JPH01211802A - Photosetting dielectric sintered paste - Google Patents

Abstract

PURPOSE:To obtain excellent thick film sintering property by including a cellulosic inductor, a photopolymerizing compound having a double bond in its molecule and a photopolymerizing initiator into a photosetting resin composition serving as a binder. CONSTITUTION:A photosetting dielectric sintered paste includes a vitreous frit and a photosetting resin composition. In the photosetting dielectric sintered paste, the photosetting resin composition incorporates a cellulosic inductor, a photopolymerizing compound having a double bond in its molecule and a photopolymerizing initiator thereinto. Using the photosetting dielectric sintered paste including the vitreous frit and the photosetting resin composition as requisite components, a predetermined pattern is printed on a ceramic board, and then it is sintered in an atmosphere of air after being subjected to photosetting, thereby obtaining a dielectric layer. The absence of solvents in the sintered paste can prevent any generation of pinholes caused by clogging of a screen board. In addition, preferable sintering property of the photosetting resin can prevent any pinhole, peeling and residual carbon caused by sintering.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photocurable dielectric firing paste using a photocurable resin composition as a binder.

(Prior Art) Conventionally, as a dielectric firing paste for forming a dielectric layer, a solvent-based dielectric or body firing paste consisting of a low melting point vitreous frit, a high melting point vitreous frit metal oxide, and an organic vehicle has been commonly used. be.

(Problems to be Solved by the Invention) However, since such a solvent-based dielectric firing paste contains a high boiling point solvent, (1) the drying time is long;
There are problems such as (2) pinholes are likely to occur due to clogging of the screen plate, (4) continuous printing is difficult due to large changes in the viscosity of the paste over time, and (5) significant pollution of the workplace environment.

A photocurable resin composition with good thermal decomposition properties has already been proposed as part of the present invention. (Unexamined Japanese Patent Publication No. 57-15299
3) It was found that when a photocurable resin composition thereof was used, the firing properties were poor if the fired film thickness was 30 μm or more.

(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of intensive research aimed at solving these drawbacks and obtaining a photocurable dielectric firing paste with excellent thick film firing properties.

That is, the present invention provides a photocurable dielectric firing paste containing a glassy frit (^) and a photocurable resin composition (B), in which the photocurable resin composition (B) contains ([) a cellulose derivative This is a photocurable dielectric firing paste characterized by containing (If) a photopolymerizable compound having a double bond in its molecule and (III) a photopolymerization initiator.

The vitreous frit (A) used in the present invention includes, for example, lead oxide, boron oxide, silicon oxide, sodium oxide,
Calcium oxide, cadmium oxide, aluminum oxide,
It is a compound such as magnesium oxide, zirconium oxide, manganese oxide, etc., and its content is 5% in the firing paste of the present invention.
It is 0 to 90% by weight. If the content is less than 50% by weight, the electrical properties of the dielectric layer will be poor, while if it exceeds 90% by weight, printability will be poor.

Next, in the photocurable resin composition (B) used in the present invention, the cellulose derivative (1) is, for example, a cellulose such as (+) methylcellulose, ethylcellulose, carboxymethylcellulose, oxyethylcellulose, benzylcellulose, propylcellulose, etc. Cellulose ethers such as.

(2) Cellulose organic acid esters such as cellulose formate, cellulose acetate, cellulose propionyl, cellulose acetylpropionyl, and cellulose methacryloyl; (3) cellulose inorganic acid esters such as cellulose nitrocellulose, cellulose sulfate, and cellulose phosphate; They may be used alone or in combination of two or more.

The content of the cellulose derivative (1) in the photocurable resin composition is 2 to 60% by weight, more preferably 5 to 55% by weight.

In addition, the molecule IIM of cellulose derivative is M≦1.00
There are 0,000 ce, molecule IM is 1,000,000
If it exceeds 0, it becomes poorly soluble in photopolymerizable compounds having a double bond in the molecule.The cellulose derivative of the present invention needs to be dissolved in the photopolymerizable compound having a double bond in the molecule. .

The photopolymerizable compound (II) having a double bond in the molecule includes, for example, (1) styrene compounds such as styrene and α-methylstyrene, (2) methyl (meth)acrylate, ethyl (meth)acrylate, Mono(meth)acrylate compounds such as tetrahydrofurfuryl (meth)acrylate, (3) alkylene glycol di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, ( 4) Trimethylolpropane tri(meth)
These include polyvalent (meth)acrylate compounds such as acrylate and pentaerythritol tetra(meth)acrylate.

(However, (meth)acrylate refers to metharylate and acrylate.) The compounding amount of these photopolymerizable compounds (ff) is preferably 40 to 95% by weight in the photocurable resin composition.

The photopolymerization initiator is, for example, a benzoin compound, a benzophenone compound, or a thioxanthone compound.

The amount of the photopolymerization initiator is 1 to 1 O in the photocurable resin composition.
Preferably, it is %.

The content of the photocurable resin composition (B) is 10 to 50% by weight of the fired paste of the present invention. When the content is less than 10% by weight, the paste viscosity becomes high and printing is difficult, while when it exceeds 50% by weight, the electrical properties of the dielectric layer become poor. A known thermal polymerization inhibitor, leveling agent, antifoaming agent, thixotropic agent, etc. are added to the photocurable resin composition (B),
It is generally used after adjusting the viscosity, storage stabilizer, printability, etc.

In the present invention, a predetermined pattern is formed on a ceramic substrate such as alumina using a photocurable dielectric firing paste containing the glassy frit (A) and the photocurable resin composition ([1) as essential components. The dielectric layer is obtained by printing, photocuring, and baking in an air atmosphere.

In the present invention, since the dielectric firing paste used for printing is a photocurable dielectric firing paste, it does not contain any solvent.
Therefore, no pinholes occur due to clogging of the screen plate. Regarding the fired base of the present invention, there are no particular limitations on the conditions for photocuring. As a light source used for light irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and the like are used.

As the substrate, an alumina substrate, a hollow substrate, a Varilia substrate, a nitrogen aluminum substrate, a silicon carbide substrate, etc. are used.

(Example) Examples will be given to explain the present invention in more detail.
The present invention is not limited to these examples in any way. In the examples, parts or % simply refer to parts by weight or % by weight. Measurements for performance evaluation were carried out by the following method. Ta.

Printability: A predetermined circuit pattern was printed using a 250-mesh stainless steel screen plate with 11 marks, and the printability was measured by the number of prints until the stainless steel screen plate became clogged.

Firing properties: Print a predetermined circuit pattern so that the fired film thickness is 40 μm or more, hold the ceramic substrate in an air atmosphere at a maximum temperature of 850°C for 15 minutes, and bake for 35 minutes to prevent pinholes and peeling. The presence or absence was determined.

Production Example 1 Ethyl cellulose i1m with an average molecular weight of 125,000,
66 parts of 2-hydroxylethyl methacrylate, 15 parts of polyethylene glycol (adduct of 14 moles of ethylene oxide) dimethacrylate, 4 parts of benzyl dimethyl ketal as a photopolymerization initiator, 4 parts of 2-ethylanthraquinone
The components were mixed and dissolved at room temperature to obtain a photocurable resin composition (a).

Similarly, photocurable resin compositions (B) and (C) containing a cellulose derivative and a photopolymerizable compound as shown in Table 1 were obtained. As the photopolymerization initiator, the same compound and the same amount as in (a) were used.

Next, vitreous frit [^5F-1360, manufactured by Asahi Glass ■] 70%, ゛ and the above photocurable resin composition (a)
30% was well kneaded using three ceramic rolls,
A photocurable dielectric firing paste l-(a') was obtained. Similarly, photocurable dielectric firing pastes (b") and (C') were obtained.

Table 1 ($1) 2-Hydroxylethyl methacrylate ($
2) Tetrahydrofurfuryl methacrylate (Umbrella 3) Polyethylene glycol [(ethylene oxide (EO)
Adduct)] Dimethacrylate Production Reference Example 1 Methyl methacrylate (HMA) with an average molecular weight of 75,000
) - 25 parts of n-butyl methacrylate (n-HMA) copolymer (HMA/n-11M^, 4G/60 weight ratio), 52 parts of 2-hydroxylethyl methacrylate, polyethylene glycol (14 moles of ethylene oxide adduct) ) dimethacrylate), 4 parts of benzyl dimethyl ketal and 4 parts of 2-ethyl anthraquinone as photopolymerization initiators were dissolved at room temperature to obtain a photocurable resin composition (d). Similarly, it is shown in Table 2. A photocurable resin composition (e) was obtained. As the photoinitiator, the same compound and the same amount as in (d) were used.

Next, 70% glassy frit [^5F-1380, manufactured by Asahi Glass ■] and the above photocurable resin composition (d) were thoroughly kneaded using a three-roll ceramic roll to form a photocurable dielectric firing paste (d' ) was obtained. Similarly, using the photocurable resin composition (e), a photocurable dielectric fired film (e') was obtained.

Production Reference Example 2 18 parts of ethyl cellulose having an average molecular weight of 25,000 and 82 parts of a solvent (terpineol/toluene = 70/30 (weight ratio)) were dissolved at room temperature to obtain a solvent-type resin composition (f).

Next, 70% of vitreous flint (Hachi5F-1380, manufactured by Asahi Glass RJ Co., Ltd.) and the above solvent-based resin composition (f) were added.
Use three ceramic rolls. Tl kneading was carried out to obtain a solvent type dielectric firing paste (f').

Table 2 (Book 4) Methyl methacrylate-methacryl butyl ester acid copolymer (HMA/n-BMA=40/60 weight ratio) (Book 5) 2
-Hydroxylethyl methacrylate (Book 6) Tetrahydrofurfuryl methacrylate (Umbrella 7) Polyethylene glycol (14 mole ethylene oxide adduct) Dimethacrylate (Part 8) Terpineol/Toluene = 70/
30 (weight ratio) Example 1 Alumina substrate (alumina content 96%, N 5 cm
A predetermined pattern was continuously printed using a stainless steel screen plate with the photo-curable dielectric firing paste (a') on a substrate (width: 5 cm x thickness: 0.6 mm).

In this case, no clogging of the screen plate occurred even when the number of printed sheets exceeded 500 sheets. The printed alumina substrate was irradiated for 10 seconds at a distance of 15C11 under a 5.6KW water-cooled high-pressure mercury lamp to harden the fired paste. Next, this alumina substrate was fired under the above-mentioned firing conditions, and then the firing properties were determined. The results are shown in Table 3.

Examples 2 and 3 Photocurable dielectric firing paste (a') in Example 1
Instead of photocurable dielectric firing paste (b') and (
A pattern was formed on an alumina substrate using C').

The results of printability and firing properties are shown in Table 3 as Examples 2 and 3, respectively.

Comparative Example 1 A pattern was continuously printed on the alumina substrate of Example 1 using a stainless steel screen plate with the photocurable dielectric firing paste (d''). The printed alumina substrate was cured by irradiation for 10 seconds under a mercury lamp at a distance of 1 5 cm.The printed alumina substrate was then fired under the above-mentioned firing conditions, and the firing properties were evaluated.

The results are shown in Table 4.

Comparative Example 2 Photocurable dielectric preforming paste (d') in Comparative Example 1
Instead, a pattern was formed on an alumina substrate using a photocurable dielectric firing paste (e'). The results of printability and firing properties are shown in Table 4.

Comparative Example 3 A pattern was continuously printed on the alumina substrate of Example 1 using a solvent-based dielectric firing paste (f'). This printed alumina substrate was dried at 150°C for 20 minutes. Next, the printed alumina substrate was fired under the above-mentioned firing conditions, and the firing properties were evaluated.

The results are shown in Table 3.

Table 3 (Effects of the Invention) The following points are listed as excellent effects of the photocurable dielectric firing paste of the present invention.

(1) Since the firing paste used is a photocurable dielectric firing paste, it does not contain any solvent and pinholes do not occur due to clogging of the screen plate.

(2) Therefore, continuous printing of patterns is possible.

(3) Since the photocurable resin has good firing properties, there are no pinholes, peeling, or carbon residue due to firing.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] Glassy frit (A), and photocurable resin composition (
In the photocurable dielectric baking paste containing B), the photocurable resin composition (B) contains (I) a cellulose derivative (II) a photopolymerizable compound having a double bond in the molecule; A photocurable dielectric firing paste characterized by containing a polymerization initiator.