JPH0459680A - Production of glazed base board - Google Patents

Abstract

PURPOSE:To increase positional accuracy of partial glaze by applying a glass paste containing a specific photosensitive resin composition and inorganic glass powder on a ceramic base plate, masking a glaze pattern part, irradiating light, developing and baking. CONSTITUTION:Glass paste 2 is obtained by mixing 0.3-2.1cm<3> photosensitive resin composition composed of a positive-type photosensitive resin, a sensitizer, a plasticizer, a binder resin and a heat stabilizer, etc., and exposed part becomes to be soluble in a developing solution with 1cm<3> glass powder having <=5mum averaged granular diameter and a solvent. Next, said glass paste 2 is applied on a ceramic base plate 1 having <=1mumRa surface roughness and dried, then desired glaze pattern part in the resultant paste layer is masked by a photomask 3, thus light 4 is irradiated and resultant system is developed to obtain a base plate form having not-exposed glass paste 6. Then, said plate is baked to afford the aimed glazed base plate 7.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a glazed substrate used for a thermal head or the like, and particularly to a method for manufacturing a glazed substrate in which a glazed layer is partially formed on the surface of a ceramic substrate.

(Prior Art) Conventionally, partially glazed substrates in which a glaze layer is formed on a portion of a ceramic surface have been produced mainly by forming a glaze layer by screen printing and then baking the glaze layer.

However, since screen printing uses a mesh, the linearity of the glaze line is poor, which has the disadvantage of causing unevenness at the top of the partial glaze. If a mesh with a small opening was used to eliminate this drawback, it would be necessary to repeat printing and drying many times in order to obtain a predetermined glaze thickness. For example, when using a 400-mesh screen with a glaze paste that had a dry film thickness of 60 μm with 60 meshes, it was necessary to repeat printing and drying four times to obtain a dry film thickness of 60 μm.

In order to eliminate these drawbacks of the screen printing method, Japanese Patent Application Laid-Open No. 63-71365 discloses a grace pattern 1 for transfer onto a base material! r: A method is disclosed in which a pattern is formed in advance and then transferred under pressure onto a ceramic substrate.

(Problems to be Solved by the Invention) However, although the method disclosed in JP-A-63-71365 improves the ability to form fine lines and form a thick glaze layer at the same time, The disadvantage was that the positional accuracy of That is, since the pattern formed on the substrate is pressed and transferred onto the ceramic substrate, misalignment is unavoidable.

The present invention has excellent fine line properties of the 9-part glaze,
The present invention provides a method for manufacturing a glazed substrate in which a thick glaze layer can be formed at one time and the positional accuracy of partial glazes is high.

(Means for Solving the Problems) The present invention provides a method for forming a desired gray pattern after coating a ceramic substrate with a glass paste containing a photosensitive resin composition and an inorganic glass powder in which the illuminated portion is soluble in a developer. The present invention relates to a method for manufacturing a glazed substrate, which is characterized by masking only a portion thereof, irradiating it with light, developing it, and then baking it.

The photosensitive resin composition used in the present invention is as follows.

For boat fishing, known positive photosensitive resin compositions can be used.

Such positive photosensitive resin compositions include, for example, a compound having an OH group such as tetrahydroxybenzophenone, bisphenol type epoxy resin, polyvinylphenol, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and Compounds with naphthoquinone diazide photosensitive groups obtained by reaction, polymeric compounds with O-nitrobenzyl photosensitive groups in side chains such as O-nitrobenzyl acrylate/methyl methacrylate/acrylic acid copolymers, polyaldehyde resins, polycarbonates The main components are a combination of a resin that decomposes with a strong acid and an onium salt compound that generates a strong acid when exposed to light, or a combination of an acrylic polymer with a vinyl group in the side chain and a monocarboxylic acid with a thiol group. It is known to contain a sensitizer, a softening agent, a binder resin, a heat stabilizer, etc. as necessary.

These resin compositions are usually used after being dissolved in a solvent.

The solvent is not particularly limited as long as it is compatible with the photosensitive resin composition. Inorganic glass powder.

In order to obtain a good partial gray pattern, it is preferable that the powder has an average particle size of 5 μm or less.

A photosensitive resin composition and a solvent for the resin composition are added to this glass powder to create a glass paste, but if too much photosensitive resin composition is added, the concentration of the glass will be low when baking to obtain a grace pattern. A glass barge appears and disappears. Furthermore, if the amount of photosensitive resin is too small, it will be difficult to form a paste. Therefore, the amount of the photosensitive resin composition added is preferably from 0.3 cm3 to Z1 cm', more preferably from 0.4 d to 1.5 am' per cm3 of volume of the glass powder. Further, a solvent is added to give the glass paste a viscosity, chikuntropy, etc. suitable for each coating method described below.

Further, as the ceramic substrate, an alumina substrate, an hlN substrate, a beryllia substrate, or the like is used. In addition, the smaller the surface roughness of the ceramic substrate, the better the glaze layer and turn.
Preferably, ld is 1 μmRa or less.

Screen printing and dipping methods are used to uniformly apply glass paste to ceramic substrates.

A roll coater method, a spin coater method, a transfer method, etc. are used, but a screen printing method is preferable because it can print thickly.

Light irradiation is performed by covering (masking) only the gray pattern portion with a film or the like that does not transmit light so that the portions other than the desired gray pattern portion are exposed to direct light. There are no special restrictions on masking methods.

The wavelength and amount of light is selected to provide sufficient photosensitivity.

After the light irradiation, it is preferable to perform a post bake as necessary. Next, the mask is removed, and the glass paste is thoroughly developed and washed with water to remove the glass paste in the areas that will not be exposed to light. The developer used is an acid, alkali, organic solvent, etc. for photosensitive resin compositions, and adhering glass powder is also removed by spraying or the like. Finally, it is fired to print a grace pattern on the substrate, but it is necessary to prevent defects from occurring in the grace pattern, so it is preferable to place it in a container with a lid and print it.

An example of the present invention will be explained using the drawings. A glass paste 2 consisting of a photosensitive resin composition, glass powder, and a solvent is applied onto the ceramic substrate l shown in Fig. 1, and after drying, the parts other than the desired gray pattern are exposed as shown in Fig. 2. A photomask 3 which has been prepared in such a manner is overlapped and light 4 is irradiated.

Next, the exposed portion is washed off to obtain a substrate shape having the glass paste 6 not exposed to light as shown in FIG. This is fired in an electric furnace or the like to obtain a glazed substrate 7 having a brace layer 8.

(Example) The present invention will be explained in detail below.

Examples The following solutions of photosensitive resin compositions were prepared.

(1) 100 parts by weight of 0-nitrobenzyl acrylate/methyl methacrylate/acrylic acid (60/30/10 weight ratio) copolymer (molecular weight approximately 30,000), 10 parts by weight of benzyl dimethyl ketal, and propylene glycol monomethyl as a solvent. 60 parts by weight of ether acetate.

■ Methyl methacrylate/allyl methacrylate 165
735 weight ratio) copolymer (molecular weight approximately 50,000), 100 parts by weight, and 30 parts by weight of mercaptoconophosphoric acid.

10 parts by weight of benzophenone, 0.3 parts by weight of 44'-bis(diethylamino)benzophenone and 60 parts by weight of propylene glycol monomethyl ether acetate.

■ Resorcinol monomethacrylate/2-ethylhexyl methacrylate (70/30 weight ratio) copolymer 1
00 parts by weight, 10 parts by weight of benzyl dimethyl ketal and 6 parts by weight of propylene glycol monomethyl ether acetate.
0 parts by weight.

Solution of photosensitive resin composition of ■, ■ or ■ and aluminum borosilicate glass powder (composition is 510240 mol
%, Altos 10 mol%, BzOs 1
5mol! %, CaO15mol, MgO5mol
% and PbO15mo1%, the average particle size is shown in Table 1) 1r: Mixed at the ratio shown in Table 1. This mixture was kneaded using a crusher while adding turpentine oil (grade 1 reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.), and the viscosity was adjusted to 500 Pa-8.
Glass pastes Nos. 1 to 10 were obtained. Apply this glass paste to 100=II using a 60 mesh screen.
! It was uniformly coated onto an alumina substrate having a thickness of Im and a surface roughness shown in Table 1. After coating, it was dried in a dryer at 80°C for 20 minutes. Width 400μm and length 100mm for dry matter
The film was covered with a film mask that exposed areas other than the patterned areas, and exposed using a high-pressure mercury lamp. Exposure amount ll″t325nm
2000 mJ/am2 for the light. The exposed sample was developed by showering with a 1% aqueous sodium hydroxide solution. After testing, the washed and drained samples were placed in a ceramic refractory container and covered with an opaque quartz plate. This was heated to 1100° C. at a rate of 150° C./hour in an electric furnace, held for 30 minutes, and then cooled in the furnace.

As a result of evaluating the width and height of the glaze line part of the cooled sample, the sample numbers were 1.2 and 3 as shown in Table 2.
, 8.9 and 1O gave good results. However, the glass bursts in No. 4, which has a large amount of resin, and conversely, the paste gels in No. 5, which has a small amount of resin, and No. 6, which has a large glass powder particle size, causes the paste to gel.
No. 4 and No. 4, which had a rough substrate surface, had a problem with the glaze line after firing.

Table 1 Table 2 Comparative Examples Aluminum borosilicate glass powder (average particle size 5 μm 5
iCh 40 mo/%, A/*0310 mo/%,
B2031'5moI! %, CaO15mot! %
, MgO5rno1% and PbO15mo/%) 10
0 parts by weight and ethyl cellulose (Kanto Kagaku 1100cp)
5 parts by weight and turpentine were mixed in a drawer. Add turpentine oil as appropriate so that the viscosity of the glass paste becomes 500 Pa-s. This paste is 100m long and 400m wide.
Emulsion thickness is 20 with 100 mesh, 200 mesh, or 400 mesh with micrometer pattern.
Using a μm screen, printing was performed on an alumina substrate with a surface roughness of 0.4 μmRa and a thickness of 100 square meters×1 Im. After drying the printed matter at 100°C for 20 minutes in a drying machine, it was placed in a ceramic refractory container, covered with an opaque quartz plate, and heated to 1100°C at a rate of 150°C per hour in an electric furnace.
After holding for 30 minutes, the mixture was cooled in the furnace. As a result of evaluating the width and height of the glaze line part of the cooled sample, the width was 600 μm ± 90 μm and the height was 40 μm ± 6 μm when using a 100 mesh screen. When using a 4QQ mesh screen, the width was 500 μm ± 40 μm and the height was 28 μm ± 3 μm, and when a 4QQ mesh screen was used, the screen was 440 μm ± 25 μm and the height was 15 μm.
It was μm±2 μm.

Compared to Sample Nos. 1, 2, 3° 8.9, and 10, which were evaluated well in the Examples, the width accuracy and height accuracy of the glaze line in the Comparative Example were poor in both.

In addition, in the case of using a 400 mesh screen, which had the best width accuracy among the comparative examples, the glaze height was as low as 15 μm, and the glaze height was as low as 1. It was not possible to form a high glaze line in the V.

(Effects of the Invention) According to the present invention, a partial glaze has excellent fine line properties and a thick glaze layer can be formed at once.

Furthermore, a glazed substrate with high positional accuracy of the partial glaze can be easily obtained.

[Brief explanation of drawings]

Figure 1 is a perspective view of a ceramic substrate coated with the glass paste of the present invention, Figure 2 is an explanatory diagram of irradiating light onto unnecessary areas of the glass paste using a #'i photomask, and Figure 3 is an illustration of removing the exposed areas. FIG. 4 is a perspective view of a glazed ceramic substrate. Explanation of symbols 1... Ceramic substrate 2... Glass paste 3... Photomask 4... Light 5... Glass paste after drying 6... Glass paste not exposed to light 7... Glazed substrate 8 ...Glaze layer agent Patent attorney Wakabayashi Japanese arrangement Figure 1 Figure 3 Figure 2 Figure 4

Claims (1)

[Claims] 1. After coating a ceramic substrate with a glass paste containing a photosensitive resin composition and inorganic glass powder that makes the exposed area soluble in a developer, mask only the desired gray pattern area and irradiate it with light. A method for producing a glazed substrate, which comprises baking after development.