JPS606314B2 - Method of forming a pattern on a sintered body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of printing a pattern or conductive circuit pattern on a composite material such as ceramics, glass, or ceramic using firing ink, and then firing the pattern to form the design.

There is already a widely used method of painting or forming conductive circuits by printing designs or conductive circuit patterns on ceramics, tiles, glass, ceramics, etc. using firing ink and then firing them at high temperatures. It's being used.
Currently, solvent-based cellulose resins such as nitrocellulose and ethylcellulose, and solvent-based (meth)acrylic resins such as polymethyl methacrylate are mainly used as binders for the firing ink used in this method.
There are problems associated with this that need to be resolved, and this has become a serious problem in the kiln industry and the electronics industry. That is {1}
Due to the use of solvent-based resins, the pollution of the workplace environment and air pollution due to solvents is significant, and urgent solutions are urgently needed from the aspects of occupational safety and health as well as pollution. The characteristics of the ink change due to the volatilization of the solvent. For example, when printing designs or conductive circuit patterns using screen printing, the screen becomes clogged, and the reproducibility of fine designs and patterns becomes extremely poor. This can be a fatal defect, especially in the case of conductive circuits, etc. '3) In order to prevent the above-mentioned screen clogging, high boiling point solvents such as butyl cellosolve, diethylene glycol monobutyl ether, etc. are generally used. Naturally, there are problems that need to be resolved, such as slow drying speeds and no improvement in productivity. - Ultraviolet curable resins, which are so-called solvent-free resins, are attracting attention as a solution to these drawbacks of solvent-based resins. As is well known, various compositions have been proposed.

Such ultraviolet curable resins include ultraviolet curable resins whose essential components are a prepolymer having a radically polymerizable unsaturated group, a polymerizable unsaturated monomer, and a photosensitizer. Therefore, it is considered a natural move to use ultraviolet curable resin as a binder for baking ink, and attempts to do so are well known (edited by the Japan Screen Printing Technology Association; Screen Printing Handbooks, p. 359, May 31, 1972). (Published on the day).
However, for example, it is extremely difficult to apply ultraviolet curable resin to ink for painting ceramics, and it has not yet reached the stage of practical use.

The reason for this is {1' The above ultraviolet curable resin is cured by ultraviolet irradiation and forms a crosslinked structure, so it has a high degree of thermal decomposition. Inorganic pigments: Pigments are repelled due to the melting and dawning of the flux or frit, and cannot be applied. -When the ultraviolet curing resin thermally decomposes, it scatters with the pigments, leaving no pattern.T3) Ceramic painting ink Because it contains a large amount of the above-mentioned pigments, it has low UV transmittance and tends to cause curing failure [4].As a result, curing wrinkles occur, and these wrinkle patterns do not disappear even after firing, making it impossible to create beautiful paintings. On the other hand, a proposal has recently been made regarding the use of an ultraviolet curable resin as a binder for baking ink used to form patterns such as conductive circuits (Tokukoku Sho 55-34211).

According to the above-mentioned publication, as a suitable ultraviolet curable resin for use in baking ink, 0.04 to 0.04 to 0.04 (meth)acryloyl groups as ethylenically unsaturated groups are added to 100 grams of the total amount of varnish.
A varnish containing 1.50 mol of a (meth)acryloyl group and a saturated polyester resin containing 0.04 to 1.50 mol of a (meth)acryloyl group and at least one of an unsaturated polyester resin and an alkyd resin are mentioned. Examples of saturated polyester resins include co-condensates of terephthalic acid or isophthalic acid and ethylene oxide.However, since the composition of the above-mentioned publication uses an ultraviolet curable resin, it cannot be used with solvent-based baking inks. Although the various drawbacks caused by the solvent have been improved, it has been found that the sinterability is still insufficient.

In other words, the publication states, ``Because the conventional solvent-based resin is simply replaced with a known ultraviolet-curable resin, the same disadvantages as those encountered when applying the ultraviolet-curable resin to ceramic painting ink as described above still remain unsolved.'' It is also stated that the sinterability is improved by adding polyester resin, etc. However, since unsaturated polyester resins and alkyd resins crosslink with ultraviolet curable resins, the sinterability is not necessarily improved. In this respect, since saturated polyester resin cannot be crosslinked with ultraviolet curable resin, it is thought that the sinterability will be improved, but there are few saturated polyester resins that have good compatibility with ultraviolet curable resin.For example, saturated polyester resin As a resin, Byron 20 manufactured by Toyobo Co., Ltd.
0 and Vylon 300 are well known, but these resins can be said to have almost no compatibility with (meth)acrylic ultraviolet curable resins. In order to satisfy the sinterability, the polymerizable compound must have a solubility of 2% by weight or more, but this is completely impossible with the above-mentioned saturated polyester resin. At present, no method of forming patterns using ultraviolet curable baking ink has been put into practical use. Taking these circumstances into consideration, the present inventors have conducted intensive research on the method of forming patterns by firing, and as a result, we have developed an ultraviolet ray ray consisting of a saturated copolymerized polyester [a} and a polymerizable compound {b} that are soluble in a polymerizable compound. By using a curable resin, he discovered and invented a method for forming fine designs and patterns on phosphor bodies such as ceramics and ceramics with good reproducibility.

That is, the present invention applies a polymerizable compound [b-soluble molecular weight 1000 to 150
Consisting of 00 saturated copolymerized polyester [a} and polymerizable compound (b') {a} no (b} = 20/80 to 7
Print an ultraviolet curable baking ink containing an ultraviolet curable resin (1), a photosensitizer (0), and a competitive solid (m) at a ratio of 0/30 (weight ratio) as essential components, and irradiate it with ultraviolet rays. This is a method of forming a pattern on a sintered body, which is characterized by forming a pattern on a sintered body by curing the sintered body and then firing it.

When a pattern is formed on the Akatsuki mating material using the method of the present invention,
．． [1] There is no clogging of screen printing plates, etc., and the reproducibility of fine pattern printing is good.
It is possible to create high-quality decorations and conductive circuits with high precision.

'2} Because UV-curable ink is used, there is little variation in the thickness of the ink layer and there is no uneven firing.

Legs Because the ultraviolet curable resin used in the present invention has much better adhesiveness and flexibility than conventional ultraviolet curable resins,
It is possible to form uniform shapes without scattering together with pigments during firing. [4] The ultraviolet curable resin used in the present invention contains saturated copolymerized polyester; It has very good photocurability and has sufficient curability even when a large amount of pigment is blended.

Therefore, since pigments and conductive particles can be mixed freely, good results can be obtained in terms of color development and conductivity after firing. There are effects such as Ultraviolet curable resin used in the present invention (1)
is a polymerizable compound 'b} with a soluble molecular weight of 1000 to 150
00 saturated copolymerized polyester [a}.

The polymerizable compound used in the present invention 'b}' is a soluble saturated copolymerized polyester having a molecular weight of 1,000 to 15,000 {a}
is a polyester synthesized from saturated polycarboxylic acids and their derivatives and polyhydric alcohols.

Examples of saturated polycarboxylic brewing ingredients include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, Examples include aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and chlorendoic acid.

These components may be used alone or in combination. It is desirable to use 5-sodium sulfoisophthalic acid as part of the saturated polycarboxylic brewing ingredients because it improves the dispersibility of pigments, conductive particles, magnetic particles, etc., which will be described later.

Examples of polyhydric alcohol components include ethylene glycol, propylene glycol, 1,4-phthanediol,
Alkylene glycols such as 1,6-hexanediol, 1,5-pentanediol, neobentyl glycol, polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol of tetra or more, dipropylene glycol, polypropylene glycol of tri or more , halogenated alkylene glycols such as dibromoneobentyl glycol, 1,4-
Examples include cyclohexanediol, an ethylene oxide or/and propylene oxide adduct of bisphenol A, an ethylene oxide and/or propylene oxide adduct of hydroxylated bisphenol A, and 1,4-cyclohexanedimethanol.

These glycol components may be used alone or in combination. As the saturated polyvalent carboxylic acid brewing component, trivalent or higher saturated carboxylic acids such as trimellitic acid and pyromellitic acid may be used in addition to the above-mentioned dicarboxylic acids.

As the polyhydric alcohol component, in addition to the above-mentioned glycols, it is also possible to use polyhydric alcohols of trihydric or higher hydricity, such as trimethylolpropane, trimethylolethane, and bentaerythritol. A small amount of carboxylic acid or monohydric alcohol may also be used in combination.These saturated copolymerized polyesters may be used alone or in combination of two or more.The method for producing the saturated copolymerized polyester 'a) used in the present invention includes There are no particular limitations, and methods such as transesterification and direct esterification may be used, and if necessary, known catalysts such as tetra-n-butyl titanate and stannous oxalate may be used.

Of the saturated polycarboxylic brewing components of the saturated copolymerized polyester [a} used in the present invention, 20 mol% or more must be aromatic dicarboxylic acids, particularly terephthalic acid and/or isophthalic acid. In the saturated copolymerized polyester 'a}, the aromatic dicarpone brewing component is preferably terephthalic acid and/or isophthalic acid, and the polyhydric alcohol component is preferably a C, to C, 2 polyhydric alcohol. If the proportion of aromatic dicarboxylic acid in the saturated polyhydric dicarboxylic acid is less than 20 mol%, an ink with poor adhesiveness and film strength will be obtained. 1000-150
00, and it is necessary that the polymerizable compound (to be described later) is soluble.

Here, the saturated copolymerized polyester soluble in the polymerizable compound {b}' refers to a saturated copolymerized polyester that is soluble in the polymerizable compound, especially acrylic esters, at least 1% by weight, preferably 2% by weight or more, and is uniform at room temperature. It is also a saturated copolymerized polyester that provides a clear solution. Highly crystalline saturated polyesters such as polyethylene terephthalate and polybutylene terephthalate have poor solubility and cannot be used. It is used by copolymerizing glycol and 1,6-hexanediol to solubilize it. In other words, examples of preferable components of the saturated copolymerized polyester (a) that satisfy the above-mentioned self-solubility include "for example, a two-component system of terephthalic acid and isophthalic acid as brewing components, a system of terephthalic acid, isophthalic acid, and adipic acid as brewing components. There are three-component systems, two-component systems of terephthalic acid and adipic acid, three-component systems of terephthalic acid, isophthalic acid, and sebacic acid, and polyhydric alcohol components include "two-component systems of ethylene glycol and propylene glycol," There are two-component systems of ethylene glycol and hexanediol to two-component systems of ethylene glycol and neobentyl glycol, but ``of course, it is not limited to these.

Also, a polymerizable compound of L saturated copolymerized polyester [a} {
Since the solubility in the saturated copolymerized polyester 'a' is greatly influenced by the saddle value and molecular weight of the saturated copolymerized polyester 'a}, the molecular weight needs to be in the range of 1000 to 15000, and the saddle number should be 50 or less. It is preferable that there be.

If the saturated copolymerized polyester contains a nitrogen atom, it is undesirable because the storage stability of the ink will be poor. It is a photopolymerizable compound, and at least one portion of the polymerizable compound has two or more double bonds in the molecule.

Examples of photopolymerizable compounds having one polymerizable double bond in the molecule include styrenic compounds such as (amount 1 styrene), a-methylstyrene to chlorostyrene, skin methyl (meth)acrylate (methyl acrylate and methyl means methacrylate.

This aircraft will be referred to as the same aircraft below. ) “Ethyl (meth)acrylate, n
- and i-propyl (meth)acrylate, Todoroki-, s
ec- and t...butyl (meth)acrylate "2-ethylhexyl (meth)acrylate..." lauryl (meth)acrylate
Acrylate Alkyl (meth)acrylates such as hestearyl (meth)acrylate or methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. Allyloxyalkyl (
Hydroxy alkyl (meth) acrylates such as meth) acrylate and hydroxyethyl (meth) acrylate to halogen-substituted alkyl (meth) acrylates, or polyoxyalkylene glycol monos such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Examples include substituted alkyl mono(meth)acrylates such as (meth)acrylates or alkoxypolyoxylalkylene glycol mono(meth)acrylates. Also, (ill)
Mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide adducts of bisphenol A, or mono(meth)acrylates of alkylene oxide adducts of hydrogenated bisphenol A, such as ethylene oxide or propylene oxide adducts of hydrogenated bisphenol A There are meta)acrylates, etc. Further, a terminal isocyanate group-containing compound obtained by reacting 0 diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds is further reacted with an alcoholic hydroxyl group-containing (meth)acrylate. Urethane-modified mono(meth)acrylate having a (meth)acryloyloxy group - or an epoxy mono(meth)acrylate obtained by reacting a compound having one or more epoxy groups in the M molecule with acrylic acid or methacrylic acid , or oligoester mono(meth)acrylate obtained by reacting acrylic acid or methacrylic acid as a side carboxylic acid component, and a polyhydric carboxylic acid and a polyhydric alcohol of dihydric or higher hydric content as an alcohol component. Examples of photopolymerizable compounds having two polymerizable double bonds include (i) ethylene glycol di(meth)acrylate to propylene glycol di(meth)acrylate "114-butanediol di(meth)acrylate" Bentyl glycol di(
meth)acrylate turtle, 146-hexanediol di(meth)acrylate, and other fullkylene glycol di(meth)acrylates to diethylene glycol di(meth)acrylatetotriyutylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , polyoxyalkylene glycol di(meth)acrylate such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, halogen-substituted alkylene glycol di(meth)acrylate, hydroxyl-substituted alkylene glycol di(meth)acrylate
Substituted alkylene glycol di(meth)acrylates such as acrylates, di(meth)acrylates of alkylene oxide adducts of bisphenol A such as ethylene oxide and/or propylene oxide adducts of bisphenol A
acrylates, di(
meth) acrylate, (ill) a terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance,
Furthermore, a urethane-modified di(meth)acrylate having two (meth)acryloyloxy groups in the molecule obtained by reacting an alcoholic hydroxyl group-containing (meth)acrylate, and a urethane-modified di(meth)acrylate having two or more epoxy groups in the molecule of G Epoxy di(meth)acrylate obtained by reacting a compound having acrylic acid or/and methacrylic acid, acrylic acid or methacrylic acid as the M carboxylic acid component, and a polyhydric carboxylic acid, and a divalent or higher polyhydric acid as the alcohol component. Oligoesterdi obtained by reacting with alcohol (
Representative examples include meth)acrylate. Examples of photopolymerizable compounds having three or more polymerizable double bonds in the molecule include (j) trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, "besotaerythritol tetra(meth) ) Polyhydric (meth)acrylate of trihydric or higher aliphatic polyhydric alcohol such as acrylate, or polyhydric (meth)acrylate of trivalent or higher halogen-substituted aliphatic polyhydric alcohol, or trivalent or higher hydroxyl substituted aliphatic Polyhydric (meth)acrylate of polyhydric alcohol, (ii) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance, and further alcoholic hydroxyl group-containing (meth)acrylate. There are urethane-modified polyvalent (meth)acrylates having three or more (meth)acryloyloxy groups in the molecule obtained by reacting acrylates.

The (meth)acrylate having two or more functionalities used as the polymerizable compound [b} is particularly di(meth)acrylate of C2 to C,2 alkylene glycol, glycerin tri(
meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)
Preferred are (meth)acrylates selected from acrylates, bentaerythritol tetra(meth)acrylates, and di(meth)acrylates of ethylene oxide and/or propylene oxide adducts of bisphenol A.

These polymerizable compounds may be used alone or in combination.

However, the polymerizable compound used in the present invention [
b), at least a portion of which must be a compound having two or more polymerizable double bonds within the molecule.
The compound having two or more polymerizable double bonds in the molecule is 1 to 10% by weight of the polymerizable compound (b), preferably 5 to 10% by weight.
9% by weight. In particular, when using a compound with one polymerizable double bond in the molecule and a compound with 2, 3 or 4 polymerizable double bonds in the molecule, two
It is preferable that the amount of the compound having at least one polymerizable double bond is 5 to 70% by weight of the polymerizable compound [b}.

Furthermore, when a compound having two polymerizable double bonds in the molecule and a compound having three or four polymerizable double bonds in the molecule are used together, two polymerizable double bonds in the molecule It is preferable that the compound having the above accounts for 85 to 95% by weight of the polymerizable compound (b).

When only a compound having one polymeric double bond in the molecule is used, a so-called crosslinking reaction cannot occur.
The purpose of the invention cannot be achieved. In the present invention, the blending ratio of the polymerizable compound (saturated copolymerized polyester {a) soluble in the polymerizable compound (b) and the polymerizable compound {b} is 20:80 by weight.
~70:30. If the blending ratio of the copolyester (a) is less than 2% by weight, it will not be possible to obtain a product with excellent sinterability, and the curability will also be extremely poor. On the other hand, if it exceeds 7% by weight, the viscosity becomes too high, leveling properties and plate separation become poor, and the printing speed becomes too slow, which is not practical. The photosensitizer (b) used in the present invention is
The compound that promotes the photopolymerization reaction of the polymerizable compound {b} is not particularly limited and includes, for example, benzoin methyl ether, benzoin ethyl ether, benzoin-i-
Penzoins such as propyl ether, benzoin, a-methylbenzoin, anthraquinones such as 9010-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, benzophenone, P-chlorobenzophenone, P-dimethylaminobenzophenone, etc. penzophenones, sulfur-containing compounds such as diphenyl disulfide and tetramethylthiuram disulfide, and pigments such as methylene blueeosin and fluorescein, which may be used alone or in combination of two or more.

The blending amount of the photosensitizer (0) is 0.05 based on the total amount of the saturated copolymerized polyester [al and polymerizable compound (b)].
~20% by weight, especially 0.5-10% by weight is preferred. In addition, in order to increase the photopolymerization reaction promoting effect of the photosensitizer (0), trietanolamine, triethylamine, N/N-diethylaminoethyl (meth)
It is also possible to use amines such as acrylates and phosphorus compounds such as triphenylphosphine.

Known thermal polymerization inhibitors, leveling agents, antifoaming agents, thickeners, thixotropic agents, etc. are added to the ultraviolet curable resin used in the present invention to adjust viscosity, storage stability, printability, etc. used.

The sinterable solid (m) used in the present invention includes heat-resistant inorganic pigments, conductive particles, magnetic particles, 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, manganese oxide, cerium oxide, nickel oxide, iron oxide, Copper trioxide, vanadium stannate, iron chromate, uranium yellow, cadmium sulfide, gold, iron titanate, uranium titanate, cadmium mooselenium red, cobalt titanate, gold chloride, manganese sulfate, vanadium pentoxide, etc. This can be cited as a representative example.

4 Conductive particles include gold powder, silver powder, tungsten powder, molybdenum powder, copper powder, aluminum powder, nickel powder, tin powder, etc., and magnetic particles include iron oxide, chromium oxide, cobalt oxide, iron-cobalt, iron-nickel. , magnetite, etc. Frit and flux are used to promote uniform color development of the heat-resistant inorganic pigment and to adjust the firing temperature by selecting their components. Its components include Li20, Na20, K2
0, Mg0, a0, B30, Zn○, Pb○, B203
, AI203, SiQ, etc., and various compositions are selected depending on the purpose. The amount of the sinterable solid (m) used in the present invention is usually 30 to 9% by weight of the ultraviolet curable baking ink.

In the present invention, as a method for printing the ultraviolet curable baking ink, screen printing, offset printing, gravure offset printing, etc. can be used, but screen printing is particularly preferable.

Light sources used to cure ultraviolet curable baking ink include high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, xenon lamps, carbon arc lamps, and metal halide lamps. If the amount of solids (m) exceeds 6% by weight, it is preferable to use metal halide lamps. The firing conditions in the present invention vary depending on the use and purpose, but it is performed in an oxidizing atmosphere when producing ceramics, glass, etc., and in a non-oxidizing atmosphere when forming a conductive circuit, etc., and the firing temperature is Usually 40,000 to 1,300 pm.

When the method of the present invention is used to decorate ceramics, glass, tiles, etc., and to form circuits on ceramics, etc., the reproducibility of fine patterns and patterns is good, and there are no skipped lines or cracks during firing. Since no waste is generated, it greatly contributes to improving the working environment, high productivity, and high precision in the kiln industry or the electronics industry, and its industrial significance is extremely large.

Examples will be given below to explain the present invention more specifically, but the present invention is of course not limited by the Examples. Reference Example 1 5 parts of saturated copolymerized polyester resin (molecular weight: 3600) synthesized by a conventional method and having the following composition, 25 parts of tetrahydrofurfuryl acrylate, 25 parts of 1,6-hexanediol diacrylate, and a polymerization inhibitor. 0.01 part of hydroquinone was mixed and dissolved at 80°C.

The resulting solution was homogeneous and clear at room temperature. Composition of saturated copolymerized polyester ■ Saturated polycarboxylic brewing component Terephthalic acid 50 mol% Isophthalic acid 50 mol% Polyhydric alcohol component Ethylene glycol 40 mol% 116-hexanediol 60 mol% Obtained solution 4 base parts,
4 parts of penzoin-i-propyl ether as a photosensitizer, 6 parts of a ceramic painting pigment (selenium red), and 2 parts of a leveling agent were branized with three rolls to obtain an ultraviolet curable baking ink.

Reference Example 2 4 parts of saturated copolymerized polyester (B) (molecular weight: 2800) synthesized by a conventional method and having the following composition, 3 parts of tetrahydrofurfuryl acrylate, and 3 parts of dimethacrylate of 4 moles of ethylene oxide adduct of bisphenol A 1 part and 0.01 part of hydroquinone were mixed and dissolved at 80°C.

The resulting solution was homogeneous and clear at room temperature. Composition of saturated copolymerized polyester legs Saturated polycarboxylic brewing ingredients Terephthalic acid 50 mol% Isophthalic acid 50 mol% Polyhydric alcohol ingredients Ethylene glycol 48 mol% Neobentyl glycol 52 mol% Obtained solution 15 parts, nickel powder 75 parts , 5 parts of low melting point glass frit, 1.5 parts of benzoin methyl ether, and 1 part of leveling agent were kneaded using three rolls to prepare an ultraviolet curable baking ink.

Reference example 3 1 part of pentaerythritol triacrylate, 28 parts of pentaerythritol tetraacrylate, 6 parts of ceramic painting pigment (selenium red), 2 parts of leveling agent, 3 parts of benzoin ethyl ether An ultraviolet curable baking ink was prepared by kneading with this roll.

Example 1 After screen-printing a pattern on ceramics using the ultraviolet curable baking ink obtained in Reference Example 1, 5. ship. W. It was cured by irradiating it with ultraviolet light at a distance of 19 degrees under a high-pressure mercury lamp at a distance of 15 degrees.

Next, this pottery was placed in an electric furnace and heated at 100oC/in air.
The temperature was raised to a maximum temperature of 850°C at a heating rate of 850°C.
When I held it for 30 minutes, fired it, and allowed it to cool naturally, I was able to get a beautiful print with no cracks or missing patterns. Example
2 A conductive circuit was screen printed on an insulating ceramic substrate using the ultraviolet curable baking ink obtained in Reference Example 2.
Pine. W. It was cured by irradiating ultraviolet rays at a distance of 10 arcs under a metal halide lamp for three periods.

Next, this substrate was placed in an electric furnace, heated at a rate of 8 mm in a nitrogen stream, fired until it reached a maximum temperature of 1,000 mm, and then allowed to cool naturally, resulting in a layer thickness of 10 mm and a line width of 100 mm. The resistance value of the enemy was 2.10/to. Comparative example
1 Pottery was painted in exactly the same manner as in Example 1, except that the ultraviolet curable firing ink obtained in Reference Example 3 was used, but the design did not jump much during firing and good results could not be obtained. .

Comparative Example 2 Saturated copolymerized polyester, Byron 300 manufactured by Toyobo Book Co., Ltd.
(Molecular weight: 22,000) I tried to mix and dissolve 5 parts of tetrahydrofurfuryl acrylate, 25 parts of 1,6-hexanediol diacrylate, and 0.01 part of hydroquinone as a polymerization inhibitor at 8 pi, but the solution was extremely high. It was not possible to form a uniform solution due to the viscosity.

Therefore, it was also impossible to prepare an ultraviolet curable baking ink. Furthermore, the same results were obtained when a saturated copolymerized polyester such as Bylon 200, 3-ho, manufactured by Toyobo Co., Ltd., was used in place of the above-mentioned Byron 300. Reference example
4 5 parts of the saturated copolymerized polyester 'B' used in Reference Example 2,
Tetrahydrofurfuryl acrylate 2 anchors, 1,6-
25 parts of hexanediol diacrylate, 5 parts of pentaerythritol tetraacrylate, and 0.02 part of hydroquinone as a polymerization inhibitor were mixed and dissolved at 80°C.

15 parts of the obtained solution, 75 parts of nickel powder, 5 parts of low melting point glass frit, 1.5 parts of beizin methyl ether,
One part of the leveling agent was milled using three rolls to prepare an ultraviolet curable baking ink. Comparative Example 3 A conductive circuit was screen printed on an insulating ceramic substrate using the ultraviolet curable baking ink obtained in Reference Example 4,
The gunwale. W. It was cured by irradiating ultraviolet rays between 6 inkstone sands at a distance of 10 cm under a metal halide lamp.

Claims (1)

[Claims] 1 Consisting of a saturated copolymerized polyester (a) with a molecular weight of 1000 to 15000 and a polymerizable compound (b) that is soluble in the polymerizable compound (b), on a sintered body base such as ceramics or ceramics, and (a)/(b) )=20/80 to 70/30 (weight ratio) of ultraviolet curable resin (I) and photosensitizer (II)
and a sintered body substrate characterized by printing an ultraviolet curable sintering ink containing sinterable solid (III) as an essential component, curing it by irradiating it with ultraviolet rays, and then sintering it to form a pattern. How to form a pattern.