JPH0645476B2 - Metal mask substrate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a metal mask substrate, and in particular, a heat-resistant insulating glass or a filler of the glass or the like in a through hole having a design pattern of metal or magnetic or non-magnetic stainless steel. The present invention relates to a metal mask substrate which is filled with the visible light curable resin and which is suitable for diversifying required characteristics for hybridizing electronic circuits.

[Conventional technology]

Typical metals conventionally used as metal mask substrates are iron, stainless steel, copper, phosphor bronze, aluminum, and aluminum alloys, and ceramic substrates are also used. It is necessary that the coefficient of linear expansion of the underlying metal selected from these and the coefficient of linear expansion of the insulating material forming the insulating portion, such as glass frit paste, match according to the operating temperature.

[Problems to be Solved by the Invention]

Among the support metals used for the metal mask substrate, magnetic and non-magnetic stainless steels have the advantage of not requiring special atmosphere treatment when they are processed because of their heat resistance and low oxidation property. It is considered to be a preferable material compared to other metals. However, since stainless steel has a weak adhesion to the resin or glass forming the insulating portion, it is difficult to weld them, and it is impossible to solder directly to the stainless steel. Therefore, in order to use stainless steel as a support material for a metal mask substrate, it is necessary to solve such a joining element. Therefore, conventionally, the surface is electrolytically or electrolessly plated with nickel of about 1 μm or less, or It has been necessary to chemically etch with hydrochloric acid or caustic soda, or to perform a pretreatment such as partial oxidation by dipping in sulfuric acid before coating or filling the insulating material.

The present invention was made in order to solve this problem, and developed a special binder to give adhesion to resin and glass to stainless steel without requiring any undercoating, and directly to stainless steel. The metal mask substrate is obtained by a technique that enables soldering and can be connected to an arbitrary portion.

[Means for Solving the Problems]

The present invention is _SiO 2 _{0 to 8%} based on the weight, _{B 2} O 3 4~
15%, P ₂ O ₅ 20-71%, ZnO 0-2%, Al
₂ O ₃ 0-10%, PbO 0-1%, ZrO ₂ 0-2
%, TiO ₂ 0 to 2%, Li ₂ O 0 to 1%, Na ₂ O
_{0~2%, K 2 O 0~11%} , 0~5% MgO,
CaO 0-14%, SrO 0-18%, BaO 0
_{~42%, Nb 2 O 5 0~1} %, Ta 2 O 5 0~4%,
La ₂ O ₃ 0 to 11%, WO ₃ 0 to 1%, Y ₂ O ₃ 0 to
It is a metal mask substrate characterized in that a high temperature insulating glass of 1% is filled in a through hole of a design pattern provided in magnetic or non-magnetic stainless steel. Further, in the present invention, it is possible to use a high temperature insulating glass in which 0 to 10% by weight of a sintered metal oxide is added to the glass having the above composition. The present invention also provides S based on weight.
iO ₂ 0-8%, B ₂ O ₃ 4-15%, P ₂ O ₅ 20-
71%, ZnO 0-2%, Al ₂ O ₃ 0-10%, P
bO 0 to 1%, ZrO ₂ 0 to 2%, TiO ₂ 0 to 2
%, Li ₂ O 0-1%, Na ₂ O 0-2%, K ₂ O
0-11%, MgO 0-5%, CaO 0-14
%, SrO 0-18%, BaO 0-42%, Nb ₂
O ₅ 0 to 1%, Ta ₂ O ₅ 0 to 4%, La ₂ O ₃ 0 to 1
1%, WO ₃ 0 to 1%, Y ₂ O ₃ 0 to 1%, a high temperature insulating glass or a high temperature insulating substance made of a sintered metal oxide, and powdered by melting and pulverizing a high temperature insulating substance 10 to 10
A metal mask substrate, characterized in that a heat-resistant insulating visible light curable resin containing 95% by weight is filled in through holes of a design pattern provided in magnetic or non-magnetic stainless steel.

The support of the mask substrate of the present invention is magnetic or non-magnetic stainless steel. Of course, a conventionally used metal support such as iron, copper, phosphor bronze, aluminum or aluminum alloy can also be used. Magnetic or non-magnetic stainless steel is particularly preferably used in the present invention.

Stainless steel is less susceptible to oxidation than other metals and has the advantage that no special atmospheric treatment is required when filling the insulating layer. Among them, a relatively low expansion coefficient (100-300
Coefficient of linear expansion alpha _{100 ~ 300} at ℃ is 110 - 140 × 10
^-7 / ° C.) is preferred.

The composition of the glass used in the present invention is the above-mentioned claim 1.
As specified in. Among them, SiO ₂ , B ₂ O ₃ and P ₂ O ₅ are used as a network structure forming oxide which forms the basic structure of glass, and also Li ₂ O, Na ₂ O, MgO, CaO.
Etc. are well known oxides for network modification. Other than the glass used in the present invention, ZnO, Al
₂ O ₃ , ZrO ₂ , La ₂ O _{3 and} other oxides are contained as additive components, and the composition range is limited in relation to the content of each component constituting the basic structure. With other compositions it is not possible to obtain glasses which achieve the intended purpose of the invention.

In addition to the above, the glass used in the present invention contains at least 1% by weight of As ₂ O ₃ and Sb ₂ O ₃ as an additive component.
The following can be included: The component acts as a fining agent when melting the glass, and when it is contained, it has a fining effect, so that it is desirable to be present.

The glasses used according to the invention can additionally contain up to 10% by weight of sintered metal oxides, for example commercially available sintered pigments and forsterite ceramics. The component is effective in improving the heat resistance of glass.
Specific examples of commercially available sintered pigments include Ti, Sb,
Cr, Fe, Ni, Al, Zn, Si, Co, Mn, Z
Sintered powders of at least two kinds of oxides such as r and Pb, that is, crushed ceramic colors (particle size <10 μm) and the like.

Table 1 shows examples of specific compositions of the glass used in the present invention.

The metal mask substrate of the present invention, a structure in which a glass having the above composition or a visible light curable resin to which the glass is added as a filler is filled as an insulating portion in a through hole having a design pattern provided on a magnetic or non-magnetic stainless steel support It is the body. This metal mask substrate has a support made of stainless steel and is rich in mechanical strength, appropriate flexibility and workability, and a large-sized deformed substrate can be manufactured. In addition, since it is possible to directly ground the stainless steel by using the unique paste which is the basis of the present invention, which will be described later, the mask substrate allows various circuit designs suitable for hybridization.

Conventionally, glass or resin filled as an insulating part in stainless steel has poor adhesion with stainless steel, so prior to lamination, the surface of the stainless steel is plated with nickel of 1 μm or less by electrolytic plating or electroless plating, or
Pretreatment such as chemical etching with hydrochloric acid or caustic soda, or partial oxidation by immersion in sulfuric acid was required.

The present invention according to claim 1 is a metal mask substrate in which such a base treatment of stainless steel is not necessary and glass having good adhesion to stainless steel is filled in the through holes provided in the support. Further, this mask substrate has improved chemical resistance and durability due to the trace components contained in the glass to be filled.

The glass filled in the stainless steel has a relatively low coefficient of thermal expansion, and it is desirable that the glass be as close as possible to the expansion coefficient of the stainless steel support. As the glass, for example, the glass having the composition shown in Table 1 may be appropriately selected and used by filling the through hole. The thickness of the substrate is arbitrary and is preferably 0.6 to 0.8 mm.

The stainless steel mask in which the through holes are filled with the above-mentioned insulating glass can be manufactured as follows.

As the glass used in the present invention, a mixture having the composition described in claims 1 and 2 (for example, one selected from those shown in Table 1) is roughly melted in a quartz crucible. The melt is once granulated and dried. The glass is then melted again in a platinum crucible.

The melting temperature and the melting time can be arbitrarily selected depending on the glass composition and are not particularly limited, but 1,200 to 1,4
The range of 90 to 150 minutes at 00 ° C is preferable. This melting is performed by optical melting because the glass is bubble-free. The molten glass can be drawn out into a flat plate shape, gradually cooled, and then cut into a desired shape, or can be granulated and dried to be used as a glass frit.

Next, a metal mask substrate is manufactured using this glass.
The case of using flat glass will be described with reference to FIGS. FIG. 1 shows a state in which a plate glass 1 is placed on a stainless steel support 2, and the support is placed on a releasable setter 4 in which magnesia or alumina is coated with boron nitride or the like. The glass is melted by heating and filled in the through holes 3 of the design pattern provided on the support as shown in FIG. After cooling, the excess glass is removed by polishing to obtain the mask substrate of FIG. The heating and melting temperature of the glass may be appropriately selected according to the composition of the glass used. 70 in general
It is 0-900 degreeC.

When insulating glass is used as the frit, the dried glass frit is first separated by a wind sieve to remove coarse particles of 10 μm or more.

A vehicle is added to the sized glass frit (particle size less than 10 μm), and the mixture is kneaded for 4 hours or more using a kneader such as a three-roll mill, and then degassed to prepare a paste.
The vehicle used here is the basis of the present invention, and a solution of 5 to 10% by weight of a cellulose derivative of butyl carbitol acetate tate or α-terpineol is used. As the cellulose derivative, alkyl cellulose such as methyl cellulose and ethyl cellulose is preferably used. This alkylcellulose is used as a solution of 5 to 10% by weight of butyl carbitol acetate for forming a glass frit into a paste in the present invention. Butyl carbitol acetate or α-terpineol is preferred as the solvent. The concentration of alkyl cellulose in the solution is important for adjusting the viscosity of the paste, and usually 5 to 5
A range of 10% by weight is preferred.

By kneading with the glass frit using this vehicle, a long-term stable paste can be prepared, and this paste can be applied to the surface of stainless steel and sintered without any pretreatment. It is possible to form a laminate excellent in adhesion. The viscosity of the paste in this case is preferably 100 to 200 poise, and can be prepared by appropriately selecting the mixing ratio of the vehicle of the above concentration and the glass frit.

The stainless steel mask substrate of the present invention when using insulating glass as a frit is a surplus after the paste is applied to a stainless steel support provided with through holes of a designed pattern to fill the through holes, dried and baked. The glass can be removed by polishing.

For example, a roll coater, a screen coater, an auto dispenser or the like may be used as the paste application method, and a conventionally known method may be used as the printing method such as screen printing.

After applying the paste and filling the through holes,
Dry at 0 to 150 ° C for about 15 minutes. Next, this is fired, but drying and firing can be performed in air, and it is preferable to make the temperature rising rate as slow as possible between 350 and 400 ° C. where the decomposition and combustion of the binder is active. The heating and cooling patterns for firing can be shown as in FIG. Increase the temperature at 350 ° C or 40 ° C / min, and
During 400 ℃, decrease the heating rate as described above,
/ Min. 750 at 10 ° C / min after reaching 400 ° C
The temperature is raised from ℃ to 850 ℃, and baked at this temperature for about 20 minutes.
After firing, allow to cool and return to room temperature.

The present invention according to claim 3 provides a fine powder of a glass or metal oxide sintered body having a composition used in the mask substrate, in a through hole of a design pattern provided in a magnetic or non-magnetic stainless steel plate-shaped support. 10 as body filler
It is a heat-resistant metal mask substrate in which visible light curable resin added by 95% by weight is filled as an insulating portion. If the content of glass in the resin is 10% by weight or less, the heat resistance of the resin is not improved, which is not preferable. From this point of view, the content of glass in the resin is preferably 50% by weight or more. Examples of the visible light curable resin used here include a commercially available acrylic resin and epoxy resin, and any of them can be used. Among them, the one-component acrylic visible light curable resin is preferable in terms of handling. There is a large difference in linear expansion coefficient between the resin and the stainless steel of the support, but there is no problem because the shrinkage rate of the resin is small.

Further, it is desirable that the refractive index (n _D ) of the visible light curable resin and the refractive index (n _D ) of the added glass are the same. If the two are different, the sharpness of the pattern decreases when filling and curing, which is not preferable in some cases. A commercially available acrylic resin or the like can be used as the visible light curable resin, and a glass having the same refractive index as that of the acrylic resin can be appropriately selected from the composition of the present invention.

This metal mask is manufactured by mixing glass frit and visible light curable resin in a predetermined ratio and kneading to form a paste, and applying this paste to a stainless steel support provided with a through hole of a design pattern to form a through hole. And a resin is irradiated with a metal halide light source (470 nm) in a nitrogen stream for several tens of seconds to several minutes to cure the resin and then the excess resin is removed by polishing. A known method can be used as the paste filling method, and among them, the method of spray coating with an automatic dispenser is preferable.

In the present invention, the binder paste of the cellulose derivative used as the vehicle is applied in advance to enable soldering to stainless steel, which has been impossible in the past. As a paste used for this purpose, 5 to 10% by weight of inorganic acid is added. That is, the composition is a paste composed of a BCA solution or an α-terpineol solution of a cellulose derivative to which an inorganic acid of 5 to 10% is added. BCA solution or α-
The concentration of the cellulose derivative in the terpineol solution is 5 to
10% by weight is preferred. Alkyl cellulose is preferable as the cellulos derivative, and methyl cellulose and ethyl cellulose are preferable. The inorganic acid to be added is preferably hydrochloric acid, hydrofluoric acid or a mixed acid of hydrofluoric acid and phosphoric acid. The composition of the mixed acid is preferably 3 to 10% by volume of phosphoric acid.

By applying or printing this paste on the soldered part of stainless steel in advance, it can be soldered to stainless steel very easily, and various characteristics required for hybridization of electronic circuits using stainless steel as a support can be achieved. It is possible to fabricate a substrate suitable for application.

〔Example〕

 The present invention will be specifically described below with reference to examples.

Example 1 Ni 74.09, Cr 15.69, Fe in wt%
9.22, Mn 0.31, Co 0.3, Si 0.
21, P 0.009, S 0.001, Cu 0.0
A plate-like support (hereinafter referred to as "A substrate") made of non-magnetic stainless steel having a composition of No. 4 (coefficient of linear expansion at 300 ° C α _{100 to 300} = 137.2 × 10 ^-7 / ° C) in Fig. 5 is used. , And B are provided with through holes having the patterns shown in FIG. A glass substrate having a composition of 3 (α ₁₀₀ to ₃₀₀ = 128 × 10 ⁻⁷ / ° C.) was filled to prepare a mask substrate (100φ).

No. The mixture having the composition of 3 was roughly dissolved in the quartz crucible of 4, then the dissolved material was granulated and dried, and then the dried product was optically melted at 1,350 ° C. using the platinum crucible of 4. The molten material was drawn out in a flat plate state, cooled and then cut into a circular plate to form a circular glass plate having a thickness of 0.8 mm and a diameter of 98 mm.

The circular glass plate 1 produced in this manner was placed in contact with the A substrate (mask substrate) 2 placed on the releasable setter 4 as shown in FIG. 1, and heated and melted in the following manner, The molten glass was filled in the through holes provided in the A substrate. As shown in Fig. 4, the heating and melting schedule is to heat up to 350 ° C at a rate of about 40 ° C / min.
Between 350 ° C and 400 ° C, slow the heating rate to 5 ° C / min,
After reaching 400 ° C., the temperature was raised to 750 ° C. at 10 ° C./minute, melted at 750 ° C. for 20 minutes, and then cooled at about 40 ° C./minute. After cooling, the mask substrate was removed from the releasable setter 4, both surfaces were polished to remove excess glass, and a mask substrate was produced. This mask substrate had the characteristic values shown in Table 2 and was an excellent mask substrate.

Example 2 Cr 16.75, Mn 0.54, Nb in wt%
0.52, Si 0.49, Cu 0.38, P 0.
Magnetic stainless steel made of Fe containing 026, C 0.015, S 0.003 (α _{100 to 300} = 110.2 × 1
^0-7 / ° C) plate-like support (hereinafter referred to as "B substrate"),
A through hole having the same pattern as that of Example 1 is provided, and the No. 1 in Table 1 is provided in this through hole. Glass having a composition of 5 (α _{100 to 300} = 105 × 10 ⁻⁷ / ° C., Tg = 607 ° C.,
A mask substrate (100φ) was prepared by filling Tc = 631 ° C.). The procedure for producing the circular glass plate and filling the through holes was exactly the same as in Example 1.

The characteristic values of the obtained mask substrate satisfied the values shown in Table 2.

Example 3 Visible light curable resin LCRX0403 manufactured by ICI
(N_D: 1.5408) and N in Table 1 as a filler
o. Glass frit of composition 8 (n_D: 1.54-1.
55) is added to the resin so that the content of the resin is 70% by weight.
A composition was prepared. The glass frit is No. Of composition 8
The mixture was roughly melted in a quartz crucible No. 4 and the melted material was dissolved in water.
Crush, dry and dry the glass using a platinum crucible 4
Melt again at 1,250 ℃, granulate and dry,
The granules were cut and 10 μm or less were used. This glass
Is α_{100 ~ 300}= 95 × 10^-7/ ° C, Tg = 485 ° C, T
It was c = 531 degreeC.

The above resin composition was kneaded with a three-roll mill for 4 hours and then degassed to obtain a paste having a viscosity of about 170 poise. This paste was compressed to an air pressure of 4.0 using a dispenser.
kg / cm ² and an air flow rate of 170 Nl / min, the A and B substrates provided with the same through holes as used in Examples 1 and 2 were spray-coated to fill the through holes, and a metal halide light source (470 nm) was used. Was used to cure the resin paste by irradiating it for 2 minutes in a nitrogen stream. Excess resin cured material other than the filled portion of the through hole was removed by polishing to prepare a mask substrate. This mask substrate satisfied the characteristic values in the use range of 200 ° C. or lower.

〔The invention's effect〕

The metal mask substrate of the present invention uses stainless steel that is not subjected to a base treatment as a support, has excellent mechanical strength, heat resistance, and workability, and meets the required characteristics for hybridizing electronic circuits, which cannot be realized by conventional insulating substrates. It is a mask substrate. In addition, the solder paste of the present invention can be used to directly ground the stainless steel support to design various electronic circuits. Further, by using magnetic stainless steel, it can be used as an electromagnetic shield substrate.

[Brief description of drawings]

1, 2, and 3 are cross-sectional views for explaining a method for manufacturing a metal mask in which through holes are filled with flat glass, and FIG. 4 shows heating and cooling patterns when baking glass paste. FIG. 5 (A) is an overall view showing an example of a mask substrate, and FIG. 5 (B) is a partially enlarged view of a through hole provided in the mask substrate. Reference numeral 1 is plate glass, 2 is a support, 3 is a through hole provided in the support, and 4 is a release setter.

Claims (3)

[Claims] 1. SiO ₂ 0-8%, B ₂ O ₃ based on weight.
4 to 15%, P ₂ O ₅ 20 to 71%, ZnO 0 to ₂ %,
_{Al 2 O 3 0~10%, PbO} 0~1%, ZrO 2 0
_{~2%, TiO 2 0~2%,} Li 2 O0~1%, Na 2
O 0-2%, K ₂ O 0-11%, MgO 0-5
%, CaO 0-14%, SrO 0-18%, BaO
0 to 42%, Nb ₂ O ₅ 0 to 1%, Ta ₂ O ₅ 0 to 4
%, La ₂ O ₃ 0 to 11%, WO ₃ 0 to 1%, Y ₂ O ₃
A metal mask substrate, characterized in that 0 to 1% of high temperature insulating glass is filled in through holes of a design pattern provided in magnetic or non-magnetic stainless steel. 2. A high temperature insulating glass obtained by adding 0 to 10% of a sintered metal oxide as an additive component to glass having the composition according to claim 1 is provided on magnetic or non-magnetic stainless steel. A metal mask substrate characterized by being filled in through holes of a designed pattern. 3. SiO ₂ 0-8%, B ₂ O ₃ based on weight.
4 to 15%, P ₂ O ₅ 20 to 71%, ZnO 0 to ₂ %,
_{Al 2 O 3 0~10%, PbO} 0~1%, ZrO 2 0
_{~2%, TiO 2 0~2%,} Li 2 O0~1%, Na 2
O 0-2%, K ₂ O 0-11%, MgO 0-5
%, CaO 0-14%, SrO 0-18%, BaO
0 to 42%, Nb ₂ O ₅ 0 to 1%, Ta ₂ O ₅ 0 to 4
%, La ₂ O ₃ 0 to 11%, WO ₃ 0 to 1%, Y ₂ O ₃
A heat-resistant insulating visible light curable resin containing 10 to 95% by weight of a powder obtained by melting and pulverizing a high-temperature insulating glass composed of 0 to 1% or a high-temperature insulating substance composed of a sintered metal oxide as a filler. A metal mask substrate, characterized by being filled in through holes of a design pattern provided in magnetic or non-magnetic stainless steel.