with additives such as surfactants, fillers, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, dispersants and the like according to the needs of those skilled in the art within the range not impairing the object of the present invention in addition to the above components. It is also possible.
The kind of surfactant is not specifically limited, For example, silicone type surfactant, fluorine type surfactant, or a mixture thereof is mentioned.
Silicone surfactants are, for example, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322 , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK -358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
Fluorine-based surfactants are, for example, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, and F-444 from DaiNippon Ink & Chemicals (DIC). , F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F -483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126 TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, TF-1535; AGC Sage Chemical's S-381, S-383, S-393, SC-101, Sc-105, KH-40, SA-100, S-611, S-386, S-221, S-231, S- 243, S-420, S-651, etc. are mentioned. These can be used individually or in mixture of 2 or more types.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
Example One
After obtaining a millbase containing 50% by weight of CI pigment white 6, 3% by weight of polyester-based dispersant and the balance of normal butyl acetate, 80% by weight of the millbase under agitation at 23 ℃, the repeating unit of formula 3 weight percent molecular weight (MW) of 4,000 binder resin containing 2 repeat units in a ratio of 1: 8, 0.5 weight percent SI-100L (Samshin Chemical) as a thermal initiator and TF-1535 (surfactant) DIC) 1% mixed, normal butyl acetate was added to the balance and mixed. The mixture was stirred for 3 hours to prepare an ink composition for roll printing.
Example 2
An ink composition for roll printing was prepared in the same manner as in Example 1 except that the ratio of the repeating unit of Formula 1 to the repeating unit of Formula 2 of the binder resin was 1: 6.
Example 3
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the ratio of the repeating unit of Formula 1 to the repeating unit of Formula 2 of the binder resin was 1:10.
Example 4
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, 4, and 6 in a ratio of 1: 5: 1: 1.
Example 5
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, 4, and 5 in a ratio of 1: 5: 1: 1.
Example 6
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, 4, and 6 in a ratio of 1: 5: 1: 2.
Example 7
An ink composition for roll printing was prepared in the same manner as in Example 1, except that 0.3 wt% of binder resin was included.
Example 8
An ink composition for roll printing was prepared in the same manner as in Example 1, except that 12 wt% of binder resin was included.
Example 9
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, and 3 in a ratio of 1: 9: 3.
Example 10
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, and 3 in a ratio of 1: 4: 1.
Example 11
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 2, and 3 in a ratio of 1: 5: 4.
Comparative example One
Roll printing was carried out in the same manner as in Example 1, except that a copolymer of methacrylic acid and benzyl methacrylate having a weight average molecular weight (MW) of 6,000 and an acid value (A / V) of 50 mgKOH / g was used as the binder resin. An ink composition was prepared.
Comparative example 2
Roll printing was carried out in the same manner as in Example 1, except that a copolymer of methacrylic acid and benzyl methacrylate having a weight average molecular weight (MW) of 5,000 and an acid value (A / V) of 50 mgKOH / g was used as the binder resin. An ink composition was prepared.
Comparative example 3
An ink composition for roll printing was prepared in the same manner as in Example 1 except that the binder resin included only the repeating unit of Formula 1.
Comparative example 4
An ink composition for roll printing was prepared in the same manner as in Example 1 except that the binder resin included only the repeating unit of Formula 2.
Comparative example 5
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 4, and 5 in a ratio of 1: 3: 1.
Comparative example 6
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 1, 4, 5, and 6 in a ratio of 1: 3: 1: 1.
Comparative example 7
An ink composition for roll printing was manufactured in the same manner as in Example 1, except that the binder resin contained the repeating units of Formulas 2, 4, 5, and 6 in a ratio of 1: 3: 1: 1.
Experimental Example
(1) heat resistance evaluation
The ink compositions of Examples and Comparative Examples were printed on a glass substrate to form a coating film, and after heating in an oven at 230 ° C. for 30 minutes, the YI-D1925 value was measured with a color difference meter (i-5, X-rite).
FIG. 2 is a photograph of a coating film formed of the composition of Example 1 and FIG. 3.
(2) printability evaluation
After printing the ink compositions of Examples and Comparative Examples on a glass substrate, the final transferred pattern shape and the degree of formation were observed under a microscope, and evaluated based on the following criteria.
<Evaluation Criteria>
(Double-circle): The ink coated on the roll is completely transferred to a board | substrate, and the pattern shape and the straightness of a pattern are very excellent.
○: The ink coated on the roll is completely transferred to the substrate, and the pattern shape and the straightness of the pattern are excellent.
(Triangle | delta): The pattern shape and pattern straightness of a pattern are not good even if the ink coated on the roll remains partially, without being fully transferred to a board | substrate.
X: Even when a large amount of ink remains on the roll or is transferred, the pattern shape and pattern straightness are not good.
(3) of pattern crack Rate of occurrence
After printing the ink compositions of Examples and Comparative Examples on a glass substrate, the final transferred pattern shape and the degree of formation were observed under a microscope, and evaluated based on the following criteria.
<Evaluation Criteria>
(Circle): There is no crack in a board | substrate whole surface.
(Triangle | delta): A crack generate | occur | produces partially.
X: The crack generate | occur | produced on the whole board | substrate.
The results are shown in Table 1 below.
Referring to Table 1, it was confirmed that the coating film formed of the ink composition for roll printing of Examples 1 to 6 had a low YI-D1925 value, so that white visibility was excellent and heat resistance was very excellent. Moreover, printability was very excellent and no crack was generated.
Referring to Figure 1, it can be seen that the coating film formed of the composition of Example 1 exhibits excellent whiteness.
The compositions of Examples 7 and 8 included the binder resin out of the preferred range so that the heat resistance or printability of the coating film formed therefrom was somewhat inferior, but still showed excellent values.
Example 9 including the repeating unit represented by the formula (3) was very excellent in printability.
Examples 10 and 11 in which the content ratio of the monomers represented by the formulas (1) to (3) were outside the preferred ranges, although the performance was slightly reduced, still showed excellent effects.
However, the coating film formed of the ink composition for roll printing of Comparative Examples 1 to 7 had a high YI-D1925 value, resulting in poor heat resistance, poor printability, and cracking.
Referring to Figure 2, the coating film formed of the composition of Comparative Example 1 can be confirmed that the yellowing phenomenon is inferior in whiteness.
Claims (12)
An ink composition for roll printing, comprising a thermal polymerization initiator comprising a sulfonium cation:
[Formula 1]
[Formula 2]
[Formula 3]
[Formula 4]
[Formula 5]
[Formula 6]
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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