JPH0458400B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to printing transfer paper for ceramic painting used when painting ceramics, and more specifically to a printing transfer paper for ceramic painting that uses a new pattern ink layer binder (hereinafter referred to as squeegee oil). This paper relates to printing transfer paper for painting ceramics. (Relationship with conventional technology) One method for painting ceramics is to print a pattern ink layer containing ceramic coloring pigments on a mount that has been coated with a glue such as a dextrin solution and dried, and then cover it. A method of using transfer paper on which a coat layer is printed is known. This method involves peeling off the integrated cover coat layer and pattern ink layer from the mount in water using a so-called "slide" transfer method using water, pasting the pattern ink layer on ceramics, drying, and then applying a cover coat at a high temperature. This is a method of painting by firing the layers, ink, and binder. Currently, solvent-based polymethacrylate resins are mainly used for the squeegee oil used in printing transfer paper for painting ceramics, but there are many problems that need to be resolved, and this has become a serious problem in the kiln industry. ing. (1) Solvent type squeegee oil generally contains high boiling point solvents, toluene, xylene, dimethylbenzene, ethylbenzene, triethylbenzene, trimethylbenzene, ethylene glycol monobutyl ether, and ethylene glycol to prevent clogging of screen printing plates. Monoethyl acetate, etc. are used, and as a matter of course the drying speed is slow and productivity does not improve. (2) Since solvent-based resins are used, the workplace environment and air pollution are significant due to the use of solvent-based resins. (3) Current solvent-based squeegee oils dry slowly and require a lot of time, especially when printing in multiple colors. , (4) Since the screen plate is easily clogged due to the use of solvent-based resin, it has many problems such as the difficulty of forming precise patterns. It is well known that ultraviolet curable resins, which are so-called solvent-free resins, have been attracting attention as a solution to these drawbacks of solvent-based resins, and a wide variety of proposals have been made. Therefore, attempts to apply ultraviolet curable resins to the decoration of ceramics are considered a natural move and are well known. For example, in Japanese Patent Application Laid-open No. 57-115390, a squeegee and transfer paper for ceramic painting using ultraviolet curable resin are disclosed.
Application to oil has been proposed, but such attempts have not yet been put into practical use. The main reasons for this are that when conventional ultraviolet curable resins are applied to squeegee oils, (1) they are not flexible and have poor adhesion, and (2) their thermal decomposition temperatures are high, resulting in poor color development when fired. This is because there are shortcomings in its performance. The present inventors had already proposed the application of squeegee oil for ultraviolet curable resin (Japanese Unexamined Patent Publication No. 57-152993), but after conducting more detailed research, it was found that flat plates, There is no problem with slide transfer on flat surfaces such as tiles, but the slide transfer performance on ceramics with many curved surfaces such as tea cups, coffee cups, rice bowls, deep plates, flower vases, and tea bowls is insufficient, and the design ink layer It was found that it was easy to tear. (Purpose of the Invention) Therefore, as a result of further intensive research to solve this problem, we have developed a squeegee oil with excellent slide transferability and color development by using polyoxyalkylene glycol diacrylate and/or dimethacrylate together. It was discovered that the following could be obtained, and the present invention was finally achieved. (Description of the structure of the invention) That is, the present invention provides a ceramic painted printing transfer paper consisting of a mount, a pattern ink layer, and a cover coat layer, in which a binder (squeegee, etc.) for the pattern ink layer is used.
oil) is a polymer or/and copolymer of a compound represented by () general formula (A) (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, or an aryl group.) () Represented by general formula (B) photopolymerizable compound (In the formula, X is hydrogen or a methyl group, m is 1-
Indicates a positive integer of 3, n is 4≦n≦100,
This is the number of moles of this compound added. ) A printing transfer paper for painting ceramics characterized by comprising () a photopolymerizable compound having a polymerizable double bond in the molecule other than the general formula (B) and () a photoinitiator. The squeegee oil used in the present invention is () a polymer or/and copolymer of a compound represented by the above general formula (A), () a photopolymerizable compound represented by the above general formula (B), () a general A photopolymerizable compound having a polymerizable double bond in the molecule other than formula (B) and () an ultraviolet curable resin containing a photoinitiator as essential components. The polymer or/and copolymer () of the compound represented by the general formula (A) used in the present invention is:
Methyl (meth)acrylate (indicates acrylic acid methyl ester and methacrylic acid methyl ester. Same abbreviation hereinafter), ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylic acid- (meth)acrylic acid alkyl esters such as i-propyl, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl (meth)acrylate;
(meth)acrylic acid cycloalkyl esters such as cyclohexyl acrylate, (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate, or (meth)acrylic acid aryl esters such as phenyl (meth)acrylate. It is a combination or/and a copolymer. In some cases, copolymers of such (meth)acrylic esters with ethylene, styrene, butadiene, isobutylene, isoprene, vinyl acetate, isobutyl vinyl ether, n-butyl vinyl ether, acrylonitrile, etc. can also be used. Preferred compounds represented by general formula (A) are C ₁ -
Among the _C4 compounds, particularly preferred are copolymers of methyl methacrylate and n-butyl methacrylate. Methyl methacrylate, methacrylic acid-
The copolymerization molar ratio of n-butyl copolymer is methyl methacrylate, n-butyl methacrylate = 10:90 ~
The ratio is 90:10, preferably 20:80 to 80:20. If the copolymerization molar ratio is other than the above, the flexibility of the pattern ink layer will not be sufficient and the printability will not be sufficient. The compounding amount of the compound () is 5 to 60% by weight, more preferably 10 to 50% by weight in the resin composition of the present invention. If the amount is less than 5% by weight, flexibility and curability will not be sufficient, and if it exceeds 60% by weight, the viscosity of the resin composition will be high and it will be difficult to handle. The photopolymerizable compound () represented by the general formula (B) used in the present invention includes the following compounds. Compounds where m=1 and n=4 are, for example, polyethylene glycol (adduct of 4 moles of ethylene oxide) di(meth)acrylate, polypropylene glycol (adduct of 4 moles of propylene oxide)
Examples include di(meth)acrylate. Compounds where m=1 and n=9 are, for example, polyethylene glycol (adduct of 9 moles of ethylene oxide) di(meth)acrylate, polypropylene glycol (adduct of 9 moles of propylene oxide)
Examples include di(meth)acrylate. Compounds where m=1 and n=14 are, for example, polyethylene glycol (14 mole adduct of ethylene oxide) di(meth)acrylate, polypropylene glycol (14 mole adduct of propylene oxide)
Examples include di(meth)acrylate. Compounds where m=1 and n=23 are, for example, polyethylene glycol (23 mole adduct of ethylene oxide) di(meth)acrylate, polypropylene glycol (23 mole adduct of propylene oxide)
Examples include di(meth)acrylate. Similarly, examples of the compound where m=2 include polytrimethylene glycol (n mole adduct of trimethylene oxide) di(meth)acrylate. As a compound where m=3, for example, polytetramethylene glycol (tetramethylene oxide n
molar adducts) di(meth)acrylates, etc. As the photopolymerizable compound represented by the general formula (B), polypropylene glycol (n mole adduct of propylene oxide) di(meth)acrylate (4≦n≦100) is particularly preferable. Regarding the photopolymerizable compound () represented by general formula (B), n, which is the number of added moles, is 4≦n≦
Must be in the range of 100. If n is less than 4, the pattern ink layer lacks flexibility, and
Slide transferability to ceramics with many curved surfaces, such as coffee cups, bowls, deep plates, vases, and bowls, is insufficient. On the other hand, if n exceeds 100, the pattern ink layer becomes too flexible, and the slideability and adhesion properties become insufficient. The proportion of the photopolymerizable compound () represented by general formula (B) is 5% by weight to 5% by weight of the resin composition of the present invention.
80% by weight, preferably 10% to 70% by weight
It is. If the proportion of the photopolymerizable compound () represented by general formula (B) is less than 5% by weight, the flexibility will be insufficient, and if it exceeds 80% by weight, the viscosity of the resin composition will increase, making it difficult to handle. It lacks. Among the photopolymerizable compounds () other than general formula (B) used in the present invention, photopolymerizable compounds having one polymerizable double bond in the molecule include (i)
Styrene compounds such as styrene, α-methylstyrene, chlorostyrene, (ii) methyl (meth)acrylate, ethyl (meth)acrylate, n-
and i-propyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate
Alkyl (meth)acrylates such as acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; or polyoxyalkylene glycol mono such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate. (meth)acrylates or substituted alkyl mono(meth)acrylates such as alkoxypolyoxylalkylene mono(meth)acrylate, heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate
There are acrylates, etc. Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include (i) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di (meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-
Examples include alkylene glycol di(meth)acrylates such as hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate. Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include (i) trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate,
Examples include poly(meth)acrylates of trivalent or higher aliphatic polyhydric alcohols such as pentaerythritol tetra(meth)acrylate, poly(meth)acrylates of trivalent or higher halogen-substituted aliphatic polyhydric alcohols, and the like. If a large amount of a photopolymerizable compound having three or more polymerizable double bonds in the molecule is used, the flexibility of the squeegee oil will decrease and it will not have a positive effect on color development when fired. Its usage must be limited to small quantities. The amount of the photopolymerizable compound () other than general formula (B) is 30% to 90% by weight, preferably 40% to 80% by weight of the resin composition of the present invention. When the amount of the photopolymerizable compound () is less than 30% by weight of the resin composition, the resin viscosity becomes high and the handleability thereof becomes poor. Furthermore, if the blending amount exceeds 90% by weight, the properties of the squeegee oil such as flexibility and hardenability will not be sufficient. The photoinitiator used in the present invention is a compound that promotes the photopolymerization reaction of a photopolymerizable compound, and includes, for example, ketals such as benzyl dimethyl ketal, benzoins such as benzoin methyl ether and benzoin ethyl ether, and 1- anthraquinones such as chloranthraquinone and 2-ethylanthraquinone; benzophenones such as benzophenone and p-dimethylaminobenzophenone;
Examples include propiophenones such as 2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, sulfur-containing compounds such as diphenyl disulfide, tetramethylthiuram disulfide, and thioxanthone. They may be used alone or in combination of two or more. The amount of the photoinitiator () is 0.05 to 20% by weight based on the total amount of the polymer or/and copolymer () of the compound represented by the general formula (A) and the photopolymerizable compound () and (). %, especially 0.5 to 10% by weight. In addition, in order to increase the photopolymerization reaction promoting effect of the photoinitiator (), amines such as triethanolamine, triethylamine, N,N-diethylaminoethyl (meth)acrylate, triphenylphosphine, etc. are used as photosensitizers. It is also possible to use phosphorus compounds in combination. The ultraviolet curable resin of the present invention uses a conventional solvent-based resin, for example, a resin made of methacrylic acid methyl ester-methacrylic acid-n-butyl ester copolymer and a solvent such as xylene, toluene, trimethylbenzene, dimethylbenzene, etc., as a cover coat layer. Although it is possible to use the cover coat layer on the pattern ink layer of the present invention, if the cover coat layer is an ultraviolet curable resin, the above-mentioned disadvantages of the solvent-based ink layer can be completely eliminated. Known thermal polymerization inhibitors, antioxidants, leveling agents, antifoaming agents, thickeners, thixotropic agents, pigments, etc. are added to the ultraviolet curable resin used for squeegee oil to improve viscosity, storage stability, It is used after adjusting printing suitability. As the mount used for the ceramic painting transfer paper of the present invention, single paper, collodion coated paper, separate paper, thermaflat paper, etc. are used. The pattern ink layer is printed on transfer paper and cured by irradiating it with ultraviolet rays. Light sources used for irradiating ultraviolet rays include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, xenon lamps, and metal halide lamps. etc. are used. (Effects of the Invention) In the present invention, by using a new ultraviolet curable resin in the squeegee oil, (a) the pattern ink layer has flexibility, so it has excellent slide transferability to ceramics with curved surfaces. There is. (b) The pattern ink layer is UV-curable, so the screen plate is less likely to clog, and precise and clear patterns can be formed. (c) The pattern ink layer does not change over time, providing excellent adhesion properties. (d) It has performance features such as being able to print patterns with good color development because it is excellent in firing. The ultraviolet curable resin of the present invention has the basic characteristics required for a squeegee oil for ceramic painting, such as firing properties and adhesion properties, and its ripple effects such as improvement of the workplace environment, high productivity, and labor saving are extremely large. It can be said that. (Examples) In order to explain the present invention in more detail, Examples are given, but the present invention is not limited to these Examples in any way. In the examples, parts or % indicate parts by weight or % by weight, respectively. The performance of the printing transfer paper for painting ceramics was evaluated by the following method. Printability: Using a 250-mesh polyester screen plate with the pattern shown in Figure 1 on a mount coated with dextrin liquid, print a pattern ink consisting of pigment and squeegee oil, Printability was evaluated based on the number of sheets printed until clogging or thin lines became missing. Adhesive suitability: Printing transfer paper for ceramic painting consisting of a mount, a pattern ink layer and a cover coat layer is applied at a water temperature of 25~25°C.
After being immersed in water at 30°C for 60 seconds, it was transferred to a plain white coffee cup and hot water cup using a rubber spatula, and the adhesion suitability of the pattern ink layer during transfer was evaluated. 〇: Good transferability, △: Torn from the pattern ink layer during transfer, ×: Difficult to slide from printed transfer paper to ceramics. Firing, color development: The coffee cup with the printed layer transferred and the hot water cup are heated to the maximum temperature at a heating rate of 300℃/hour.
Firing was performed until the temperature reached 800°C, and firing and color development were evaluated based on the extent to which pinholes, scratches, and wrinkles occurred in the pattern after firing. Production example Methyl methacrylate (MMA)-n-butyl methacrylate (n-
BMA) copolymer (MMA/n-BMA=40/60,
weight ratio) 25 parts, tetrahydrofurfuryl methacrylate 55 parts, lauryl methacrylate 5 parts, polyethylene glycol (ethylene oxide 14 mole adduct) dimethacrylate 10 parts, polypropylene glycol (propylene oxide 14 mole adduct) dimethacrylate 5 parts, 2 parts of a leveling agent and 6 parts of benzyl dimethyl ketal and 2 parts of 2-ethylanthraquinone as photoinitiators were mixed and dissolved at room temperature, and an ultraviolet curing resin for squeegee oil was prepared.
I got (A). In the same manner, ultraviolet curable resins (B) to (D) for squeegee oil were obtained in which polymers and photopolymerizable compounds were compounds shown in Table 1. As the photoinitiator and leveling agent, the same compounds and the same amounts as in (A) were used.

[Table] Reference production example 25 parts of methyl methacrylate-n-butyl methacrylate copolymer (mentioned above) with an average molecular weight of 75,000, 60 parts of tetrahydrofurfuryl methacrylate,
1,6-hexanediol dimethacrylate 15
1 part, 2 parts of a leveling agent, and 6 parts of benzyl dimethyl ketal and 2 parts of 2-ethylanthraquinone as photoinitiators were mixed and dissolved at room temperature to obtain an ultraviolet curable resin (E) for squeegee oil. In the same manner, ultraviolet curable resins (F) to (G) for squeegee oil were obtained in which polymers and photopolymerizable compounds were compounds shown in Table 2. As the photoinitiator and leveling agent, the same compounds and the same amounts as in (E) were used.

[Table] Example 1 A UV-curable ceramic painting pattern consisting of 60% by weight of selenium red pigment and 40% by weight of the UV-curable resin (A) for squeegee oil of Production Example 1 was applied to a sheet of paper coated with dextrin liquid. The pattern shown in Figure 1 (height 17 cm x width 4 cm x thickness approx. 10 μm) was printed using a polyester screen plate with 250 mesh ink. At this time, even after printing more than 1,000 sheets, no clogging of the screen plate or missing thin lines was observed. This printing transfer paper was printed under a 5.6KW water-cooled high-pressure mercury lamp.
The ink was irradiated for 14 seconds at a distance of 15 cm and cured to form a patterned ink layer. Next, a commercially available solvent-based cover coat resin () (manufactured by Mitsubishi Rayon Co., Ltd.) was printed on the pattern ink layer using a 100-mesh polyester screen plate with dimensions of 18 cm long x 4.5 cm wide x 20 μm thick. did. Printed cover coat layer at 40℃, 50℃
It was left to dry in a dryer at %RH for 1 hour. The obtained printed transfer paper was transferred to plain white coffee cups and hot water cups by a wet method, and the adhesion suitability was evaluated. Next, add the above coffee cup and hot water cup.
The product was fired at a heating rate of 300°C/hour until a maximum temperature of 800°C was reached, and the firing and coloring properties were tested. The test results for adhesion suitability, firing, and color development are shown in Table 3. Examples 2 to 5 The ultraviolet curing type ink for ceramic painting in Example 1 contained selenium red as a pigment instead of selenium red.
A printing transfer paper for painting ceramics was produced in the same manner as in Example 1, except that it contained the pigments shown in the table and used (B) to (D) instead of (A) as the ultraviolet curable resin for squeegee oil. did. Printing suitability, adhesion suitability and firing of printing transfer paper,
The color development properties are shown in Table 3.

[Table] Comparative Example 1 A sheet of paper coated with the dextrin of Example 1 was coated with 60% by weight of the pigment selenium red in the same manner as in Example 1.
The pattern shown in Figure 1 (height 17cm x width 4
cm x thickness of approximately 10 μm) and cured. Next, use a 100 mesh polyester screen plate to apply commercially available solvent-based cover coat resin () (described above) onto the pattern ink layer, 18 cm in length.
It was printed with dimensions of x 4.5 cm wide x 20 μm thick. The printing transfer paper was evaluated in the same manner as in Example 1. The results are shown in Table 4. Comparative Examples 2 to 3 The UV-curable ceramic pattern ink in Example 1 contained the pigments shown in Table 4, and was used as the UV-curable resin for squeegee oil.
Example 1 except that (F) or (G) is used instead of (A)
Printing transfer paper for ceramic painting was produced in the same manner as above. Table 4 shows suitability for printing on transfer paper, suitability for pasting, firing, and color development. Comparative Example 4 A pattern was printed on a sheet of paper coated with the dextrin of Example 1 in the same manner as in Example 1 using 60% by weight of the pigment selenium red and a solvent-type squeegee oil resin (H). Solvent type squeegee/oil resin (H)
When using , the screen plate became clogged when the number of copies exceeded 20. This pattern layer is 40
It was left to dry in a dryer at 50% RH for 1 hour. A solvent-based cover coat resin (2) was used on this pattern layer in the same manner as in Example 1 to produce a printing transfer paper for ceramic decoration. Table 4 shows the printing suitability, pasting suitability, firing and coloring properties of the printing transfer paper.

【table】 [Brief explanation of drawings]

FIG. 1 shows a picture pattern.

Claims (1)

[Scope of Claims] 1. A printing transfer paper for ceramic painting comprising a mount, a pattern ink layer, and a cover coat layer, in which the binder of the pattern ink layer is () a polymer of a compound represented by the general formula (A) or/and copolymer, (In the formula, R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, or an aryl group.) () Represented by general formula (B) photopolymerizable compound, (In the formula, X is hydrogen or a methyl group, m is 1-
Indicates a positive integer of 3, n is 4≦n≦100,
This is the number of moles of this compound added. ) A printing transfer paper for painting ceramics, comprising () a photopolymerizable compound having a polymerizable double bond in the molecule other than general formula (B), and () a photoinitiator.