JPH0459681A - Production of glazed base board - Google Patents

Abstract

PURPOSE:To increase positional accuracy of partial glaze by applying specific glass paste on a ceramic base plate, masking parts except a desired 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 photosensitive resin in which exposed part becomes to be insoluble in a developing solution, a photosensitizer, a photoinitiator and a plasticizer, etc., 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 >=mumRa surface roughness and dried, then parts except desired glaze pattern of the resultant paste layer is masked with a photomask 3, thus light 4 is irradiated and the resultant system is developed to obtain a base plate having light-irradiated 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 glaze 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. To eliminate this drawback, if you use a mesh with a small opening,
It was necessary to repeat printing and drying many times to achieve the desired glaze thickness. For example, using glaze paste i that had obtained a dry film thickness of 60 μm with 60 meshes,
When used for mesh screen printing, it was often necessary to repeat printing and drying four times to obtain a dry 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 method in which a glaze pattern for transfer is previously formed on a base material and this pattern is transferred under pressure onto a ceramic substrate. Disclosed.

(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 is that the position ff degree of the position decreases. That is, since the pattern formed on the substrate is pressure-transferred onto the ceramic substrate, misalignment is unavoidable.

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

(Means for Solving the Problems) The present invention provides a method of applying a glass paste containing a photosensitive resin composition and an inorganic glass powder whose exposed portions are insoluble in a liquid to a ceramic substrate, and then applying a glass paste containing a desired clay to a ceramic substrate. t: It relates to a method for manufacturing a glazed substrate characterized by masking a portion other than the pattern portion, irradiating it with light, first developing it, and then baking it.

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

For boat fishing, known negative photosensitive resin compositions can be used. Such negative photosensitive resin compositions include, for example, trimethylolpropane, pentaerythritol,
Unsaturated group-containing compounds obtained by reacting polyhydric alcohols such as tetraethylene glycol with unsaturated monocarboxylic acids such as acrylic acid; unsaturated group-containing compounds obtained by reacting epoxy resins with unsaturated monocarboxylic acids. , dihydric alcohol and unsaturated dihydric carboxylic acid (or its anhydride)
The product is a compound having a reactive unsaturated group such as an unsaturated polyester resin obtained by reacting with a photoinitiator, a sensitizer, and a plasticizer as necessary.

Those containing reactive diluents, binder resins, heat stabilizers, etc. are known. 'Also. A composition containing an epoxy resin and an aromatic onium salt compound as its photoinitiator can also be used as a negative photosensitive resin composition.

These photosensitive 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. In order to obtain a good partial glaze pattern, the inorganic glass powder has an average particle size of 5 μm.
The following are preferred. A photosensitive resin composition and a solvent for the resin composition are added to this glass powder to create a glass paste, but when 8 units more of the photosensitive resin composition is added.

When baking to obtain a glaze pattern, glass barge occurs due to the low concentration of the glass.

However, 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 crIi' to Z
1 cm', more preferably 0.4 cm' to 1.5 cm'. Further, a solvent is added to give the glass paste a viscosity, thixotropy, etc. suitable for each coating method described below. Ceramic substrates are alumina substrates and AI! N board, PEJ rear board, etc. are used. In addition, a better glaze pattern can be obtained when the surface roughness of the ceramic substrate is smaller, and it is preferable that Fi1
μmR,a or less.

How to uniformly apply glass paste to a ceramic substrate
h Screen printing method, date printing method.

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) other parts with a film or the like that does not transmit light so that only a desired glaze pattern part is exposed. There are no particular restrictions on the masking method. The wavelength and amount of light is selected to provide sufficient sensitization. It is preferable to perform post-baking as necessary after light irradiation. Next, the mask 't* is removed, and the image is sufficiently developed and washed with water to remove the glass paste in the areas that are not exposed to j1 light. An acid, alkali, organic solvent, etc. for the developer rri photosensitive resin composition is used, and adhering glass powder is also removed by spraying or the like. A method of blowing with compressed air may also be used. Finally, the substrate is fired to print the glaze pattern on the substrate, but it is necessary to prevent defects from occurring in the glaze pattern, so it is preferable to place it in a container with a lid and bake it.

An example of the present invention will be explained using all the drawings. A photosensitive resin composition is placed on the ceramic substrate l shown in FIG.

A glass paste 2 made of glass powder and a solvent is applied, and after drying, a photomask 3 prepared so as to expose only a desired glaze pattern portion is applied to the dried glass paste 5 as shown in FIG. The light 4 is applied over the top.

Next, the unexposed portions are washed off to obtain a substrate having the glass paste 6 irradiated with light as shown in FIG. This is developed in an electric furnace or the like to obtain a glazed substrate 7 having a glazed layer 8.

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

Examples The following solutions of photosensitive resin compositions were prepared.

■ After the addition reaction of phenol novolak type epoxy resin and acrylic acid at a ratio of (acid equivalent)/(epoxy equivalent) of 1.0, tetrahydrophthalic anhydride is added to (acid anhydride equivalent)/(epoxy group and carboxyl 100 parts by weight of an unsaturated group-containing compound obtained by addition reaction at a ratio of 0.4 (equivalents of hydroxyl groups produced by reaction with groups), 6 parts by weight of benzophenone, 0.6 parts by weight of 44'-bis(diethylamino)benzophenone, and 60 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

■ 70 parts by weight of methacrylic acid/methyl methacrylate/butyl acrylate (20/7515 weight ratio) copolymer (molecular weight approximately 70,000), 30 parts by weight of trimethylolpropane triacrylate, 2-methyl-1-(4-methylthio phenyl)-2-morpholino-propane-1 (manufactured by Cipakaigyi).

IRGACURE 907) 6 parts by weight, 0.6 parts by weight of 4,4'-bis(diethylamino)benzophenone, and 6 parts by weight of propylene glycol monomethyl ether acetate
0 parts by weight.

■ Methyl methacrylate polymer (molecular weight approximately 20,000) 70 parts by weight, 3 parts dipentaerythritol hexamethacrylate
0 parts by weight, 6 parts by weight of benzophenone.

4.4'-bis(diethylamino)benzophenone0.
6 parts by weight and 60 parts by weight of 0-xylene.

Solution of the photosensitive resin composition of ■, ■ or ■ and aluminum borosilicate glass powder (composition is S i 0240 mo
l%, Aj'20310moI! %, B2O31
5rno1%, CaO15m01! s, Mg05m
O/% and Pb015m0/%, the average particle size of which is shown in Table 1) were mixed in the proportions shown in Table 1. This mixture was kneaded using a grinder while adding turpentine oil (Wako Tsumugi Pharmaceutical Co., Ltd. reagent grade 1), and the viscosity was adjusted to 500 Pa-s.

Glass pastes Nos. 1 to 10 were obtained. Apply this glass paste for 1r using a 60 mesh screen and 100 plate angles.
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. The dried product was covered with a film mask capable of exposing only a pattern portion having a width of 400 μm and a length of 100 marks, and exposed to light using a high-pressure mercury lamp. The exposure amount was 700 mJ/cm'' for 325 nm light.The sample after exposure was
No. 9 to No. 9 were developed by applying a shower of aqueous sodium carbonate solution, and No. 10 Fil, 1.1-) was developed by applying a shower of dichloroethane. After development, the samples were washed with water, drained, and placed in a ceramic refractory container, which was covered with an opaque quartz plate. This was heated to 1100°C in an electric furnace at a rate of 150°C per hour.

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 portion of the cooled samples, as shown in Table 2, good results were obtained for samples with sample numbers 1.2.3, 8.9, and 1OO. but.

No. 4, which has a large amount of resin, causes the glass to burst, conversely, No. 5, which has a small amount of resin, causes the paste to gel, and No. 6, which has a large glass powder particle size, and No. 4, which has a rough substrate surface, have problems with the glaze line after firing. Ta.

Table 1 Table 2 Comparative Examples Aluminum borosilicate glass powder (average particle size 5pm 8
iQ240mol! %, A/20310mi! '
%, Btu315mol/%, CaO15mol%
, Mg 0.5mo/% and Pb015mo1%)1
00 parts by weight, ethyl cellulose (Kanto Chemical Layer, 100C
1)) 5 parts by weight and turpentine were mixed in a grinder. Turpentine oil was appropriately added so that the viscosity of the glass paste was 500 Pa, s. This paste was made into 100 meshes with a length of 100 openings, a width of 400 μm, and 2
Emulsion thickness 2 with 00 mesh or 400 mesh
1100trr angle Xl using 0 ttm screen
Printing was carried out on an alumina substrate having a thickness of a and a surface roughness of 0.4 μmPa. After drying the printed matter in a dryer at 100°C for 20 minutes,
The containers were placed in a ceramic refractory container, covered with a temporary lid made of opaque quartz, heated to 1100°C at a rate of 150°C per 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 ta of the cooled sample, 10
When using a screen with 0 mesh, the width is 600 μm.
±90μm and height 40μm±6μm, 9,20
Width: 500μm± when using a 0.0mm screen
When a 4QQ mesh screen of 40 μm and a height of 28 μm±3 μm was used, it was found to be 440 μm±25 μm and a height of 15 μm±2 μm.

Sample numbers 1, 2, and 3°8.9E that were evaluated well in the examples
Both the width accuracy and height accuracy of the glaze line were inferior in the ratio ffMJ compared to the glaze line width and height.

Furthermore, 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 it was not possible to form a very high glaze line.

(Effects of the Invention) According to the present invention, a nine-part 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 the drawing]

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 the required areas of the glass paste using a photomask, and Figure 3 is a diagram showing the removal of unexposed areas. A perspective view of the ceramic substrate, and FIG. 4 is a perspective view of the glazed substrate. Explanation of symbols 1...Ceramic substrate 2...Glass paste 3
...Photomask 4...Light 5...Glass paste after drying 6...Glass paste irradiated with light

Claims (1)

[Claims] 1. After coating a ceramic substrate with a glass paste containing a photosensitive resin composition and inorganic glass powder whose exposed areas are insoluble in a developer, masking areas other than the desired glaze pattern area and irradiating with light; A method for producing a glazed substrate, which is characterized in that it is then developed and then baked.