WO2013047962A1 - Encre d'impression pour une surface céramique et procédé d'impression pour une surface céramique l'utilisant - Google Patents

Encre d'impression pour une surface céramique et procédé d'impression pour une surface céramique l'utilisant Download PDF

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Publication number
WO2013047962A1
WO2013047962A1 PCT/KR2012/001351 KR2012001351W WO2013047962A1 WO 2013047962 A1 WO2013047962 A1 WO 2013047962A1 KR 2012001351 W KR2012001351 W KR 2012001351W WO 2013047962 A1 WO2013047962 A1 WO 2013047962A1
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Prior art keywords
ceramic surface
printing
ink
ceramic
weight
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PCT/KR2012/001351
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English (en)
Korean (ko)
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박충권
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(주)더몰론코리아
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Publication of WO2013047962A1 publication Critical patent/WO2013047962A1/fr

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/34—Printing on other surfaces than ordinary paper on glass or ceramic surfaces
    • 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

Definitions

  • the present invention relates to a ceramic surface printing ink and a ceramic surface printing method using the same, and more particularly, by printing a ceramic surface by using a ceramic surface printing ink made of a polyester-modified silicone resin, a heat-resistant pigment, etc.
  • the present invention relates to a ceramic surface printing ink and a ceramic surface printing method using the same, which can be printed as well as have excellent adhesion to a printing film.
  • ceramic products that are applied to various fields such as daily necessities, electronic components, etc., have a labeling or logo on the surface thereof.
  • the decorative method for marking a logo on the ceramic surface is repeated 2 to 3 times by coating the ceramic ink by the screen printing method, as known in the Republic of Korea Patent Publication No. 10-0302113, and then heating the ceramic coating film After dissolving, the relief of ceramic products is decorated, or before printing, the surface of the ceramic material is processed by uneven method such as casting, laser processing, extrusion molding, etc., and then coating ceramic paint thereon. Labeling or logos are indicated.
  • the coating film formed on the ceramic surface is formed of C 1 to C 4 , such as methyl, ethyl, propyl, butyl, etc.
  • Low surface activity is formed by the alkyl group, and low surface energy is formed on the surface of the coating film due to floating and adsorption on the surface of the coating film of silane oligomers having low surface energy formed during curing of the film of the coating film.
  • the surface of the coating film cured by the above methods has a water contact angle of about 70 ° or more, resulting in a low surface energy, thereby degrading wettability of the ink and adhesion after curing.
  • the coating film surface of the organic binder ink causes wettability and deterioration of adhesion.
  • a general printing method for marking labels or logos on a ceramic coating film based on an organic modified silicone resin paint as a binder is a high heat-resistant printing ink. It is not adhered properly to the wetted area, the bond strength with the coating film is lowered, even when using various kinds of inks, the ink did not have sufficient adhesion even after the dry curing, and this did not apply commercially.
  • the present invention can be simply printed on the ceramic surface using the ink for printing the ceramic surface made of polyester modified silicone resin, heat-resistant pigment, etc. as a means for printing the ceramic surface as a solution for solving the problems as described above.
  • the present invention relates to an ink for printing a ceramic surface and a method of printing a ceramic surface using the same, which can impart excellent adhesion to a printing film.
  • the present invention in printing on the ceramic surface using the ink for printing the ceramic surface, by performing a flame treatment of about 10 seconds to the portion to be printed on the surface of the ceramic to be adhered by a pretreatment method, an organic modified silicone resin To improve the wettability and adhesion by converting the low surface energy (water contact angle of 70 ° or more) of the adherend with the heat-resistant ceramic coating film as a binder into high surface energy (water contact angle of 30 ° or less) through the flame spinning treatment as described above.
  • Another object of the present invention is to provide a ceramic surface printing method using the ceramic surface printing ink.
  • alumina powder Allumina Powder
  • fumed silica 0.5 to 5% by weight
  • the ink for ceramic surface printing which consists of 29 to 45 weight% of solvents makes a solution to a subject.
  • pre-treatment step (S1) for flame treatment by spinning a flame of 1200 °C ⁇ 2000 °C for 5 seconds to 10 seconds on the ceramic surface of the adherend ;
  • the modified silicone resin is a polymerized silicone resin to a polyester resin, the content of the silicone resin is preferably 40 to 90% by weight.
  • the solvent is propylene glycol methyl ether acetate (PMA), isopropyl alcohol (Iso Propyl Alcohol, IPA), butyl acetate (Butyl Acetate, BA) or Cocosol # 150 (Kocosol # 150 , SK Corp.) It is preferable to use at least one selected from the group consisting of.
  • the printing step (S2) after leaving the patterned silk screen plate on the ceramic surface, it is preferable to pour the ink for printing the ceramic surface on the silk screen plate, and to print by pushing with a roller or a blade.
  • the printing step (S2) after pouring the ink for printing the ceramic surface to the patterned copper plate, pressurized the silicon pad to transfer the pattern to the silicon pad, and then press the silicon pad transferred the pattern on the ceramic surface It is preferable to print by.
  • the present invention uses the ink for printing the ceramic surface made of polyester modified silicone resin, heat-resistant pigment, etc. as a means for printing the ceramic surface as a solution for solving the problems as described above, the pretreatment method to print the ceramic surface of the adherend Flame treatment for about 10 seconds on the part, and then the pattern is simply printed, dried and cured, which not only makes it easy to print on the ceramic surface but also gives excellent adhesion to the printing film. There is an advantage.
  • FIG. 1 is a flow chart showing a ceramic surface printing method using the ink for printing the ceramic surface according to an embodiment of the present invention.
  • the ink for printing the ceramic surface according to the present invention modified silicone resin 20 to 60% by weight, heat-resistant pigment 10 to 40% by weight, alumina powder (Alumina Powder) 0.5 to 10% by weight, fumed silica (fumed silica) 0.5 to 5 It is characterized by consisting of 29% by weight to 45% by weight and a solvent.
  • alumina powder Allumina Powder
  • fumed silica fumed silica
  • the modified silicone resin used in the present invention is a modified silicone resin having a content of 40 to 90% by weight of a silicone resin, which is added as a binder and polymerized with a silicone resin to a polyester resin, which is commonly applied to conventional paints. Apply.
  • the modified silicone resin is 20 to 60% by weight is mixed, when the mixed amount of the modified silicone resin is less than 20% by weight, there is a risk that the role of the binder is insufficient, when it exceeds 60% by weight, other There is a fear that the function of the ink may be lowered due to the lack of other mixtures.
  • the modified silicone resin has a lower heat resistance when the silicon content is less than 40% by weight, and when the silicon content is more than 90% by weight, the adhesion and pigment dispersibility are increased as the content of the polyester resin is increased. There is a risk of deterioration.
  • the heat-resistant pigment used in the present invention is a pigment having heat resistance (400 °C or more), inorganic colored pigments such as heat-resistant white pigment (Titanium dioxide), black pigment (Copper chrome black), blue pigment (Cobalt aluminate blue spinel) (Inorganic color pigment) Select one or more from the group and use them together.
  • inorganic colored pigments such as heat-resistant white pigment (Titanium dioxide), black pigment (Copper chrome black), blue pigment (Cobalt aluminate blue spinel) (Inorganic color pigment) Select one or more from the group and use them together.
  • the heat-resistant pigment is 10 to 40% by weight is mixed, if the mixing amount of the heat-resistant pigment is less than 10% by weight, there is a fear that the corresponding color may not be expressed, when it exceeds 40% by weight, relatively other mixtures There is a possibility that the function of the ink may be degraded due to the lack of.
  • the alumina powder used in the present invention is to improve the compactness of the coating film and to improve the abrasion resistance of the coating film. If the mixing amount of the alumina powder is less than 0.5% by weight, the density of the coating film is insufficient and there is a fear of cracking after curing. and a, there is a fear that the function of the ink decreases, the other the lack of other compounds if it exceeds 10% by weight.
  • Fumed silica used in the present invention is added to improve the dispersibility of each mixture to control the viscosity of the ink, and if the mixed amount of fumed silica is less than 0.5% by weight, each mixture may not be dispersed well. If there is more than 5% by weight, the viscosity may be too low.
  • the solvent used in the present invention is mixed in order to improve the shelf life and workability of the ink, Propyleneglycol Methyl ether Acetate (PMA), Iso Propyl Alcohol (IPA), Butyl At least one selected from the group consisting of acetate (Butyl Acetate, BA) or cocosol # 150 (Kocosol # 150, SK) is used in combination.
  • PMA Propyleneglycol Methyl ether Acetate
  • IPA Iso Propyl Alcohol
  • Butyl At least one selected from the group consisting of acetate (Butyl Acetate, BA) or cocosol # 150 (Kocosol # 150, SK) is used in combination.
  • the solvent is mixed 29 to 45% by weight, when the mixing amount of the solvent is less than 29% by weight, there is a risk that the storage and workability of the ink may be lowered, if the solvent exceeds 45% by weight, the print film defect Or the residual solvent may lower the physical properties of the printing film.
  • pre-treatment step (S1), printing step (S2), drying step (S3), curing step (S4) and cooling It comprises a step S5.
  • the pretreatment step (S1) is a step of flame treatment on the ceramic surface of the adherend, a conventional flame spinning means equipped with a torch (torch) in the fuel gas (propane, butane, LPG, LNG, etc.) After forming a blue flame (1200 ⁇ 2000 °C), it is spin-treated on the ceramic surface for 5 seconds to 10 seconds.
  • the flame spinning treatment time is less than 5 seconds, there is a risk that the oxidation and removal effects as described above are inadequate, and if it exceeds 10 seconds, there is a fear that a grind is formed on the ceramic surface or a crack occurs on the ceramic surface. .
  • the adherend having the ceramic surface means an adherend formed by coating and curing an organic modified silicone resin binder paint containing an organic modified silicone resin, a silica sol and an inorganic pigment on the surface thereof to form a ceramic coating film.
  • the present invention converts the low surface energy (water contact angle of 70 ° or more) of the adherend on which the heat-resistant ceramic coating film formed of an organic modified silicone resin as a binder into high surface energy (water contact angle of 30 ° or less) through the flame spinning treatment as described above. It is to improve the wettability and adhesion.
  • the printing step (S2) is a step of printing using a ceramic surface printing ink on the ceramic surface subjected to the pretreatment step (S1), it is possible to apply a variety of printing methods, in the present invention, as an embodiment, silk screen The printing method or pad printing method was applied.
  • a silkscreen plate engraved with a pattern is placed on a ceramic surface, and then the ink for printing the ceramic surface is poured on the silkscreen plate, and then printed by pushing with a roller or a blade.
  • the pad printing method is to pour the ink for printing the ceramic surface on the copper plate, the pattern is imprinted, press the silicon pad to transfer the pattern to the silicon pad, and then press the printed silicon pad on the ceramic surface to print. .
  • the drying step (S3) is a step of drying the ink printed on the ceramic surface for 5 to 20 minutes at room temperature (20 ⁇ 25 °C), when the drying time is less than 5 minutes, the printed ink is not completely dried If it exceeds 20 minutes, the drying degree of the ink is no longer improved compared to the drying time, which may lower the production efficiency.
  • the curing step (S4) is a step of curing the ink printed on the ceramic surface in a curing furnace of 250 ⁇ 320 °C 10-30 minutes, the curing furnace can be applied to a variety of means that can cure the ink In addition to the usual curing furnaces, ovens and the like can be used.
  • the adherend that passed through the curing step (S4) is cooled to room temperature (20 ⁇ 25 °C) by the cooling step (S5) to print the ink for printing the ceramic surface on the ceramic surface.
  • a coating material of an organic modified silicone resin paint as a binder to the surface of the adherend made of aluminum material and forming a ceramic coating film through high-temperature firing, thereafter, in the pretreatment step (S1), the flame spinning treatment on the ceramic surface of the adherend
  • a torch is mounted in butan gas and the lock valve of the torch is opened to release butane gas and ignited using a suitable ignition source.
  • the amount of emitted gas is adjusted so that the color of the ignited flame becomes blue (when a blue flame is produced, the temperature of the flame reaches a level at which flame treatment is possible at 1200 ° C. or higher).
  • the ink for printing the ceramic surface on the silkscreen plate (modified silicone resin) 60% by weight, heat-resistant pigment 10% by weight, alumina powder 0.5% by weight, fumed silica 0.5% by weight and a solvent of 29% by weight) was pushed with a roller to print.
  • the drying step (S3) the ink printed on the ceramic surface is dried for 10 minutes at room temperature (22 °C), and in the curing step (S4), the ink printed on the ceramic surface in a curing furnace of 300 °C 10 After curing for a minute, as the cooling step (S5), the adherend that passed through the curing step (S4) was completed by cooling at room temperature (22 °C).
  • the coating material which consists of an organic modified silicone resin coating material as a binder is apply
  • a torch is mounted on butane gas and the lock valve of the torch is opened to release butane gas and ignite using an appropriate ignition source. Let's do it.
  • the amount of emitted gas is adjusted so that the color of the ignited flame becomes blue (when a blue flame is produced, the temperature of the flame reaches a level at which flame treatment is possible at 1200 ° C. or higher).
  • the pad printing method is applied without any delay after the flame treatment, and the ceramic surface printing ink (20 wt% modified silicone resin, 40 wt% heat-resistant pigment, alumina powder Powder) 10% by weight, fumed silica (5% by weight) and 45% by weight of solvent), and the silicone pad is pressurized to transfer the pattern to the silicon pad, and then the silicon pad to which the pattern is transferred is ceramic Press to print on the surface.
  • the ceramic surface printing ink (20 wt% modified silicone resin, 40 wt% heat-resistant pigment, alumina powder Powder) 10% by weight, fumed silica (5% by weight) and 45% by weight of solvent
  • the drying step (S3) the ink printed on the ceramic surface is dried for 10 minutes at room temperature (22 °C), and in the curing step (S4), the ink printed on the ceramic surface in a curing furnace of 300 °C 10 After curing for a minute, as the cooling step (S5), the adherend that passed through the curing step (S4) was completed by cooling at room temperature (22 °C).
  • Example 1 The same method as in Example 1 was applied, but did not undergo the flame spinning process, which is a pretreatment step (S1) of Example 1, and applied to CMW Senotherm 3300 ink, not ink printed on the ceramic surface of Example 1. It was.
  • Example 2 The same method as in Example 2 was applied, but did not undergo the flame spinning process, which is the pretreatment step (S1) of Example 2, and applied CNT's Senotherm 3300 ink, not ink printed on the ceramic surface of Example 2. It was.
  • Examples 1 and 2 were 20 °, but the water contact angles of Comparative Examples 1 and 2 were 80 °. That is, in Examples 1 and 2, the silane oligomers absorbed and adhered to the ceramic surface of the adherend are oxidized and removed through the flame spinning process, which is a pretreatment step (S1), and at the same time, the contaminated organic matter and moisture are determined to be removed. do.
  • Examples 1 and 2 were not scratched at all even in 5H, Comparative Examples 1 and 2 The scratches were visually confirmed even at 3H. That is, it can be seen that Examples 1 and 2 are also excellent in hardness.
  • the modified silicone resin is a polymerized silicone resin to a polyester resin, the content of the silicone resin is preferably 40 to 90% by weight.
  • the solvent Propyleneglycol Methyl ether Acetate (PMA), Iso Propyl Alcohol (IPA), Butyl Acetate (Butyl Acetate, BA) or Cocosol # 150 (Kocosol # 150 , SK Corp.) It is preferable to use at least one selected from the group consisting of.
  • the present invention in the ceramic surface printing method using the ink for printing the ceramic surface, the pretreatment step of performing a flame treatment by spinning a flame of 1200 °C ⁇ 2000 °C for 5 seconds to 10 seconds on the ceramic surface of the adherend (S1); A printing step (S2) of printing using a ceramic surface printing ink on the ceramic surface which has undergone the pretreatment step (S1); Drying step (S3) for drying the ink printed on the ceramic surface for 5 to 20 minutes at 20 ⁇ 25 °C; A curing step of curing the ink printed on the ceramic surface in a curing furnace at 250 to 320 ° C. for 10 to 30 minutes (S4); And a cooling step (S5) of cooling the adherend that has undergone the curing step (S4) at 20 to 25 ° C .; .
  • the ink for printing the ceramic surface 20 to 60% by weight of modified silicone resin, 10 to 40% by weight of heat-resistant pigment, 0.5 to 10% by weight of alumina powder, 0.5 to 5% by weight of fumed silica and solvent 29 to 45 It is preferably made up by weight%.
  • the printing step (S2) after fixing the silkscreen plate engraved with the pattern on the ceramic surface, it is preferable to pour the ink for printing the ceramic surface on the silkscreen plate, and to print by pushing with a roller or a blade.
  • the printing step (S2) after pouring the ink for printing the ceramic surface to the patterned copper plate, pressurized the silicon pad to transfer the pattern to the silicon pad, and then press the silicon pad transferred the pattern on the ceramic surface It is preferable to print by.
  • the present invention is a means for printing a ceramic surface using a ink for printing a ceramic surface made of a polyester modified silicone resin, heat-resistant pigments, etc., so that not only can be easily printed on the ceramic surface but also to give an excellent printing coating film adhesion
  • the organic modified silicone resin paint is applied by performing flame treatment for about 10 seconds to the portion to be printed on the surface of the ceramic to be adhered by a pretreatment method.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une encre d'impression pour une surface céramique et un procédé d'impression pour une surface céramique l'utilisant. En particulier, la surface céramique, consistant en 20-60 % en poids d'une résine de silicone modifiée, 10-40 % en poids d'un pigment résistant à la chaleur, 0,5-10 % en poids de poudres d'aluminium, 0,5-5 % en poids de silice fumée et 29-45 % en poids d'un solvant, est imprimée, permettant ainsi à l'encre d'être facilement imprimée sur la surface céramique et fournissent également une bonne adhésion d'un film imprimé. Egalement, la présente invention concerne un procédé d'impression pour une surface céramique à l'aide de l'encre d'impression pour une surface céramique, caractérisé en ce que l'aptitude au mouillage et l'adhésion peuvent être améliorées par conversion de la faible énergie de surface (angle de contact avec l'eau de 70° ou plus) d'un objet sur lequel un film imprimé de céramique résistant à la chaleur contenant une peinture de résine de silicone modifiée organique comme liant est formé, en énergie de surface élevée (angle de contact avec l'eau de 30° ou moins) par un traitement à la flamme, à l'aide du procédé d'impression pour une surface céramique, les procédés d'impression comprenant : une étape de prétraitement (S1) consistant à effectuer un traitement à la flamme en soumettant l'objet à une flamme de 1200°C-2000 °C pendant 5-10 secondes ; une étape d'impression (S2) d'impression de la surface céramique, qui a subi l'étape de prétraitement (S1), en utilisant l'encre d'impression pour une surface céramique ; une étape de séchage (S3) de séchage de l'encre imprimée sur la surface céramique à 20°C-25 °C pendant 5-20 minutes ; une étape de durcissement (S4) de durcissement de l'encre imprimée sur la surface céramique dans un four de durcissement à 250°C-320°C pendant 10-30 minutes ; et une étape de refroidissement (S5) de refroidissement à 20°C-25°C de l'objet qui a subi l'étape de durcissement (S4).
PCT/KR2012/001351 2011-09-27 2012-02-22 Encre d'impression pour une surface céramique et procédé d'impression pour une surface céramique l'utilisant WO2013047962A1 (fr)

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KR10-2011-0097530 2011-09-27
KR1020110097530A KR101296245B1 (ko) 2011-09-27 2011-09-27 세라믹 표면 인쇄용 잉크를 이용한 세라믹 표면 인쇄방법

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CN113543490A (zh) * 2021-07-08 2021-10-22 江西晶弘新材料科技有限责任公司 一种增加油墨在陶瓷基板上附着力的方法

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KR101573790B1 (ko) * 2015-07-28 2015-12-02 (주) 더몰론코리아 항균기능이 있는 세라믹 프린팅 잉크 조성물
KR101941747B1 (ko) * 2015-10-14 2019-01-23 박란수 세라믹 코팅용 전사지, 이를 사용한 조리용기 및 조리용기의 제조방법
KR102032024B1 (ko) * 2017-09-15 2019-10-14 김기범 실리콘부착을 위한 접착제용 잉크 조성물 제조방법 및 그 잉크 조성물
CN109293396A (zh) * 2018-09-30 2019-02-01 何兴安 一种锗元素环保陶瓷及其制作方法
KR102400074B1 (ko) * 2020-02-28 2022-05-23 (주)다대메이커스 내구성이 우수한 세라믹 타일 및 그 제조방법
KR102465073B1 (ko) 2022-06-23 2022-11-10 대한화인세라믹 주식회사 도안이 표현되는 반투명 도막층을 구비하는 주방기물 코팅방법과 이에 의해 제조된 주방기물

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CN103881474A (zh) * 2014-02-26 2014-06-25 金甲化工企业(中山)有限公司 一种耐高温不黄变油墨
CN113543490A (zh) * 2021-07-08 2021-10-22 江西晶弘新材料科技有限责任公司 一种增加油墨在陶瓷基板上附着力的方法
CN113543490B (zh) * 2021-07-08 2023-01-10 江西晶弘新材料科技有限责任公司 一种增加油墨在陶瓷基板上附着力的方法

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