JPH0120080B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a ceramic painting transfer paper used when painting ceramics or glass. One method for painting ceramics, glass, etc. is to print a pattern ink layer containing ceramic pigments on a mount that has been coated with a glue such as dextrin solution and dried, and then print a cover coat layer on top of that. There is a known method of using printed transfer paper. This method uses a so-called "slide" transfer method using water, where the integrated cover coat layer and pattern ink layer are peeled off from the backing paper in water, and the pattern ink layer is attached to ceramics or glassware, dried, and then heated to a high temperature. In this method, the cover coat layer and ink binder are fired and painted. At present, solvent-based methacrylic resins are mainly used in the pattern ink layer of transfer paper for painting ceramics, but there are problems associated with this that need to be resolved, and this has become a serious problem in the kiln industry. In other words, (1) the use of solvent-based resins causes significant contamination of the workplace environment and air pollution due to the solvents, and urgent solutions are needed from the perspectives of occupational safety and health as well as pollution; (2) solvent-based resins Pattern inks generally contain high boiling point solvents such as sorbet, butanol, etc. to prevent clogging of screen printing plates.
xylene, butyl cellosolve, terpineol,
Cellosolve acetate, etc. are used, and as a matter of course, the drying speed is slow and productivity does not improve. (3) Current solvent-based pattern inks dry slowly and are prone to blocking phenomenon due to residual solvent. 4) For this reason, it is necessary to insert parapine paper or the like to prevent blocking in the current transfer paper for painting ceramics, which requires a great deal of expense and labor. (5) Ceramics using current solvent-based design inks Transfer paper for transfer paper tends to change over time, and suffers from many problems such as loss of flexibility during storage and markedly poor adhesion properties. As a solution to these drawbacks of solvent-based resins, ultraviolet curable resins, which are so-called solvent-free resins, have been attracting attention, and it is well known that various compositions have been proposed. Therefore, it seems natural to apply ultraviolet curable resin to the painting of ceramics and glass, and attempts to do so are well known (edited by the Japan Screen Printing Technology Association; Screen Printing Handbook, P359, May 31, 1978). (Published on the day). However, it is extremely difficult to apply ultraviolet curable resins to transfer paper for painting ceramics, and the application has not yet reached the stage of practical use. The reason for this is that when conventional ultraviolet curable resins are applied to pattern ink layers, (1) the thermal decomposition temperature is high, and before the carbonized residue completely disappears, heat-resistant inorganic pigments, which are ceramic painting pigments, As the flux or frit begins to melt and sinter, pigments, etc. are repelled, making it impossible to paint. (2) When the ultraviolet curable resin thermally decomposes, it scatters together with the pigments, leaving no pattern behind. (3) The pattern ink layer Because it contains 40 to 70% by weight of the above pigments, it has low ultraviolet transmittance and is prone to curing failure.
(4) As a result, hardening wrinkles occur, and these wrinkle patterns do not disappear even after firing, making it impossible to create beautiful paintings.
Furthermore, (5) the pattern ink used in the transfer paper of the present invention is required to have flexibility in the coating film after curing, in addition to the above-mentioned sinterability and curability. There are many reasons why I am not satisfied with this. As described above, transfer paper for ceramic painting using ultraviolet curable resin has not yet been developed, and the development of such paper is strongly desired by the kiln industry. The inventors of the present invention have conducted intensive research to solve the above-mentioned problems and meet the demands of the industry. As a result, the design ink layer of transfer paper for painting ceramics contains (meth)acrylic acid ester polymers, polymerizable compounds, and light. The inventors discovered that by using an ultraviolet curable ink consisting of a sensitizer and a pigment for ceramic painting, it was possible to obtain a transfer paper for ceramic painting that has firing properties equivalent to or better than conventional solvent-based transfer paper, and finally arrived at the present invention. . That is, the present invention provides a transfer paper for ceramic painting comprising a mount, a pattern ink layer, and a cover coat layer, in which the pattern ink layer is made of a polymer or copolymer () of a compound represented by the following general formula (A), a polymer This transfer paper for ceramic painting is characterized in that it is a layer obtained by photo-curing an ultraviolet curable ink containing a chemical compound (2), a photosensitizer (2), and a ceramic painting pigment (3) as essential components. General formula (A) (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group having a carbon number of C ₁ to C ₂₀ , an aralkyl group,
It is an aryl group. ) In the present invention, since the pattern ink layer is the above-mentioned ultraviolet curable ink, it has a firing property equal to or higher than that of conventional solvent-based transfer paper, and has the following characteristics. (b) There is no clogging of screen printing plates, etc., and the reproducibility of fine pattern printing is good, making it possible to create high-quality decorations. (b) There is little variation in the film thickness of the pattern ink layer, and there is little unevenness in firing. (c) The UV-curable resin of the pattern ink layer is much more flexible than conventional UV-curable resins, so uniform firing is possible without scattering together with pigments during thermal decomposition. The pattern ink layer of the ceramic painting transfer paper used in the present invention contains a polymer or copolymer () of the compound represented by the general formula (A), a polymerizable compound (), a photosensitizer () and An ultraviolet curable ink containing ceramic painting pigment () as an essential ingredient is used. The polymer or copolymer () of the compound represented by the general formula (A) used in the present invention refers to a polymer or copolymer () of a (meth)acrylic acid ester such as methyl (meth)acrylate or ethyl (meth)acrylate. It may be used alone or as a copolymer, or as a copolymer of (meth)acrylic acid esters and styrene, α-methylstyrene, vinyltoluene, butadiene, acrylonitrile, or the like. Particularly preferred polymers include polymethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, and methyl methacrylate-ethyl methacrylate copolymer.
These include propyl methacrylate copolymer, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-lauryl methacrylate copolymer, and the molecular weight thereof is 10,000 to 1 million, preferably 2.
It is between 10,000 and 800,000. These polymers or copolymers may be used alone or in combination of two or more. The polymerizable compound () used in the present invention is a photopolymerizable compound having one or more polymerizable double bonds in the molecule. Examples of photopolymerizable compounds having one polymerizable double bond in the molecule include (i) styrene, α
- Styrenic compounds such as methylstyrene and chlorostyrene, (ii) methyl (meth)acrylate (meaning methyl acrylate and methyl methacrylate, hereinafter similarly abbreviated), ethyl (meth)acrylate, n- and i-propyl ( meth)acrylate, n-, sec- and t-butyl (meth)acrylate, 2-ethylhexyl (meth)
Acrylate, lauryl (meth)acrylate,
Alkyl (meth)acrylates such as tetrahydrofuryl (meth)acrylate and stearyl (meth)acrylate, or alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and phenoxyethyl Allyloxyalkyl (meth)acrylate such as (meth)acrylate, hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, halogen-substituted alkyl (meth)acrylate, or polyethylene glycol mono(meth)acrylate, polypropylene glycol mono( Examples include polyoxyalkylene glycol mono(meth)acrylate such as meth)acrylate, and substituted alkyl mono(meth)acrylate such as alkoxypolyoxylalkylene mono(meth)acrylate. (iii) Mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide or/and propylene oxide adducts of bisphenol A, or ethylene oxide and/or propylene oxide adducts of hydrogenated bisphenol A, etc. Examples include mono(meth)acrylates of alkylene oxide adducts of hydrogenated bisphenol A. moreover
(iv) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance, is further reacted with an alcoholic hydroxyl group-containing (meth)acrylate. (meth)Urethane modified mono(meth) having acryloyloxy group
Acrylate, or (v) Epoxy mono(meth)acrylate obtained by reacting acrylic acid or methacrylic acid with a compound having one or more epoxy groups in the molecule, or (vi) Acrylic acid or methacrylic acid as a carboxylic acid component. , and oligoester mono(meth)acrylate obtained by reacting a polyhydric carboxylic acid with a polyhydric alcohol having a valence of 2 or more as an alcohol component. Examples of photopolymerizable compounds having two polymerizable double bonds in the molecule include (i) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate. ) acrylate, alkylene glycol di(meth)acrylate such as neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, di propylene glycol di(meth)acrylate,
Polyoxyalkylene glycol di(meth)acrylate such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, substituted alkylene such as halogen-substituted alkylene glycol di(meth)acrylate, hydroxyl group-substituted alkylene glycol di(meth)acrylate, etc. glycol di(meth)acrylate, (ii) di(meth)acrylate of alkylene oxide adducts of bisphenol A, such as ethylene oxide or/and propylene oxide adducts of bisphenol A, ethylene oxide or/and propylene of hydrogenated bisphenol A; Di(meth)acrylates of alkylene oxide adducts of hydrogenated bisphenol A such as oxide adducts, (iii) terminal isocyanate group-containing compounds obtained by reacting in advance a diisocyanate compound and a compound containing two or more alcoholic hydroxyl groups. , and a urethane-modified di(meth) having two (meth)acryloyloxy groups in the molecule obtained by further reacting an alcoholic hydroxyl group-containing (meth)acrylate.
acrylate, (vi) epoxy di(meth)acrylate obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or/and methacrylic acid, (v) acrylic acid or methacrylic acid as a carboxylic acid component, Representative examples include oligoester di(meth)acrylate obtained by reacting a polyhydric carboxylic acid with a polyhydric alcohol having a valence of 2 or more as an alcohol component. Examples of photopolymerizable compounds having three or more polymerizable double bonds in the molecule include (i) trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth) Polyhydric (meth)acrylates of trivalent or higher aliphatic polyhydric alcohols such as acrylates, polyhydric (meth)acrylates of trivalent or higher halogen-substituted aliphatic polyhydric alcohols, or hydroxyl-substituted aliphatic polyhydric alcohols of trivalent or higher hydrides Polyhydric (meth)acrylate of alcohol,
(ii) Three or more terminal isocyanate group-containing compounds obtained by reacting a diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds in advance, and further reacting with an alcoholic hydroxyl group-containing (meth)acrylate. There are urethane-modified polyvalent (meth)acrylates having (meth)acryloyloxy groups. The di(meth)acrylates used as the polymerizable compound () are particularly di(meth)acrylates of _C2 to _C12 alkylene glycols,
Glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and di(meth)acrylate of ethylene oxide and/or propylene oxide adducts of bisphenol A. ) is preferably a (meth)acrylate selected from acrylates. These polymerizable compounds () may be used alone or in combination. 1 in the molecule in the polymerizable compound () of the ultraviolet curable ink used in the pattern ink layer of the present invention.
The proportion of the compound having 2 polymerizable double bonds is not particularly limited, but is 10 to 100% by weight, preferably 30 to 100% by weight.
Weight%. The blending ratio of the polymer or copolymer () of the compound represented by the general formula (A) and the polymerizable compound () in the ultraviolet curable ink used in the present invention is ():()=5:95-90 :10, preferably
The hours are 20:80-80:20. The photosensitizer () used in the present invention is
Compounds that promote the photopolymerization reaction of the polymerizable compound () are not particularly limited, and include, for example, benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin, and a-methylbenzoin; Anthraquinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, benzophenones such as benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, diphenyl disulfide, tetramethylthiuram Examples include sulfur-containing compounds such as disulfide, pigments such as methylene blue, eosin, and fluorescein, and these may be used alone or in combination of two or more. The blending amount of the photosensitizer () is 0.052 to 20% relative to the total amount of the polymer or copolymer () of the compound represented by the general formula (A) and the polymerizable compound ().
% by weight, especially 0.5-10% by weight is preferred. In addition, in order to increase the photopolymerization reaction promoting effect of the photosensitizer (), amines such as triethanolamine, triethylamine, N,N-diethylaminoethyl (meth)acrylate, and triphenylphosphide are used as photosensitizers. It is also possible to use phosphorus compounds such as phosphorus in combination. Pigments for painting ceramics used in the present invention include heat-resistant inorganic pigments, frits, fluxes, and the like. Heat-resistant inorganic pigments () include magnesia, alumina, titania, tin oxide, antimony oxide, platinum, palladium, chromium oxide, cobalt oxide, manganese oxide, cerium oxide, nickel oxide, iron oxide, copper oxide, vanadium stannate, Lead chromate, uranium yellow, cadmium sulfide, gold, iron titanate, uranium titanate, cadmium-selenium red, cobalt titanate, gold chloride, manganese sulfate,
Typical examples include vanadium pentoxide. Frits and fluxes promote uniform color development of pigments by selecting their ingredients.
It is used to adjust the firing temperature. Its components include Li ₂ O, Na ₂ O, K ₂ O,
MgO, CaO, BaO, _ZnO , PbO, _B2O3 , _{Al2O3 ,}
SiO ₂ and the like, and various compositions are selected depending on the purpose. The amount of the ceramic painting pigment used in the present invention is usually 40 to 70% by weight of the ultraviolet curable ink. In the transfer paper for ceramic painting of the present invention, the cover coat layer is made of a conventional solvent-based resin, such as LR-
1292, LR-1014 (manufactured by Mitsubishi Rayon), LR-1042
(manufactured by Yamashiro Ink), LO-649Z, LO-649ZD (manufactured by Goutou Kagaku), etc. can also be used, but polymers or copolymers () of the compound represented by the general formula (A), polymerization It is more preferable to use an ultraviolet curable resin containing a chemical compound () and a photosensitizer () as essential components, since the various disadvantages of solvent-based resins can be overcome. The polymer or copolymer () of the compound represented by the general formula (A), the polymerizable compound (), and the photosensitizer (), which are components of the ultraviolet curable resin used in the cover coat layer, are the components of the ultraviolet curable resin used in the cover coat layer. The compounds to be used in the ultraviolet curable ink used in the pattern ink layer are appropriately selected and used in the proportions described above. Known thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, thixotropic agents, etc. are added to the ultraviolet curable ink used for the above-mentioned pattern ink layer and the ultraviolet curable resin used for the cover coat layer. It is used by adjusting its viscosity, storage stability, printability, etc. The mount for the ceramic painting transfer paper of the present invention includes:
Single paper, collodion coated paper, separate paper, thermal flat paper, etc. are used. The transfer paper for painting ceramics of the present invention is produced by printing a pattern on the above-mentioned mount with the ultraviolet curable ink by a method such as screen printing or gravure offset printing, irradiating it with ultraviolet rays and curing it, and then applying the ultraviolet curable ink as a cover coat layer. It is made by printing resin onto a pattern and curing it by irradiating it with ultraviolet light. The light source used to irradiate ultraviolet rays is
Sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, etc. are used. The transfer paper for ceramic decoration of the present invention not only has the basic characteristics required for a transfer paper for ceramic decoration, such as firing properties and adhesion properties, but also has the ability to create fine patterns because it uses ultraviolet curing ink. The reproducibility of images is extremely good, and the ripple effects are significant, such as improving the work environment, increasing productivity, and saving labor. The transfer paper for painting ceramics of the present invention takes advantage of these advantages and is used for painting sintered bodies such as ceramics, porcelain, glass, tiles, and ceramics. EXAMPLES Examples will be given below to explain the present invention in more detail, but the present invention is not limited by the Examples in any way. Reference production example 1 Methyl methacrylate-n-butyl methacrylate copolymer 40 with a molecular weight of 75,000 and a glass transition point of 50°C
1 part, 55 parts of hydroxyethyl methacrylate, 5 parts of ethylene glycol dimethacrylate, 1 part of a leveling agent, and 10 parts of benzoin ethyl ether as a photosensitizer were mixed and dissolved at room temperature to obtain an ultraviolet curable resin (A) for cover coat. Ta. Reference production example 2 30 parts of methyl methacrylate-ethyl methacrylate copolymer with a molecular weight of 115,000 and a glass transition point of 65°C, 55 parts of hydroxyethyl methacrylate, 15 parts of tetrahydrofurfuryl acrylate, leveling agent 1
7, benzoin methyl ether as a photosensitizer
The components were mixed and dissolved at room temperature to obtain an ultraviolet curable resin (B) for cover coating. Reference production example 3 20 parts of hydroxyethyl methacrylate, 25 parts of ethylene glycol dimethacrylate, 50 parts of diacrylate of 4 moles of ethylene oxide adduct of bisphenol A, 1 part of leveling agent, and 7 parts of benzoin methyl ether as a photosensitizer at room temperature. The mixture was mixed and dissolved to obtain an ultraviolet curable resin (C) for cover coat. Production example 1 Methyl methacrylate-n-butyl methacrylate copolymer 40 with a molecular weight of 75,000 and a glass transition point of 50°C
parts, 30 parts of tetrahydrofurfuryl acrylate,
30 parts of 1,6-hexanediol diacrylate were mixed and dissolved at room temperature to obtain a uniform and transparent resin. 40 parts of the obtained resin, 4 parts of benzoin ethyl ether as a photosensitizer, 60 parts of ceramic painting pigment (selenium red)
1 part and 2 parts of the leveling agent were kneaded using three rolls to obtain an ultraviolet curable ink (i). Production Example 2 20 parts of n-butyl methacrylate polymer with a molecular weight of 220,000 and a glass transition point of 20°C, 25 parts of hydroxyethyl methacrylate, 5 parts of ethyl methacrylate,
30 parts of diacrylate of 4 moles of ethylene oxide adduct of bisphenol A and 20 parts of ethylene glycol dimethacrylate were mixed and dissolved at room temperature to obtain a homogeneous transparent resin. 35 parts of the obtained resin, 4 parts of benzoin methyl ether as a photosensitizer, 65 parts of a ceramic painting pigment (glossy black), and 2 parts of a leveling agent were kneaded using three rolls to obtain ultraviolet curable ink (ii). Ta. Production example 3 12 parts of pentaerythritol triacrylate,
28 parts of pentaerythritol tetraacrylate,
4 parts of benzoin ethyl ether as a photosensitizer;
60 parts of ceramic painting pigment (selenium red) and 2 parts of leveling agent are kneaded using 3 rolls to create UV-curable ink.
I got (iii). Example 1 A pattern was screen printed on a piece of paper coated with a dextrin solution using the ultraviolet curable ink (i) of Production Example 1, and the ink was cured by irradiating it with ultraviolet rays for 10 seconds at a distance of 15 cm under a 5.6 KW high-pressure mercury lamp. Ta. Next, the ultraviolet curable resin (A) of Reference Production Example 1 was used as a cover coat layer.
was printed on the pattern and cured by irradiating it with ultraviolet rays for 15 seconds to obtain a transfer paper for ceramic painting of the present invention.
The resulting transfer paper was transferred to ceramics using a wet method, and 100%
When fired at a heating rate of ℃/hour until it reached a maximum temperature of 850℃, a beautiful painting was created without any cracks or missing patterns. Note that under these firing conditions, the cover coat layer begins to discolor from around 180℃ and reaches 380℃.
At ~450℃, it completely disappeared. Examples 2 to 3 and Comparative Examples 1 to 2 Various types of ceramics were prepared using various ultraviolet curable resins for cover coats obtained in reference production examples and ultraviolet curable inks for designs obtained in production examples in the same manner as in Example 1. Transfer paper for painting was obtained. Table 1 shows the results of evaluation of the adhesion suitability and sinterability of the obtained transfer paper. 【table】

Claims (1)

[Scope of Claims] 1. A transfer paper for ceramic painting comprising a mount, a pattern ink layer, and a cover coat layer, in which the pattern ink layer is a polymer or copolymer () of a compound represented by the following general formula (A). , polymerizable compound (),
A transfer paper for painting ceramics, characterized by having a layer made of a photo-cured ultraviolet curable ink containing a photosensitizer (2) and a ceramic painting pigment (2) as essential components. General formula (A): (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having from C ₁ to C ₂₀ , an aralkyl group, or an aryl group.)