JP2000151080A - Transfer print patterning method and glass with print pattern formed thereon using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer print patterning method capable of simply and accurately forming a print pattern such as a thin-film electrical circuit and the like on a large area substrate. SOLUTION: An electrical circuit is screen-printed on a transfer paper 10 in which a removable layer 20 is formed on the surface (a), and this electrical circuit is heat-transferred on a substrate 20 such as a glass and the like. In heat-transferring, the transfer paper 10 is pressed with a press plate 24, and heated while pressing the electrical circuit to the substrate 22 (b, c). Thus, the substrate 22 transferred with the electrical circuit pattern is heated and fired, thermoplastic resin contained in the electrical circuit pattern is removed, and the electrical circuit pattern is printed on the substrate 22 (d). As a result, a desired electrical circuit is formed on the substrate 22.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer-type printing pattern forming method for forming a printing pattern such as an electric circuit, an electronic component, and a light-shielding pattern on a substrate such as glass by transfer, and a glass having a printing pattern formed by the method. About.

[0002]

2. Description of the Related Art Various methods are used for forming a pattern such as an electric circuit on a substrate. For example, in a semiconductor element, a photolithography / etching method is adopted. This method is excellent in workability of a fine pattern on the order of submicrons.

However, this method requires large-scale and complicated facilities such as a clean room. Further, the etching time is long, and particularly when a multilayer electric circuit is formed, the production time is long. There is no problem in the case where the thickness of the formed film is less than submicron, but there is a problem that it takes time to form a film having a thickness of several μm or more.

[0004] A sputtering method has also been put into practical use for imparting functionality to the substrate surface. in this way,
It is possible to apply a thin film uniformly on the substrate surface from a small area to a large area with a thickness of submicron or less. However, it is difficult to control gas molecules by an electric field in a closed space, and it is difficult to perform patterning when forming a circuit. There are also problems such as low productivity and high cost.

Therefore, although the drawing performance is not as high as that of the photolithography / etching method, a film thickness of several μm to several hundred μm can be drawn at high speed with accuracy of several tens μm even under rough environmental conditions with low cleanliness. In some cases, possible screen printing methods are employed. In this method, a multilayer electric circuit can be formed by printing, and is widely used for electronic components, printed circuits, and the like. Further, as compared with the sputtering method, it is excellent in that the patterning property and the productivity are high and the cost is low.

[0006]

However, in the above-mentioned conventional screen printing method, when a small area multi-layered electric circuit or a printed pattern such as a light shielding pattern is formed on a large area substrate, the positional accuracy of the substrate is reduced. It is necessary to perform positioning and multi-layer printing while maintaining a high level, and a large-scale drying facility and a high-precision positioning device are required, resulting in an increase in cost.

For this reason, it is conceivable to form an electric circuit by mounting an element such as a chip component on a substrate. The above thickness results in a problem that the mountability of the substrate is hindered.

As described above, the conventional screen printing method has a problem that it is difficult to form a printing pattern such as a thin film electric circuit or a light-shielding pattern on a large-area substrate.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to easily form a printed pattern such as a thin-film electric circuit or a light-shielding pattern on a large-area substrate with high accuracy. An object of the present invention is to provide a transfer printing pattern forming method.

[0010]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have conducted various studies, developed a transfer technique used for painting in the field of ceramics, and completed the present invention. Reached. When painting on conventional ceramics, it is necessary to use a base paper, water-soluble glue, and an organic film such as polyethylene.
Using a transfer paper having a layer structure, a predetermined paste is printed in a desired pattern on an organic film by a screen printing method to form a pattern, and the pattern is dried. This paste is obtained by forming a kneaded substance of an inorganic pigment and a glaze made of glass powder into a paste with an organic vehicle and a solvent.

The transfer paper on which the picture is formed is immersed in water to separate the base paper from the patterned organic film, and the organic film is adhered to the ceramic substrate as the substrate by the adhesiveness of the water-soluble glue. dry. Further, in the heat treatment step of the substrate, the organic film is thermally decomposed and vaporized, and the pattern is transferred to the ceramic by baking the pattern.

However, if this technique is applied directly to, for example, transfer of an electric circuit or an electronic component, there is a step of immersion in water during the transfer step, so that the metal constituting the electric circuit is deteriorated by moisture or the like. is there. For this reason, in the present invention, transfer can be performed without immersing transfer paper on which an electric circuit or the like is formed using glass paste without immersing it in water. That is, in the present invention, a pattern such as an electric circuit is transferred onto a substrate by thermal transfer. The glass paste in the present invention contains at least a low melting point glass powder, an organic binder, and a solvent (volatile solvent).
The organic binder is preferably a thermoplastic resin that melts and decomposes and volatilizes in the firing step of the glass paste.
Furthermore, as optional components depending on the use, fillers such as alumina powder and zirconia powder for adjusting the expansion coefficient, etc., conductive materials such as silver powder for providing conductivity, and inorganic materials for providing a light shielding function. Insulating materials, semiconductor materials, resistive materials, magnetic materials, and the like are added in addition to heat-resistant pigments, dielectric materials such as high dielectric constant ceramic powder for adjusting the dielectric constant, and low dielectric constant ceramic powders.

The present invention described above is a transfer-type printing pattern forming method, in which a printing pattern is formed on a transfer film by using a glass paste, the printing pattern is thermally transferred onto a substrate, and the printing pattern is thermally transferred onto the substrate. It is characterized in that the printing pattern is fired. The pattern of the printing pattern here is, for example, an electric circuit pattern, a coloring pattern,
For example, a light-shielding pattern.

[0014] In the above-mentioned transfer type printing pattern forming method, the printing pattern formed on the transfer film may be:
It contains at least one selected from conductive materials, insulating materials, dielectric materials, semiconductor materials, resistive materials, magnetic materials, and inorganic heat-resistant pigments, and contains a thermoplastic resin that melts and decomposes and evaporates during the firing process. And The conductive material mentioned here is, for example, a metal such as silver, copper, platinum, gold,
The conductive material is a conductive oxide such as TO, the insulating material is an oxide such as SiO ₂ or MgO, the dielectric material is an oxide such as BaTiO ₃ , and the semiconductor material is
For example, a semiconductor such as Si or GaAs, the resistive material is a conductor such as a metal, a material other than a conductor, or a mixture thereof, and the magnetic material is a metal such as Fe, for example.
Alloys such as FeNiCo and oxides such as ferrite.
Examples of the inorganic heat-resistant pigment include copper-chromium oxide, iron-manganese oxide, and magnetite.

[0015] In the transfer printing pattern forming method, the thermoplastic resin may be one or more selected from thermoplastic polyester resins, thermoplastic cellulose derivatives, thermoplastic acrylic resins, and thermoplastic vinyl acetate resins. It is a mixed resin.

Further, in the above transfer type print pattern forming method, the print pattern formed on the transfer film may be:
It is characterized in that it has a single layer structure or a laminated structure of two or more layers.

Further, in the above transfer type printing pattern forming method, the substrate is made of glass or ceramics.

Further, in the above-mentioned transfer type printing pattern forming method, the printing method formed on the transfer film is characterized in that an adhesion aid is applied in advance.

Further, in the above-mentioned transfer printing pattern forming method, an adhesion aid is applied in advance on the print pattern formed on the transfer film, the decomposition temperature of the adhesion aid is set to T ₁ , and the decomposition of the thermoplastic resin is performed. Assuming that the temperature is T ₂ and the sintering start temperature of the glass paste is T ₃ , (T ₁ −T ₂ ) is 5
C. to 20 ° C., and (T ₃ −T ₁ ) is 10 ° C. or more.

Further, in the above transfer type printing pattern forming method, the printing pattern is an electric circuit pattern. Here, “the printed pattern is an electric circuit pattern” means that the pattern of the printed pattern thermally transferred onto the substrate is an electric circuit pattern.

The present invention also relates to a glass on which a printed pattern is further formed, wherein the transfer-type printed pattern forming method forms a printed pattern on a kind selected from glass for automobiles, glass for buildings, and glass for displays. It is characterized by having been done.

According to each of the above constructions, the print pattern formed on the transfer paper in advance is transferred onto the substrate, instead of forming the print pattern directly on the substrate such as glass by sequentially printing and drying it in multiple layers. And a highly accurate print pattern can be formed. The printed pattern thus formed is integrated with the substrate by heat-treating the substrate.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The transfer film in the present invention may be a film on which an easily peelable layer, which is an organic layer such as silicon or acrylic, is formed. One having an easily peelable layer formed thereon can be used. Since such a transfer film is thinner than glass or the like serving as a substrate, the cooling time when heating and drying a glass paste (such as an electronic material paste) when performing screen printing on the transfer film is short. Good efficiency in multi-layer printing of electric circuit patterns and the like. For this reason, productivity can be improved.
The transfer film in the present invention is preferably transfer paper.

Hereinafter, embodiments of the present invention (hereinafter, referred to as embodiments) will be described with reference to the drawings, taking as an example a case where a transfer film is transfer paper.

FIGS. 1A and 1B are explanatory views showing a case where a desired print pattern is formed on a transfer paper 10 in the transfer type print pattern forming method according to the present invention.
1A, a print pattern such as an electric circuit pattern or a light-shielding pattern is formed on a transfer paper 10 by a screen printing method. In the example shown in FIG. 1A, an electric circuit pattern to be formed on the transfer paper 10 is formed on a screen plate 12 used for screen printing. The electric circuit pattern is screen-printed on the transfer paper 10 by extruding the electronic material paste 14 placed on the screen plate 12 along the electric circuit pattern formed on the screen plate 12 with a squeegee 16. By repeating such screen printing one or more times on the transfer paper 10, a planar or multilayer electric circuit pattern (print pattern) is formed.

FIG. 1B is a sectional view of the transfer paper 10 on which the electric circuit pattern is screen-printed as described above. In FIG. 1B, the transfer paper 10 is a base paper 1
8 has a two-layer structure in which an easily peelable layer 20 is formed. Further, in the example shown in FIG.
The multilayer electric circuit pattern has a two-layer structure of a second layer and a second layer.

As described above, the easily peelable layer 2 is formed on the base paper 18.
By forming 0, the electric circuit pattern formed on the transfer paper 10 is easily peeled. This facilitates transfer of the electric circuit pattern from the transfer paper 10 to the base material.

In the above-described screen printing, an electronic material paste 1 used when forming an electric circuit pattern
4, according to the intended electric circuit and electronic element, one or more of electronic material components of a conductor, a semiconductor, a resistor, an insulator, a dielectric, and a magnetic material or a mixture of all of them as appropriate. To adjust. Such a mixture is first processed into a powder form, and is kneaded with a glass frit, that is, a low-melting glass powder, a thermoplastic resin (organic binder), and a volatile solvent, so as to adjust the viscosity to allow screen printing. Here, the glass frit softens and flows in a temperature range of a firing process of a substrate such as glass or ceramics, and is added for the purpose of bonding the substrate to an electronic material component of an electric circuit pattern.

The thermoplastic resin has a function of converting the electronic material component and the glass frit into a paste state.
It also has the function of adhering the electric circuit pattern to the substrate during heat drying and thermal transfer during screen printing. When the electric circuit pattern on the transfer paper 10 shown in FIGS. 1A and 1B is thermally transferred to a substrate, if the adhesion between the substrate and the electronic material paste 14 is not sufficient, a subsequent heat treatment is performed. Peeling occurs from the insufficiently adhered portion in the firing step. The above-mentioned thermoplastic resin is used to secure this adhesion. If the thermoplastic resin has a hot-melt adhesive function, the adhesion can be further improved.

From the above, it is preferable to use a thermoplastic resin as the organic binder. In addition, the thermoplastic resin is also suitable in this respect because bubbles generated when the resin is decomposed and volatilized during firing are easily degassed. The reason is that the air bubbles may adversely affect the characteristics and quality of the fired electric circuit pattern.

The thermoplastic resin is preferably a thermoplastic polyester resin, a thermoplastic cellulose derivative, a thermoplastic acrylic resin, or a thermoplastic vinyl acetate resin.
One or a mixture of two or more of these resins is used. For example, thermoplastic polyester resins such as polyethylene terephthalate, thermoplastic cellulose derivatives such as ethyl cellulose, thermoplastic acrylic resins such as acrylate copolymers and methacrylate copolymers, and vinyl acetate homopolymers and copolymers And other thermoplastic vinyl acetate resins.

The volatile solvent added when preparing the electronic material paste 14 is used for adjusting the viscosity of the electronic material paste 14 to a viscosity that allows screen printing. The characteristics required for this volatile solvent include a compatibility with the thermoplastic resin and a moderately high boiling point so that the change in viscosity characteristics with time is small.

The electronic material paste 14 described above corresponds to the glass paste according to the present invention. The glass paste is not limited to the above-mentioned electronic material paste 14, but may contain, for example, an inorganic heat-resistant pigment for forming a light-shielding pattern instead of an electronic material such as a conductor.

FIG. 2 shows a step of thermally transferring the electric circuit pattern from the transfer paper 10 on which the electric circuit pattern shown in FIG. 1 is printed to a substrate such as glass or ceramic. The glass used as the substrate can be selected from automotive glass, architectural glass, display glass, and the like.

In FIG. 2A, the electric circuit pattern formed on the easily peelable layer 20 of the transfer paper 10 is arranged so as to face the substrate 22 of glass or ceramics, and is shown in FIG. 2B. Thus, the transfer sheet 10 is pressed by the press plate 24 at a predetermined pressure. At this time, heating is also performed at the same time. The heating temperature is a temperature at which adhesiveness is exhibited by the thermoplastic resin contained in the electronic material paste 14 constituting the electric circuit pattern. The pressure applied by the press plate 24 is controlled so that the electric circuit pattern is not deformed when the electric circuit pattern is transferred.

Through the above steps, as shown in FIG. 2C, the electric circuit pattern is adhered to the substrate 22 by the thermoplastic resin, and is thermally transferred. In this state,
Electric circuit patterns do not have sufficient circuit functions. This is because the electric circuit pattern contains a thermoplastic resin. Therefore, as shown in FIG.
The substrate 22 is baked, and the thermoplastic resin is decomposed and volatilized and removed, thereby exhibiting a circuit function.

In the baking step by this heat treatment, if there is a portion having insufficient adhesion between the substrate 22 and the electric circuit pattern, air may be contained here. Also, bubbles are generated when the thermoplastic resin contained in the electric circuit pattern is decomposed and volatilized. However, bubbles generated by these are sufficiently removed, and do not adversely affect circuit characteristics. By using, for example, a thermoplastic polyester as the thermoplastic resin, the bubbles can be removed more efficiently. That is, the firing step is performed at about 600 to 700 ° C., but the thermoplastic resin decomposes at, for example, a temperature of about 300 ° C. or higher and starts to vaporize. In the case of a thermoplastic polyester resin, for example, it decomposes at 440 ° C. and starts to vaporize. At this time, since the thermoplastic resin is in a molten state, the generated air bubbles move in the molten thermoplastic resin and are radiated to an external space. Thus, the electric circuit pattern can be sufficiently adhered to the substrate 22. Furthermore, this electric circuit pattern is
By heating to about 0 to 700 ° C., the glass frit included in the electric circuit pattern is melted, adhered to the substrate 22 such as glass, and can be integrated with the substrate.

When the above-mentioned thermoplastic polyester resin or the like is used as the thermoplastic resin, since the resin has flexibility, when the electric circuit pattern is formed on the transfer paper 10, the transfer paper 10 Even when the electric circuit pattern is bent, the electric circuit pattern can be prevented from peeling off from the transfer paper 10.

When an adhesive resin having an adhesive action, for example, an acrylic resin excellent in combustibility is applied as an adhesion aid on the electric circuit pattern formed on the transfer paper 10 described above, The heating temperature for transferring the electric circuit pattern onto the substrate 22 shown in FIG. 2B can be reduced, or the pressure applied at this time can be reduced.

FIG. 3 shows an example in which an adhesion aid 26 is applied on the electric circuit pattern shown in FIG. 1 (b). In FIG. 3, the adhesive assistant 26 is printed and formed so as to cover the electric circuit pattern. The adhesion auxiliary agent 26 has a low adhesiveness when the thermoplastic cellulose derivative having low adhesion to the glass or the ceramic substrate 22 is used as an organic binder when it is made into a paste, or has a small organic binder when it is made into a paste. In this case, it can be used to sufficiently adhere the electric circuit pattern to the substrate 22.
In particular, in the case of a thermoplastic cellulose derivative widely used for screen printing, it is necessary to increase both the pressure and the heating temperature when transferring without using the adhesion aid 26, which may break the pattern of the electric circuit. It is preferable to use the adhesion auxiliary agent 26 because of its property.

FIG. 4 shows a step of thermally transferring the electric circuit pattern on which the adhesive aid 26 shown in FIG. 3 is formed from the transfer paper 10 to the substrate 22 such as glass or ceramic. In FIG. 4A, the electric circuit pattern covered with the adhesion aid 26 is arranged so as to face the substrate 22, and as shown in FIG. Pressurized with pressure. At this time, heating is also performed at the same time, and the electric circuit pattern is sufficiently adhered to the substrate 22 by the adhesive force of the adhesive assistant 26.

When a thermoplastic resin such as a thermoplastic cellulose derivative is used in the electronic material paste 14 which is a material of the electric circuit pattern, the pressure-sensitive adhesive 26 has a higher thermal decomposition temperature than the thermoplastic resin. Need to be high. As shown in FIG. 4C, the adhesion aid is interposed between the electric circuit pattern and the substrate 22, but the thermal decomposition temperature of the adhesion aid 26 is lower than the thermal decomposition temperature of the thermoplastic resin in the electronic material paste 14. If the temperature is lower than the above, the thermoplastic resin in the electric circuit pattern is not decomposed at the time of sintering, so that the adhesive agent 26 decomposed earlier is not sufficiently released, which causes cracking or peeling at the time of sintering. . Therefore, adhesion aid 2
Assuming that the thermal decomposition temperature of T6 is T ₁ and the thermal decomposition temperature of the thermoplastic resin in the electronic material paste 14 is T ₂ , (T ₁ −T ₂ )
Is preferably 5 ° C to 20 ° C. If (T ₁ −T ₂ ) is less than 5 ° C., cracking or peeling may occur during sintering. When (T ₁ -T ₂ ) exceeds 20 ° C., the thermal decomposition of the thermoplastic resin becomes too large, and it may be difficult to maintain the shape of the electric circuit pattern until the tackifier is decomposed.
Note that (T ₁ −T ₂ ) is more preferably 5 ° C. to 10 ° C. Outside this range, there is a high possibility that the fired electric circuit pattern will crack or peel.

When the sintering start temperature of the electronic material paste 14 as the glass paste according to the present invention is T ₃ , (T ₃ −T ₁ ) needs to be 10 ° C. or more, preferably 20 ° C. It is preferable that this is the case. (T ₃ −
If T ₁ ) is lower than this, the electric circuit pattern starts to flow and solidify before the thermal decomposition of the pressure-sensitive adhesive agent 26, and cracks or peeling may occur in the fired electric circuit pattern.

The above phenomenon is remarkable when the thickness of the electric circuit pattern exceeds 20 μm, and controls the thermal decomposition temperature of the adhesion promoter and the thermoplastic resin (organic binder) and the sintering start temperature of the glass paste. Is preferred. Here, the thermal decomposition temperature is defined as a temperature at which 98% of the weight of the measurement sample is decomposed when the temperature is increased at a rate of 20 ° C./min by thermogravimetry. Further, the sintering start temperature is determined by firing the glass paste at various temperatures and checking the presence or absence of sintering by visual observation.

The thickness of the layer of the above-mentioned adhesion aid 26 is preferably as thin as possible within the range in which the adhesion can be imparted, and is preferably 1 to 3 μm. If it is less than 1 μm, it may not be possible to impart sufficient adhesiveness, and if it is 3 μm, it takes time to decompose and release the adhesion promoter 26, which may cause cracking or peeling of the fired electric circuit pattern.

According to the above-described method of the present invention, not only an electric circuit pattern but also a dielectric print pattern, an insulator print pattern, a resistor print pattern, a colored pattern, a light-shielding pattern, and other inorganic materials are used as print patterns. Functional films and the like can also be transferred. Further, it is possible to form a print pattern on a non-planar substrate, which is difficult to print by direct printing on a substrate by a screen printing method.

A specific example of the transfer printing pattern forming method according to the present invention described above will be described as an example. Examples 1 to 5 below are cases where the printing pattern is an electric circuit pattern. In addition, the glass substrate 22 (200
× 100 mm; thickness 3.5 mm) for specific resistance (μ
Ω · cm), tensile strength (kgf), color difference (ΔE), and quality were measured. The measurement results are shown in Table 1. In addition, these measuring methods are described below. However,
For Examples 2 and 3, the specific resistance and tensile strength were not measured.

Specific resistance: The electric resistance R was measured using a digital multimeter manufactured by Advantest Corporation. Furthermore, the cross-sectional shape was measured using Surfcom (trade name) manufactured by Tokyo Seimitsu Co., Ltd., and the cross-sectional area S was calculated by the integration method.
R × S ÷ L was calculated using the above R and S, and this was defined as the specific resistance. Here, L is the length of the conductive wire. The specific resistance in the case of printing and firing directly on a glass substrate instead of the transfer according to the method of the present example was about 3.8. If the specific resistance of the transfer conductor does not significantly change as compared with this value, it can be determined that the conductor (conductive filament) has been sintered well.

Tensile strength: The Sn-plated copper terminal bonded to the conductor with solder (adhesion area: 25 mm ² ) is pulled by applying a force, and the force when the Sn-plated copper terminal comes off is measured using a small tensile gauge. did. We have 15
A value exceeding kgf was regarded as an allowable range. In other words, if it is 15 kgf or more, it can be determined that the conductor is well seized on the substrate.

Color difference: The square difference of the conductive line of the glass plate with the conductor transferred by the method of the present embodiment, when viewed from the side where the conductive paste is not printed and fired, ΔE (JIS Z8730 6.1)
Was measured using a CR200 type spectrophotometer (trade name) manufactured by Minolta Co., Ltd. When the paste was printed and baked directly on a glass substrate and when the paste was prepared by transfer, the color difference ΔE value of the glass baked surface was 1 or less. In addition, non-conductors were measured in the same manner, and the goodness of the seizure state with the substrate was confirmed.

Quality: The presence or absence of bubble bubbling in the fired pattern was visually examined. When no foaming occurred, the circuit was judged to be well seized on the glass substrate.

[0052]

Embodiment 1 A conductive material was used as an electronic material. Common conductive materials are copper, aluminum, gold, silver,
A metal such as nickel or a conductive oxide such as ITO can be used, and any of them can be used. Here, silver is used because of the availability of the material and the high conductivity. As the silver, flake silver powder having a particle size of about several μm was used. As the low melting point glass powder (glass frit), a low melting point B ₂ O ₃ —SiO ₂ —PbO-based glass frit having a melting point equal to or lower than the softening point of soda lime silica glass as a substrate was used. Table 1 shows the composition of this glass frit.
Are shown as "low melting point glass composition". As a thermoplastic resin (organic binder) to paste silver,
A thermoplastic polyester resin with a molecular weight of about 16,000,
Those having a Tg (glass transition point) of about −25 ° C. were used.
As the volatile solvent, cyclohexanone and BCA (butyl carbitol acetate: boiling point: about 150 ° C.) were used. The silver powder, glass frit, thermoplastic polyester resin, and volatile solvent (solvent) described above were mixed at the ratio shown in Table 1, and kneaded with a mortar and three rolls to form a paste.

[0053]

[Table 1] The screen plate 12 has 150 mesh and an emulsion thickness of 10 μm.
Stainless steel mesh was used. The printing pattern used was a line having a length of 20 cm and a width of 1 mm.

The transfer paper 10 has S
One having an i-layer was used. The produced silver paste was screen-printed on the Si layer of the transfer paper 10 and dried at 120 ° C. Further, this is placed on a glass substrate at 180 ° C.
And baked at 660 ° C. In the case of this example, the thermal decomposition temperature T ₂ of the thermoplastic polyester resin is 440 ° C., while the sintering start temperature T ₃ of the silver paste is 450 ° C., and T ₃ is 10 ° C. higher than T ₂ . Therefore, before the sintering of the silver paste starts, the thermoplastic polyester resin is thermally decomposed, and after the pyrolysis gas is released, the silver paste is sintered. For this reason, there is little possibility that a crack occurs in the fired printing pattern or the printing pattern peels off from the glass substrate.
Here, the sintering starting temperature T ₃ is baking the paste at various temperatures is a value determined by examining the presence or absence of sintering by visual observation. In this example, no adhesion aid was used.

As shown in Table 1, an electric circuit pattern having good specific resistance, tensile strength, and seizure characteristics (color difference, quality) as a conductor after transfer and firing was formed on a glass substrate. .

[0056]

Embodiment 2 An insulator was used as an electronic material. Common insulating materials are low melting glass, SiO ₂ , Zr
Oxides such as O ₂ and MgO can be mentioned, and any of them can be used. Here, low melting point glass powder was used in consideration of availability of materials and adhesion to automobile glass as a substrate. . As the low melting point glass powder, B ₂
An O ₃ —SiO ₂ —PbO-based glass frit having a particle size of about several μm was used. Table 1 shows the composition of this glass frit.
Are shown as "low melting point glass composition".

A thermoplastic polyester resin and a volatile solvent were mixed with the above glass frit in the ratio shown in Table 1,
A paste was formed in the same manner as in Example 1. Next, the paste was screen-printed on the transfer paper 10 and then dried. Then, it was transferred onto a glass substrate and baked. In the case of this embodiment, the thermal decomposition temperature T of the thermoplastic polyester resin
₂ was 440 ° C., while the sintering onset temperature T ₃ of the paste was between the glass transition point Tg of glass frit = 470 ° C. and the softening point Ts = 560 ° C. Therefore, T ₃ becomes T ₂
30 [deg.] C. or more, and as in Example 1, the fired print pattern is less likely to be cracked or peeled off from the glass substrate. In this example, no adhesion aid was used.

As shown in Table 1, an insulator having good seizure characteristics (color difference and quality) after transfer and firing was formed on the glass substrate.

[0059]

Embodiment 3 A dielectric was used as an electronic material. The dielectric material is included in the insulating material. Particularly, a material having a high or low dielectric constant is electrically effective. Typical dielectric materials are low melting glass, SiO ₂ , ZrO ₂ , MgO, BaTiO.
₃ , PbTiO ₃ , PbZrO ₃ , PbSrO ₃ , CaTi
Oxides such as O ₃ can be mentioned, and any of them can be used. Here, CaTiO ₃ having low dielectric constant is used. Since CaTiO ₃ alone cannot secure the adhesion to the substrate glass, CaTiO ₃ mixed with a B ₂ O ₃ —SiO ₂ —PbO-based glass frit having a particle size of about several μm was mixed. The mixing ratio was as shown in Table 1.

These were pasted in the same manner as in Example 1, screen-printed on transfer paper 10, and dried. Then, it was transferred onto a glass substrate and baked. Also in the case of this embodiment,
Thermal decomposition temperature T ₂ of thermoplastic polyester resin is 440 ° C
The sintering start temperature T ₃ of the paste is glass transition point Tg of glass frit = 450 ° C. and softening point Ts = 570 ° C.
Was between. Therefore, similarly to the second embodiment, there is little possibility that the fired print pattern is cracked or peeled off from the glass substrate. In this example, no adhesion aid was used.

As shown in Table 1, a dielectric having good seizure characteristics after transfer and firing was able to be formed on a glass substrate.

[0062]

Embodiment 4 In this embodiment, silver powder was used as an electronic material in the same manner as in Embodiment 1. Ethyl cellulose, which is a thermoplastic cellulose derivative, was used as a thermoplastic resin (organic binder) for forming a silver powder into a paste. These were mixed with the low melting point glass powder and the solvent at the ratios shown in Table 2 to form a paste. Using this silver paste,
After screen printing and drying on the transfer paper 10 to form a print pattern, the adhesive aid 26 shown in Table 2 was printed on the print pattern at 3 μm. The adhesion aid 26 is used to supplement the adhesion of the print pattern because ethyl cellulose used as the organic binder has low adhesion. The adhesion aid 26 is an acrylic resin, and has a thermal decomposition temperature T ₂ (= 375 ° C.) of ethyl cellulose in the silver paste.
Those thermal decomposition temperature T ₁ is higher 5 ° C. than (T ₁ = 38
0 ° C). Then, it was transferred to a glass substrate and baked at a temperature of 660 ° C.

As described above, since T ₁ is 5 ° C. higher than T ₂ , ethyl cellulose is decomposed during firing before the acrylic resin. As a result, ethyl cellulose is released from the print pattern formed of the silver paste and becomes coarse, and the decomposition gas of the acrylic resin that is subsequently decomposed in the pores is easily released. Can be prevented.

In this embodiment, since the sintering start temperature T _{3 of} the silver paste is 70 ° C. higher than the above T ₁ , the pressure-sensitive adhesive agent 2
After the decomposition and volatilization of 6 are sufficiently performed, the silver paste is sintered. Therefore, this also causes cracks in the printed pattern,
Peeling can be prevented.

As shown in Table 2, an electrical circuit pattern having good specific resistance, tensile strength, and seizure characteristics (color difference, quality) as a conductor after transfer and firing was formed on a glass substrate. .

[0066]

[Table 2]

[0067]

Embodiment 5 In this embodiment, silver powder was used as an electronic material in the same manner as in Embodiment 4. Further, a thermoplastic acrylic resin was used as a thermoplastic resin (organic binder) for forming silver into a paste. These were mixed with the low melting point glass powder and the volatile solvent (solvent) at the ratios shown in Table 2 to form a paste. Using this silver paste, screen printing was performed on the transfer paper 10 and dried to form a print pattern, and then the adhesive agent 26 shown in Table 2 was printed 3 μm on the print pattern in the same manner as in Example 4. Then, it was transferred to a glass substrate and baked.

The acrylic resin used as the organic binder in this embodiment is different from the acrylic resin (OS2000 manufactured by Ryogo Kagaku Kogyo Co., Ltd.) used as the adhesion promoter 26, and its thermal decomposition temperature T ₂ is 370 ° C. Since the thermal decomposition temperature T ₁ of the acrylic resin used as the adhesion aid 26 is 380 ° C., which is 10 ° C. higher than T ₂ , the organic binder is also used during the firing in this embodiment.
Decomposed earlier. Therefore, cracking and peeling of the fired print pattern can be prevented.

Also in the case of the present embodiment, since the sintering start temperature T _{3 of the} silver paste is 70 ° C. higher than the above-mentioned T ₁ , cracks and peeling of the fired print pattern can also be prevented.

As shown in Table 2, it was possible to form an electric circuit pattern having good specific resistance, tensile strength, and seizure characteristics (color difference and quality) as a conductor after transfer and firing on a glass substrate. .

[0071]

Embodiment 6 In this embodiment, a black inorganic heat-resistant pigment was used in place of an electronic material, and a low-melting glass powder, a thermoplastic resin (organic binder) and a solvent (volatile) were used in proportions as shown in Table 2. (Solvent) and mixed to form a black ceramic paste. Here, as shown in Table 2, as the low melting point glass powder, PbO—SiO ₂ —Ti
O ₂ -based crystallized glass was used. In addition, a thermoplastic cellulose derivative was used as the organic binder.

Using the above black ceramic paste,
After screen printing and drying were performed on the transfer paper 10 to form a print pattern, the adhesive agent 26 shown in Table 2 was printed on the print pattern at 3 μm in the same manner as in Example 4. Then, it was transferred to a glass substrate and baked.

The thermal decomposition temperature T ₂ of the thermoplastic cellulose derivative used as the organic binder in this example was 370.
° C, and the thermal decomposition temperature T ₁ of the acrylic resin as the adhesion assistant 26 is 380 ° C. Therefore, since T ₁ is higher than T ₂ by 10 ° C., the thermoplastic resin is also decomposed before the adhesion promoter 26 during firing in this embodiment. Therefore, cracking and peeling of the fired print pattern can be prevented.

In this embodiment, the sintering start temperature T ₃ of the black ceramic paste is between the glass transition point Tg = 450 ° C. and the softening point Ts = 570 ° C. of the low melting glass powder. 70 ° C. or higher than ₁ . Therefore,
This can also prevent cracking and peeling of the fired print pattern.

[0075]

As described above, according to the present invention,
It is possible to easily provide a printed pattern of a high-precision thin-film electric circuit or the like on a large-area glass substrate to provide a functional glass, and to cope with high-mix low-volume production.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram in a case where a desired electric circuit pattern is formed on transfer paper in a transfer type printing pattern forming method according to the present invention.

FIG. 2 is a process chart when an electric circuit pattern is thermally transferred from the transfer paper shown in FIG. 1 to a substrate.

FIG. 3 shows a method for forming a transfer-type print pattern according to the present invention, in which a desired electric circuit pattern is formed on transfer paper;
It is explanatory drawing in the case of forming an adhesion auxiliary agent.

FIG. 4 is a process chart when an electric circuit pattern is thermally transferred from the transfer paper shown in FIG. 3 to a substrate using an adhesive aid.

[Explanation of symbols]

Reference Signs List 10 transfer paper, 12 screen plate, 14 electronic material paste, 16 squeegee, 18 base paper, 20 easy release layer, 22 substrate, 24 press plate, 26 adhesive aid.

Claims (9)

[Claims] 1. A transfer-type print pattern forming method, comprising: forming a print pattern on a transfer film using a glass paste; thermally transferring the print pattern onto a substrate; and firing the print pattern thermally transferred onto the substrate. Method. 2. The transfer pattern forming method according to claim 1, wherein the print pattern formed on the transfer film includes a conductive material, an insulating material, a dielectric material, a semiconductor material, a resistive material, and a magnetic material. A transfer printing pattern forming method, comprising: at least one selected from a material and an inorganic heat-resistant pigment; and a thermoplastic resin that is melted and decomposed and volatilized in the baking step. 3. The method according to claim 2, wherein the thermoplastic resin is selected from the group consisting of a thermoplastic polyester resin, a thermoplastic cellulose derivative, a thermoplastic acrylic resin, and a thermoplastic vinyl acetate resin. Alternatively, a transfer-type printing pattern forming method characterized by using a mixed resin of two or more types. 4. The transfer-type print pattern forming method according to claim 1, wherein the print pattern formed on the transfer film has a single-layer structure or a multilayer structure of two or more layers. A method for forming a transfer-type print pattern. 5. The transfer printing pattern forming method according to claim 1, wherein the substrate is made of glass or ceramic. 6. The transfer-type printing pattern forming method according to claim 1, wherein an adhesion assistant is applied in advance on the printing pattern formed on the transfer film. A method for forming a transfer-type print pattern, comprising: 7. The transfer-type print pattern forming method according to claim 1, wherein an adhesive aid is applied in advance on a print pattern formed on the transfer film, Assuming that the decomposition temperature of the adhesion promoter is T ₁ , the decomposition temperature of the thermoplastic resin is T ₂ , and the sintering start temperature of the glass paste is T ₃ , (T ₁ −T ₂ ) is 5 ° C. to 20 ° C. , (T ₃ −T ₁ ) is 10 ° C. or higher. 8. The transfer printing pattern forming method according to claim 1, wherein the printing pattern is an electric circuit pattern. 9. The transfer pattern forming method according to any one of claims 1 to 8, wherein a print pattern is formed on a kind selected from glass for automobiles, glass for buildings, and glass for displays. A glass having a printed pattern formed thereon.