JPWO2019219691A5

JPWO2019219691A5 -

Info

Publication number: JPWO2019219691A5
Application number: JP2020562123A
Authority: JP
Publication date: 2023-09-29
Anticipated expiration: 2039-05-14

Description

本開示に従う鉱物インクがインクジェット印刷法に用いられるとき、従来技術のインクを用いて得られたものと比較して、特に細かいグラフィック要素を有するエナメル模様の製造を可能にする。例えば、本発明に従う鉱物インクは、０．０５ｍｍオーダーの幅を有する同種の線、又は０．０５ｍｍオーダーの直径を有する同種のドットを創出することができる。エナメルの厚さは、１μｍのオーダーに達することができる。
When mineral inks according to the present disclosure are used in inkjet printing methods, they allow the production of enamel patterns with particularly fine graphic elements compared to those obtained using prior art inks. For example, mineral inks according to the invention can create homogeneous lines with widths on the order of 0.05 mm, or homogeneous dots with diameters on the order of 0.05 mm. The thickness of enamel can reach the order of 1 μm.

鉱物インク中のガラスフリットの重量割合は、有利には、５０～６５％の間である。有機溶媒は、好ましくは、鉱物インクの、有機溶媒、分散剤、及び界面活性剤の混合物の重量に対して、８０％である。用いられるインクジェット装置の技術的制約と、製造上の制約に従って、有機溶媒の種類と量を調整してもよい。
The weight proportion of glass frit in the mineral ink is advantageously between 50 and 65 %. The organic solvent is preferably 80% based on the weight of the mixture of organic solvent, dispersant, and surfactant of the mineral ink. The type and amount of organic solvent may be adjusted according to technical constraints and manufacturing constraints of the inkjet device used.

本発明の鉱物インクの特定の一実施態様によれば、有機溶媒は、有機溶媒、分散剤、及び界面活性剤の合計重量パーセントに対して、有利には７０～９０％の間である。そのような量の溶媒は、ほとんどのインクジェット印刷装置に好適である。
According to one particular embodiment of the mineral ink of the invention, the organic solvent is advantageously between 70 and 90 % relative to the total weight percentage of organic solvent, dispersant and surfactant. Such amounts of solvent are suitable for most inkjet printing devices.

実施例Ｅ２及びＣＥｘ１の二つのガラス－セラミック板について、エナメルの耐金属摩擦性を、次の手順に従って評価した。先ず、ガラス－セラミック板のエナメル加工された領域の表面を、コイン並びに金属及び／又はエナメル鍋のようないくつかの金属要素を用いて、往復運動を伴って、連続して擦った。そして、調理板の洗浄用に特に設計された市販の種々の洗剤製品を用いて、表面を洗浄した。エナメル加工された表面の劣化を、０～２０のスケールで視覚的に評価する；程度０はエナメル表面が完全に劣化していることに相当し、程度２０は劣化が全く発生していないことに相当する。すなわち、程度が高いほど、エナメルの耐金属摩擦性が高い。
The metal abrasion resistance of the enamel was evaluated for two glass-ceramic plates, Examples E2 and CEx1, according to the following procedure. First, the surface of the enamelled area of the glass-ceramic plate was rubbed continuously with several metal elements, such as a coin and a metal and/or enamel pan, with reciprocating movements. The surfaces were then cleaned using a variety of commercially available detergent products specifically designed for cleaning cooktops. The deterioration of the enamelled surface is visually evaluated on a scale of 0 to 20; a degree of 0 corresponds to complete deterioration of the enamel surface and a degree of 20 corresponds to no deterioration at all. Equivalent to. That is, the higher the degree, the higher the metal abrasion resistance of the enamel.

Claims

A mineral ink for inkjet printing on mineral substrates containing a glass frit, an organic solvent, a dispersant, and a surfactant, the ink comprising:
Mineral ink for inkjet printing on mineral substrates, characterized in that said glass frit contains the following components in the weight range defined below, expressed as a weight percent of said glass frit:
35-50% SiO ₂ ,
15-25% Al ₂ O ₃ ,
1.5-4% Li ₂ O,
22-32% B ₂ O ₃ ,
0-2% Na ₂ O,
2-5% K ₂ O,
1-5% CaO,
1-4% ZrO ₂ .

The mineral ink of claim 1, wherein the glass frit represents 50-65 % by weight of the mineral ink.

The mineral ink according to claim 1 or 2 , wherein the mineral ink further contains a mineral pigment.

4. The mineral ink of claim 3 , wherein the sum of the weight percentages of said glass frit and said mineral pigment corresponds to 50-80% by weight of said mineral ink.

Mineral ink according to claim 3 or 4 , wherein the weight percentage of the glass frit corresponds to 65 to 90% by weight of the sum of the weight percentages of the glass frit and the mineral pigment.

Mineral ink according to any one of claims 3 to 5 , wherein the particle size distribution D90 of the mixture of glass frit and mineral pigment is between 1 μm and 2 μm.

Mineral ink according to any one of the preceding claims, wherein the organic solvent represents 70-90% by weight of the sum of the weight percentages of the organic solvent, the dispersant and the surfactant.

The organic solvent is an organic compound having at least one alcohol functional group and liquid at room temperature, or a mixture of organic compounds having at least one alcohol functional group and liquid at room temperature. 7. The mineral ink according to any one of 7 .

Mineral ink according to any one of the preceding claims, wherein the dispersant is a copolymer having at least one acid function or a mixture of copolymers having at least one acid function.

Mineral ink according to any one of the preceding claims, wherein the surfactant is a polyether or a mixture of polyethers .

A method for manufacturing mineral ink, including the following steps:
a. providing said glass frit containing the following components in the weight ranges defined below, expressed as weight percent of the glass frit;
35-50% SiO ₂ ,
15-25% Al ₂ O ₃ ,
1.5-4% Li ₂ O,
22-32% B ₂ O ₃ ,
0-2% Na ₂ O,
2-5% K ₂ O,
1-5% CaO,
1-4% ZrO ₂ ;
b. mixing said glass frit with a mineral pigment;
c. adding an organic solvent and a dispersant to the mixture obtained in step (b);
d. recirculating milling the mixture obtained in step (c) until the particle size distribution D90 of the mixture of glass frit and mineral pigment is between 1 μm and 2 μm;
e. Adding a surfactant to the milled preparation obtained in step (d).

A method for manufacturing enamelled glass-ceramic plates, including the following steps:
a. providing a glass-ceramic mother glass plate;
b. depositing green enamel on the surface of said plate of mother glass by the method of inkjet printing of mineral inks according to any one of claims 1 to 10 ;
c. heat treating said plate of glass-ceramic mother glass with said green enamel according to the following ceramization cycle:
i. Maintaining nucleation between 650 and 860°C for 15 minutes to 4 hours,
ii. Growth is maintained between 860-1100°C for 10 minutes to 2 hours.

The method of manufacturing an enamelled glass-ceramic plate according to claim 12 , wherein the inkjet printing method is a drop-on-demand inkjet printing method.

said plate of glass-ceramic mother glass is formed of a lithium aluminosilicate glass, said lithium aluminosilicate glass containing the following components in the weight ranges defined below, expressed as weight percentages of said glass: , a method for producing an enamelled glass-ceramic plate according to claim 12 or 13 :
SiO ₂ 52-75%,
Al ₂ O ₃ 12-27%,
Li ₂ O 1.5-5.5%,
Na ₂ O 0-3%,
K ₂ O 0-3%,
CaO 0-5%,
MgO 0-5%,
SrO 0-5%,
BaO 0-5%,
ZnO 0-5%,
TiO ₂ 1-6%,
ZrO ₂ 0-3%,
P ₂ O ₅ 0-8%.