JPH0780399B2 - Printing transfer paper for ceramic painting - Google Patents

Description

TECHNICAL FIELD The present invention relates to a ceramic transfer printing transfer paper used for painting ceramics, and more specifically to a ceramic painting using a new cover coat agent. The present invention relates to print transfer paper.

(Prior Art) As one of the methods for painting ceramics, a pattern ink layer containing a coloring pigment for ceramics is printed on a base paper that has been coated with a sizing agent such as dextrin solution and dried, and then a cover coat is applied. It is known to use transfer paper with printed layers. This method is a so-called "slide" transfer method using water, in which the cover coat layer and the pattern ink layer that are integrated with each other are peeled from the mount in water, the pattern ink layer is attached to the ceramic and dried, and then the cover coat is applied at high temperature. It is a method of baking a layer, ink, and a binder for painting.

At present, solvent-based polymethacrylate resin is mainly used for the cover coat layer of this ceramic transfer printing paper, but there are many problems to be solved, and the ceramic industry strongly requests its solution. Has been done.

That is, (1) the solvent type cover coat resin generally has a high boiling point solvent such as toluene, xylene, dimethylbenzene, ethylbenzene, triethylbenzene, trimethylbenzene, ethylene glycol monobutyl ether to prevent clogging of the screen printing plate, Since ethylene glycol monoethyl acetate etc. are used, naturally the drying speed is slow and the productivity does not improve,
(2) Solvent-type resin is used, so the pollution of the work environment and the air pollution due to the solvent is remarkable, and there is an urgent need to solve it in terms of occupational safety and health and pollution.
(3) The current solvent-type cover coat resin is slow to dry, so it tends to cause printing transfer paper blocking due to residual solvent. (4) For this reason, the current printing transfer paper for ceramic painting is used for blocking prevention. Paraffin paper etc. 1
It needs to be sandwiched one by one, which requires cost and labor. (5) The ceramic printing transfer paper using the current solvent-type cover coat resin is liable to change with time and has flexibility during storage. It suffers from many problems such as loss and poor aptitude.

As a solution to such drawbacks of solvent-type resins, UV-curable resins, which are so-called solventless resins, have been attracting attention, and it is well known that various proposals have been made. Therefore, an attempt to apply the ultraviolet curable resin to the painting of ceramics is considered to be a natural movement and is known.

For example, Japanese Patent Application Laid-Open No. 57-115390 proposes application of a UV-curable resin to a cover coat layer of a printing transfer paper for ceramic painting, but such an attempt has not yet been put to practical use. The reason for this is that, when a conventional UV curable resin is applied to the cover coat layer, (1) it lacks flexibility and lacks applicability, and (2) its thermal decomposition temperature is high and its firing colorability is poor. However, (3) there is a defect in its performance such as high resin viscosity and insufficient printability.

(Problems to be Solved by the Invention) The present inventors have already proposed application of a UV-curable resin to a cover coat layer (Japanese Patent Laid-Open No. 142385/1982), but thereafter conducted further detailed research. At the same time, it was found that the printability of the cover coat layer was not always sufficient especially during high-speed printing, and bubbles were liable to be generated, which had a problem in appearance. It was also found that when the thickness of the cover coat layer was 25 μm or more, poor firing occurred, and the pattern layer was likely to bleed and wrinkle.

(Means for solving the problem) Then, as a result of further intensive research to solve this problem, as a result of using a specific nonionic surfactant in the composition of the cover coat layer, printability and baking property are improved. It was found that an excellent cover coat layer can be obtained and finally reached the present invention.

That is, the present invention relates to a ceramic transfer printing paper comprising a mount, a pattern ink layer and a cover coat layer, wherein the cover coat layer is (I) a polymer or / and a copolymer of the compound represented by the general formula (A). (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group.) (II) Represented by the general formula (B) Photopolymerizable compound (In the formula, X is hydrogen or a methyl group, m is a positive integer of 1 to 3, n is 4 ≦ n ≦ 100, and is the number of moles added to this compound.) (III) General formula (B Other than), a photopolymerizable compound having a polymerizable double bond in the molecule (IV) a photoinitiator and (V) at least one nonionic activator selected from the group represented by or of This is a printing transfer paper for painting with ceramics.

(In the formula, R is an alkyl group having 6 to 40 carbon atoms, an aryl group, or an allyl group.

R'is hydrogen, R, OCR.

X is hydrogen or a methyl group.

m'is an integer of 1 to 3.

n'is 1≤n'≤50. The polymer or / and copolymer (I) of the compound represented by the general formula (A) used in the present invention means methyl (meth) acrylate (acrylic acid methyl ester and methacrylic acid methyl ester). The same applies hereinafter), ethyl (meth) acrylate, -n-propyl (meth) acrylate, i-propyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as (meth) acrylic acid-n-butyl, (meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclohexyl (meta) ) Polymers or / and copolymers of (meth) acrylic acid aralkyl esters such as acrylic acid cycloalkyl esters, benzyl (meth) acrylic acid or (meth) acrylic acid aryl esters such as phenyl (meth) acrylate. It is a polymer.

Preferred compounds represented by the general formula (A) are C _{1 to} C ₄ compounds, and particularly preferred are methyl methacrylate and -n-butyl methacrylate copolymers. The copolymerization molar ratio of methyl methacrylate and methacrylate-n-butyl copolymer is methyl methacrylate and methacrylate-n-butyl = 10: 90 to 90:10, preferably 20:80 to 80:20. is there. When the copolymerization molar ratio is outside the above range, the flexibility of the pattern ink layer cannot be said to be sufficient and the printability cannot be said to be sufficient.

The compounding amount of the compound (I) is 5 to 60 in the resin composition of the present invention.
%, More preferably 10 to 50% by weight. If the blending amount is less than 5% by weight, flexibility and curability are not sufficient, and if the blending amount exceeds 60% by weight, the viscosity of the resin composition becomes high, resulting in poor handleability.

The photopolymerizable compound (II) represented by the general formula (B) used in the present invention is the following compound.

The compound of m = 1 and n = 4 is, for example, polyethylene glycol (ethylene oxide 4 mol adduct) di (meth).
There are acrylate, polypropylene glycol (propylene oxide 4 mol addition product) di (meth) acrylate, and the like.

The compound of m = 1 and n = 9 is, for example, polyethylene glycol (ethylene oxide 9 mol adduct) di (meth).
Acrylate, polypropylene glycol (addition product of 9 mol of propylene oxide) di (meth) acrylate, and the like.

The compound of m = 1 and n = 14 is, for example, polyethylene glycol (ethylene oxide 14 mol adduct) di (meth).
Acrylate, polypropylene glycol (propylene oxide 14 mol adduct) di (meth) acrylate and the like.

The compound of m = 1 and n = 23 is, for example, polyethylene glycol (ethylene oxide 23 mol adduct) di (meth).
Acrylate, polypropylene glycol (23 mol addition product of propylene oxide), di (meth) acrylate and the like.

Similarly, as the compound of m = 2, for example, polytrimethylene glycol (trimethylene oxide nmole adduct) di (meth) acrylate or the like is used.

As the compound of m = 3, for example, polytetramethylene glycol (tetramethylene oxide nmole adduct)
Examples include di (meth) acrylate.

As the photopolymerizable compound represented by the general formula (B), particularly polypropylene glycol (propylene oxide n
Molar adduct) di (meth) acrylate (4 ≦ n ≦ 100)
Is preferred.

Regarding the photopolymerizable compound (II) represented by the general formula (B), it is necessary that the number of addition moles, n, is in the range of 4 ≦ n ≦ 100. When n is less than 4, the pattern ink layer lacks flexibility, and only hot water, coffee cup, bowl,
Sliding transferability to ceramics with many curved surfaces such as deep plates, vases, and bowls is insufficient. On the other hand, n is 100
When it exceeds, the pattern ink layer becomes too flexible,
On the contrary, the slidability and sticking suitability are insufficient.

The mixing ratio of the photopolymerizable compound (II) represented by the general formula (B) is 5% by weight to 80% by weight, preferably 10% by weight to 70% by weight of the resin composition of the present invention. If the proportion of the photopolymerizable compound (II) represented by the general formula (B) is less than 5% by weight, the flexibility is insufficient, and if it exceeds 80% by weight, the viscosity of the resin composition becomes high and the handling becomes difficult. Lacks sex.

Among the photopolymerizable compounds (III) other than the general formula (B) used in the present invention, examples of the photopolymerizable compound having one polymerizable double bond in the molecule include (i) styrene and α -Styrene compounds such as methylstyrene and chlorostyrene, (ii) methyl (meth) acrylate, 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 stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) Alkoxyalkyl (meth) acrylates such as acrylate, phenoxyethyl (Meth) aryloxyalkyl (meth) acrylates such as acrylate, 2
-Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, and heterocycle-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate.

Examples of the photopolymerizable compound having two photopolymerizable double bonds in the molecule include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,4-butanediol (meth) acrylate. , Neopentyl glycol di (meth) acrylate,
Alkylene glycol di (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, oxyalkylenes such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate Examples include glycol di (meth) acrylates.

Examples of the photopolymerizable compound having 3 or more photopolymerizable double bonds in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate. And poly (meth) acrylates of trihydric or higher aliphatic polyhydric alcohols.

When a large amount of a photopolymerizable compound having 3 or more polymerizable double bonds in the molecule is used, the flexibility of the cover coat layer is lowered, and it does not have a good influence on the firing color development. The amount used should be limited to a small amount.

The compounding amount of the photopolymerizable compound (III) other than the general formula (B) is 30% by weight to 90% by weight of the resin composition of the present invention,
It is preferably 40% by weight to 80% by weight. When the compounding amount of the photopolymerizable compound (III) is less than 30% by weight of the resin composition,
The resin viscosity becomes high and the handling property is poor. On the other hand, when the content is more than 90% by weight, various properties such as flexibility, sticking suitability and curability of the cover coat layer are not sufficient.

The photoinitiator used in the present invention is a compound that accelerates the photopolymerization reaction of a photopolymerizable compound, and examples thereof include ketals such as benzyl dimethyl ketal, benzoyl methyl ether, benzoin ethyl ether, and benzoin-i-propyl ether. Benzoins such as benzoin and α-methylbenzoin, anthraquinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone and 2-ethylanthraquinone, benzophenone, p-chlorobenzophenone, p-dimethylamino Benzophenones such as benzophenone, 2-hydroxy-2-methylpropiophenone, propiophenones such as 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropiophenone, dibenzosuberone, etc. Suberon, Phenylalanine THIS Ruff Id, tetramethylthiuram Soo Ruff Id, sulfur-containing compounds such as thioxanthone, methylene blue, eosin, etc. dyes such as fluorescein and the like, are used in combination alone or two or more.

The blending amount of the photoinitiator (IV) is based on the total amount of the polymer or / and copolymer (I) of the compound represented by the general formula (A) and the photopolymerizable compounds (II) and (III). 0.05
-20% by weight, particularly 0.5-10% by weight is preferred.

Further, in order to increase the photopolymerization reaction accelerating action of the photoinitiator (IV), amines such as triethanolamine, triethylamine, N, N-diethylaminoethyl (meth) acrylate, triphenylphosphine are used as photosensitizers. It is also possible to use phosphorus compounds such as

The ultraviolet curable resin of the present invention is a conventional solvent type resin, for example, methacrylic acid methyl ester-methacrylic acid-n-.
It is also possible to use it on a pattern ink layer using a resin composed of a butyl ester copolymer and a solvent such as xylene, toluene, trimethylbenzene, or dimethylbenzene as a binder, but when the binder is an ultraviolet curable resin. Will completely eliminate the above-mentioned drawbacks of the solvent type.

The nonionic surfactant (V) represented by the general formula or represented by the formula (1) used in the present invention has an oxyalkylene unit. For example, in the formula, R ′ is H, polyethylene glycol monolauryl Ether, polyethylene glycol monooleyl ether,
Polyethylene glycol mono higher alkyl ethers such as polyethylene glycol mono stearyl ether, polyethylene glycol mono octyl phenyl ether, polyethylene glycol mono nonyl phenyl ether and polyethylene glycol mono higher alkyl phenyl ethers, wherein R'is R Is a polyethylene glycol diether obtained by etherifying the OH terminal of a compound in which R'is H in the formula with a higher alcohol such as lauryl alcohol, oleyl alcohol, stearyl alcohol or a higher alkylphenol such as octylphenol or nonylphenol. And R'is H in the formulas and formulas, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene Polyethylene glycol mono-higher fatty acid esters such as lenglycol monostearate, wherein R'is OCR in the formula, the compound in which R'is H in the formula is OH terminal of lauric acid, oleic acid, stearic acid, etc. Polyethylene glycol di-higher fatty acid esters obtained by esterification with a fatty acid or the like, and compounds in which R'is OCR in the formula include lauric acid, oleic acid, stearic acid at the OH end of the compound in which R'is H in the formula. Polyethylene glycol higher alkyl and higher alkyl phenyl ether higher fatty acid esters obtained by esterification of the higher fatty acids mentioned above.

Regarding the nonionic surfactant (V) represented by the general formula or, the number of carbon atoms of the alkyl group, the aryl group and the allyl group is 6 to 40, and particularly preferably 8
Is ~ 20. If the number of carbon atoms is less than 6 or more than 40, printability and baking properties will be insufficient. The number of moles of added alkylene oxide, n ', is in the range of 1≤n'≤50, and particularly preferably 1≤n'≤30. n '
If it exceeds 50, the printability and firing properties will be insufficient.

Examples of the oxyalkylene unit include oxyethylene, oxypropylene, oxytrimethylene, oxytetramethylene, and the like, but these are not limited to one and may be contained in two or more kinds. Preferred are oxyethylene units.

The HLB value of the nonionic surfactant represented by the formula or is in the range of 1 to 25.

Further, when a surfactant other than the nonionic surfactant (V) represented by the general formula or is used, for example, a cationic surfactant or an anionic surfactant, printability and baking properties are insufficient. .

The compounding amount of the nonionic surfactant (V) represented by the general formula or is the polymer or / and copolymer (I) of the compound represented by the general formula (A) and the photopolymerizable compound (II) and ( It is preferably 0.5 to 10% by weight, particularly 1 to 5% by weight, based on the total amount of III). When the compounding amount of the nonionic surfactant (V) is less than 0.5% by weight, the printability of the cover coat layer becomes insufficient. Further, if the blending amount exceeds 10% by weight, the firing property becomes insufficient.

A known thermal polymerization inhibitor, antioxidant, ultraviolet absorber, colorant, leveling agent, etc. may be added to the ultraviolet curable resin used in the cover coat layer.

As the backing paper used for the transfer paper for porcelain painting of the present invention, single paper, collodion-coated paper, separate paper, thermflat paper and the like are used.

The cover coat layer is printed on a transfer paper on which a pattern is printed and is cured by irradiating with ultraviolet rays, and the light source used for irradiating with ultraviolet rays is a solar ray, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, Xenon lamps and metal halide lamps are used.

(Effect of the invention) By using the cover coat layer of the present invention, (1) the cover coat layer has excellent printability,
No bubbles are generated even at high speed printing.

(2) Because the cover coat layer has excellent thermal decomposability, 25
Even with a film thickness of up to 35 μm, the baking property is good, and bleeding and scratching do not occur.

(3) Since the cover coat layer is flexible, it is excellent in slide transferability to a ceramic having a curved surface. (4) Since the cover coat layer is an ultraviolet curing type, it does not substantially contain a solvent and remains. Does not cause blocking due to solvent, (5) Therefore, there is no need to insert blocking paper etc. to prevent blocking, (6) There is no change over time in the cover coat layer, and excellent sticking suitability can be maintained. It has performance advantages such as.

(Examples) In order to describe the present invention in more detail, examples will be given, but the present invention is not limited to these examples.

In the examples, "part" or "%" means "part by weight" or "% by weight", respectively. The performance of the printing transfer paper for painting with ceramics was evaluated by the following method.

Printability: 100 cm mesh polyester screen plate on the picture ink layer formed on the mount coated with dextrin solution (see Fig. 1), length 18 cm x width 4.5 cm x
A cover coat layer having a thickness of 30 μm was printed at a printing speed of 500 mm / sec, and it was examined whether bubbles were generated immediately after printing.

◯: Printability is good (no bubbles are generated), Δ: Bubbles are generated in a part of the cover coat layer, ×: Bubbles are generated in the entire surface of the cover coat layer.

Applicability: A ceramic transfer printing paper consisting of a backing paper, a pattern ink layer and a cover coat layer is placed in water at a water temperature of 25 to 30 ° C.
After soaking for a second, a rubber spatula was used for transfer only to a plain white coffee cup and hot water, and the suitability for application of the cover coat layer during transfer was evaluated.

◯: Transferability is good, Δ: Cover coat layer is torn during transfer, ×: Slide transfer from printing transfer paper to ceramics is difficult.

Blotting property: The printing surface of the printing transfer paper for ceramic painting is overlapped with the back side of the paper.
The test was performed on each sheet to evaluate the blocking property.
Of the 100 sheets of print transfer paper, the number showing the blocking is shown.

Blotting test conditions: load: 17 g / cm ² , temperature: 25 ° C, humidity: 60% RH, leaving time: 24 hours.

Baking and color development: Only the transferred coffee cup and hot water are heated to 300 ° C.
Baking was performed at a heating rate of 1 hour per hour until the maximum temperature reached 800 ° C., and after firing, the degree of occurrence of pinholes, scratches, and wrinkles in the pattern layer was evaluated for firing and color development.

Production Example Methyl methacrylate (MMA) / n-butyl methacrylate (n-BMA) copolymer having a molecular weight of 75,000 (MMA / n-BMA = 4)
0/60 weight ratio) 27 parts, tetrahydrofurfuryl methacrylate 56.4 parts, polyethylene glycol (ethylene oxide 14 mol adduct) dimethacrylate 6 parts, polypropylene glycol (propylene oxide 23 mol adduct) dimethacrylate 5.6 parts, leveling agent 3 Parts and 6 parts of benzyl dimethyl ketal as a photoinitiator, 2 parts of 2-ethylanthraquinone, polyethylene glycol monolauryl ether (5 mol of ethylene oxide adduct)
4 parts were mixed and dissolved at room temperature to obtain an ultraviolet curable resin (A) for cover coat. In the same manner, UV curable resins (B) to (D) for cover coat, in which the polymer, the photopolymerizable compound and the nonionic surfactant were the compounds shown in Table 1, were obtained. As the photoinitiator and the leveling agent, the same compounds as in (A) were used in the same amounts.

Reference Production Example Methyl methacrylate (MMA) -n-butyl methacrylate (n-BMA) copolymer having a molecular weight of 75,000 (MMA / n-BMA = 6)
0/40 weight ratio) 27 parts, tetrahydrofurfuryl methacrylate 55 parts, 1,6-hexanediol dimethacrylate 1
5 parts, 3 parts of a leveling agent and 6 parts of benzyl dimethyl ketal as a photoinitiator and 2-ethylanthraquinone 2
Parts and 4 parts of sodium dioctylsulfosuccinate as an anionic surfactant were mixed and dissolved at room temperature to obtain an ultraviolet curable resin (E) for cover coat.

Similarly, the polymer and the photopolymerizable compound are compounds shown in Table 2 for the ultraviolet curable resin (F) for cover coat
(I) was obtained. As the photoinitiator and the leveling agent, the same compounds as in (E) were used in the same amount.

Example 1 On a dextrin-coated single paper, 60% by weight of selenium red as a pigment, 40 parts by weight of binder (I) (methyl methacrylate-n-butyl methacrylate copolymer) and sorbetso #
100, "Etsuso Standard Petroleum Co., Ltd., 60 parts by weight) 40% by weight solvent-based pattern ink for ceramic painting
The pattern shown in Fig. 1 using a 250 mesh polyester screen plate (length 17 cm x width 4 cm x thickness about 10 μm)
Printed.

This print transfer paper was dried for 1 hour under the conditions of 40 ° C. and 50% RH to form a pattern ink layer. Then, the ultraviolet curable resin (A) for cover coat of Production Example was printed on the pattern ink layer using a 100 mesh polyester screen plate. Even when the number of printed sheets exceeded 1,000, the screen plate was not clogged at all, and no bubbles were generated. Printed cover coat layer is 5.6KW under water-cooled high pressure mercury lamp 15c
It was cured by irradiation at a distance of m for 10 seconds.

The obtained print transfer paper was transferred by a wet method only to a white plain coffee cup and hot water, and the sticking suitability was evaluated. Then, only this coffee cup and hot water were baked, and the baking and color development were tested.

Also, the blocking property of the printed transfer paper was measured.

Table 3 shows the test results of the UV-curable resin (A) for printing suitability, sticking suitability, blocking property, baking and color forming property.

Examples 2 to 4 In the solvent-based ceramic painting pattern ink of Example 1, the pigments shown in Table 3 were used instead of selenium red as the pigment, and (A) was used as the UV curable resin for the cover coat. , (B) to (D) were used in the same manner as in Example 1 to obtain a printing transfer paper for pottery painting.

Table 3 shows the test results of the printability, the stickability, the blocking property, the baking property, and the color forming property of the cover coat layer.

Comparative Example 1 Into the dextrin-coated single paper of Example 1, the same method as in Example 1 was used, and the dissolving type ceramic picture ink (pigment: 60% by weight of selenium red and 40% by weight of binder (I)) was used. And printed the pattern.

Then, the UV curable resin (E) of Reference Production Example was printed on the pattern ink layer using a 100 mesh polyester screen plate.

Curing of the printed covercoat layer and testing of the print transfer paper were performed as in Example 1. The result is the fourth
Shown in the table.

Comparative Examples 2 to 5 The pigments shown in Table 4 were used as the pigments of the pattern ink for melting type ceramics painting in Example 1, and (F) to (F), instead of (A) as the ultraviolet curable resin for the cover coat.
A print transfer paper for painting with ceramics was obtained in the same manner as in Example 1 except that (I) was used.

Table 4 shows the test results of the printability, stickability, blocking property, baking, and color developability of the cover coat layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a picture pattern.

Claims (1)

[Claims] 1. A ceramic transfer printing transfer paper comprising a mount, a pattern ink layer and a cover coat layer, wherein the cover coat layer comprises (I) a polymer or / and a copolymer of a compound represented by the general formula (A). , (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group.) (II) Represented by the general formula (B) A photopolymerizable compound, (In the formula, X is hydrogen or a methyl group, m is a positive integer of 1 to 3, and n is 4 ≦ n ≦ 100, which is the number of moles added to this compound.) (III) General formula (B) A photopolymerizable compound having a polymerizable double bond in a molecule other than (IV) a photoinitiator and (V) at least one nonionic activator selected from the group represented by or Characteristic printing transfer paper for ceramic painting. (In the formula, R is an alkyl group, an aryl group, or an allyl group having 6 to 40 carbon atoms. R'is hydrogen, R, or OCR. X is hydrogen or a methyl group. M'is an integer of 1 to 3. n'is 1 ≦ n ′ ≦ 50.)