JP2002333719A - Supporting body for forming pattern, paste composition and method for forming pattern by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a uniform pattern having high accuracy of the form and the dimension and large film thickness. SOLUTION: The supporting body for forming a pattern is used to form a pattern by using a paste composition to form a specified pattern and then transferring the formed pattern to an objective body. The contact angle of the supporting body with the paste composition is specified to >=30 deg.. A paste composition having >=30 Pa.s viscosity at 4 s<-1> shear rate at the drying temperature is used for the paste composition to be used to form the pattern on the supporting body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming support, a paste composition, and a pattern forming method using the same.

[0002]

2. Description of the Related Art In recent years,
With the downsizing of mobile communication devices, satellite broadcasting receivers, computers, etc., the high-frequency electronic components used in them are being reduced in size and performance, and the wiring patterns of high-frequency electronic components are also increasing in density. In addition, there is a strong demand for high-speed signal transmission. In order to increase the density of wiring patterns of high-frequency electronic components and increase the speed of signal transmission, there is an increasing demand for uniform, finer, and thicker wiring patterns.

Meanwhile, as a method of forming a circuit in an electronic component, conventionally, a thick film wiring pattern is formed on a sintered substrate by a screen printing method using a paste composition containing an inorganic powder and an organic binder. A method of forming a thick film circuit, which is dried and then fired, is widely used.
However, in the case of this method, there is a problem that it is difficult to form a sufficiently uniform pattern because a mesh mark of the screen plate remains.

As a method for forming a uniform thick film wiring pattern, a paste composition is screen-printed on a support such as a polyethylene terephthalate (PET) film so that a predetermined pattern is formed, and the pattern is formed. Japanese Patent Application Laid-Open No. 61-34992 discloses a method of transferring a pattern onto a sintered substrate by superimposing and pressing the sintered substrate and the sintered substrate, followed by baking. However, even when this method is used, the width and pitch of a pattern that can be formed by the screen printing method are limited to about 50 μm, and it is difficult to form a finer pattern than that.

[0005] As a method of miniaturizing a thick film wiring pattern, a predetermined pattern is formed by exposing and developing a photosensitive paste applied on a support using a paste composition containing a photosensitive organic component. A photosensitive paste method for forming is known (Japanese Patent Application Laid-Open No. 63-25979).

Further, as a method of miniaturizing a thick film wiring pattern on a support such as a carrier film, a method using a photosensitive paste method containing a photosensitive organic component is known (Japanese Patent Laid-Open No. 4-139733). No.).

However, the above-mentioned Japanese Patent Application Laid-Open No.
It is not always easy to form a pattern having a desired accuracy and a large film thickness on an arbitrary object by the method disclosed in Japanese Patent Application Laid-open No. Hei. In fact, there is a strong demand for a method of forming a pattern having a greater film thickness that is more excellent in uniformity and shape accuracy.

In addition, from the viewpoint of heat dissipation and reliability,
Ceramic multilayer substrates have been widely used for high-frequency electronic components.In recent years, ceramic multilayer substrates have also been required to cope with higher densities and higher signal speeds. The demand for film formation is increasing.

By the way, a pattern is formed on a support,
This is transferred to a transfer substrate such as a sintered substrate or ceramic green sheet to form a pattern. On a support that has not been subjected to a release treatment, the pattern is formed by a screen printing method or a photosensitive paste method. However, there is a problem that the adhesion between the pattern and the support is too strong, and the pattern cannot be reliably transferred to the transfer target.

When a ceramic green sheet and a support that has not been subjected to a mold release treatment are overlaid and pressed together, the adhesion between the ceramic green sheet and the support becomes too strong, and the ceramic green sheet is removed from the support. When peeling off, there is a problem that the ceramic green sheet is damaged. Therefore, some release treatment is required for the support.

However, a normal release treatment is performed,
When a light-peelable support is used, when a pattern is to be formed by a screen printing method, the pattern shape is not maintained in a step of drying the paste composition by placing the support on which the pattern is formed in an oven or the like. There is a problem.

That is, the light-peelable support has a strong repulsive force against the paste composition, and the paste composition has a predetermined viscosity in order to maintain the shape of the pattern formed thereon. Is required. However, in the step of drying the paste composition by placing the support on which the pattern is formed in an oven or the like, the temperature around the pattern increases, and the viscosity of the paste composition exceeds the limit required to maintain the pattern shape. And the pattern shape is not maintained.

The present invention solves the above-mentioned problems, and provides a pattern forming support, a paste composition, and a pattern useful for forming a pattern having a uniform thickness, high shape accuracy and high dimensional accuracy, and a large film thickness. A pattern forming method using the same,
High-speed signal production using the pattern forming method,
It is an object of the present invention to provide a method of forming a circuit board and a ceramic multilayer board which sufficiently cope with high-density wiring.

[0014]

In order to achieve the above object, a support for pattern formation according to the present invention (claim 1) comprises:
A step of forming a predetermined pattern on a support using a paste composition, and a step of transferring the pattern formed on the support onto a transfer-receiving member. The surface treatment is performed so that the contact angle with the paste composition is 30 degrees or more.

After a predetermined pattern is formed using the paste composition, the formed pattern is transferred onto a transfer-receiving member to form a pattern-forming support which is used to form a pattern. By using a pattern-forming support that has been subjected to a surface treatment so as to have a contact angle of 30 ° or more, a low shear viscosity during drying (for example, a viscosity at a drying temperature and a shear rate of 4 s ⁻¹ ) is used.
When a paste composition having a large size is used, a predetermined pattern can be reliably formed on the surface of the pattern forming support, and the pattern formed on the pattern forming support can be coated. Transfer onto a transfer body can be reliably performed, and a uniform, high-accuracy, high-dimensional accuracy and large-thickness pattern can be formed.

In the present invention, the phrase "surface-treated so that the contact angle with the paste composition is 30 degrees or more" means that the pattern-forming support has a contact angle of 30 degrees or more. In addition to the case where a predetermined surface treatment has been applied, the contact angle can be obtained without performing any special surface treatment due to the material constituting the pattern formation support and the method of forming the pattern formation support. Is a concept including a pattern forming support having the above range.

The paste composition of the present invention (Claim 2) is a paste composition used for forming a pattern on the pattern-forming support of Claim 1, and has a shear rate at a drying temperature. The viscosity at 4 s ^-1 is 30
Pa · s or more.

When a pattern is formed using a support for pattern formation having a contact angle of 30 ° or more with the paste composition, it is difficult to maintain the shape of the pattern on the support for pattern formation during drying. When a paste composition having a viscosity of 30 Pa · s or more at a shear rate of 4 s ⁻¹ is used, the pattern can be maintained in a desired shape even in the drying step, and the pattern forming support can be used. On the surface of the, it is possible to reliably form a predetermined pattern, and it is possible to reliably transfer the pattern formed on the pattern-forming support onto the object to be transferred, It is possible to form a pattern with high shape accuracy and dimensional accuracy and a large film thickness.

In other words, when a pattern is formed on a substrate for pattern formation at a drying temperature using a paste composition having a viscosity of 30 Pa · s or more at a shear rate of 4 s ⁻¹ , the pattern and the substrate for pattern formation However, by using a pattern forming support having a contact angle of 30 degrees or more with the paste composition, without impairing the stability of the pattern on the surface of the pattern forming support, The pattern formed on the pattern forming support can be reliably transferred onto the transfer target.

Further, the paste composition according to the third aspect is a paste composition used for forming a pattern on the pattern forming support according to the first aspect, wherein the paste composition contains a photosensitive organic component. It is characterized by.

By forming a pattern on the pattern-forming support of the present invention by using a paste composition (photosensitive paste) containing a photosensitive organic component, a uniform and accurate shape can be obtained by the photosensitive paste method. In addition, a pattern having high dimensional accuracy and a large film thickness can be formed.

Further, according to the pattern forming method of the present invention (claim 4), a predetermined pattern is formed on the pattern forming support according to claim 1 using the paste composition according to claim 2 or 3. And a step of transferring the pattern formed on the pattern formation support onto a transfer target.

After a predetermined pattern is formed on the pattern forming support of the present invention (Claim 1) using the paste composition of the present invention (Claim 2 or 3), the pattern is formed on the pattern forming support. By transferring the formed pattern onto the transfer object, the pattern formed on the pattern forming support can be reliably transferred onto the transfer object, resulting in uniform shape accuracy and dimensions. It is possible to form a pattern with high accuracy and a large film thickness.

By using a photosensitive paste containing a photosensitive organic component as the paste composition, the photosensitive paste applied to the pattern forming support is exposed and developed to form a predetermined pattern. By the conductive paste method, it is possible to form a uniform pattern having high shape accuracy and dimensional accuracy and a large film thickness.

According to a fifth aspect of the present invention, in the pattern forming method, the step of forming a predetermined pattern on the pattern forming support comprises the step of forming a paste containing a photosensitive organic component on the pattern forming support. Paste) and a step of exposing and developing the photosensitive paste applied on the pattern forming support to form a predetermined pattern.

In the step of forming a predetermined pattern on the support for pattern formation, a photosensitive paste is applied on the support for pattern formation, and then the applied photosensitive paste is exposed and developed to form fine patterns. The pattern can be efficiently formed on the pattern forming support.

According to a sixth aspect of the present invention, in the pattern forming method, the object to be transferred is formed by forming a slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder, and a plasticizer into a sheet. It is characterized by being a ceramic green sheet.

When the transfer object is a ceramic green sheet formed by molding a slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder, and a plasticizer into a sheet, a predetermined surface is formed on the surface. It is possible to reliably form a ceramic green sheet on which a pattern is provided, and by using the ceramic green sheet, it is possible to efficiently manufacture a multilayer electronic component such as a circuit board or a ceramic multilayer board. Become.

According to a seventh aspect of the present invention, in the pattern forming method, the object to be transferred is formed by forming a slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder, and a plasticizer into a sheet. Wherein the volume ratio of the organic binder to the inorganic powder is such that the amount of organic binder / the amount of inorganic particles ≦ 0.25 (volume ratio).

As the ceramic green sheet, the volume ratio of the organic binder to the inorganic powder is determined by the ratio of the amount of the organic binder /
By using the inorganic particles having an amount of 0.25 (volume ratio), the degreasing property when firing the ceramic green sheet can be improved.

In the pattern forming method according to the present invention, the object to be transferred is formed by forming a slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder and a plasticizer into a sheet. Ceramic green sheet, wherein the volume ratio of the plasticizer and the inorganic powder is
The amount of plasticizer / the amount of inorganic powder ≦ 0.15 (volume ratio).

As the ceramic green sheet, the volume ratio of the plasticizer and the inorganic powder is such that the amount of the plasticizer / the amount of the inorganic powder ≦ 0.
In the case where a material having a volume ratio of 15 (volume ratio) is used, the above-mentioned claim 8 is also used.
As in the case of the pattern forming method, the degreasing property when firing the ceramic green sheet can be improved.

Further, a method of manufacturing a circuit board according to the present invention (claim 9) includes a step of forming a predetermined pattern on a substrate by the pattern forming method according to any one of claims 4 to 8. It is characterized by.

By forming a predetermined pattern on the substrate by the pattern forming method according to any one of claims 4 to 8, a pattern having uniformity, high shape accuracy and high dimensional accuracy, and a large film thickness is provided. Thus, it is possible to reliably manufacture a circuit board which can sufficiently cope with high-speed signal transmission and high-density wiring.

According to the method for manufacturing a ceramic multilayer substrate of the present invention (claim 10), a ceramic green sheet on which a predetermined pattern is formed is laminated and fired by the pattern forming method according to any one of claims 4 to 8. It is characterized by having a step of performing.

According to the method for forming a pattern according to any one of claims 4 to 8, a ceramic green sheet on which a predetermined pattern is formed is laminated and fired, so that the ceramic green sheet is uniform, has high shape accuracy and high dimensional accuracy. It is possible to reliably manufacture a ceramic multilayer substrate having a pattern having a large thickness and capable of sufficiently responding to high-speed signal transmission and high-density wiring.

The circuit board according to the present invention (claim 11) is manufactured by the method for manufacturing a circuit board according to claim 9.

The circuit board manufactured by the method according to the ninth aspect is uniform, has a high pattern accuracy and dimensional accuracy, and has a pattern with a large film thickness, and can sufficiently cope with high-speed signal and high-density wiring. Characteristics can be realized.

A ceramic multilayer substrate according to the present invention (claim 12) is manufactured by the method for manufacturing a ceramic multilayer substrate according to claim 10.

The ceramic multilayer substrate manufactured by the method according to the tenth aspect is uniform, has a high pattern accuracy and high dimensional accuracy, and has a pattern with a large film thickness.
Characteristics that can sufficiently cope with high-density wiring can be realized.

Hereinafter, the present invention will be described in more detail. For example, as shown in FIG. 1, to transfer the pattern 2 on the support 1 to the transfer target 3, the pressure applied to the pattern 2 may be smaller than the adhesive force F ₁ between the support 1 and the pattern 2 during pressing. it becomes necessary and a requirement that the larger the adhesion force F ₂ between the transfer member 3.

When the transfer object 3 is a ceramic green sheet, in order to prevent the ceramic green sheet 3 from being damaged, the ceramic green sheet 3 is further required to have an adhesive force F ₃ between the support 1 and the ceramic green sheet 3. it becomes necessary and a requirement that the larger the tensile strength F ₄ of the seat 3 (FIG. 1).

As shown in FIG. 2, the droplets 4
When, for example, the paste composition 5 is dropped, the surface tension of the droplet (liquid) 4 is γ _L , and the surface tension of the support 1 is γ
_S, if the interfacial tension of the droplet (liquid) 4 and the support 1 and gamma _SL, as shown in FIG. 2 (a), reaches an equilibrium contact angle theta.

As shown in FIG. 2B, when the paste composition 5 is applied on the support 1, the contact angle θ (FIG.
the force F ₅ to try to reach equilibrium (a)), when the paste composition 5 is applied on the support 1 is a resistance force F ₆ to be holding the original equilibrium, on the support 1 The paste composition 5 does not form droplets but forms a uniform layer (FIG. 2).
(b)).

On the other hand, in the step of drying the paste composition 5 is applied, the temperature of the paste composition 5 is viscosity decreases increased, the upper limit value F ₆₀ of the resistance force F ₆ the contact angle θ
To become smaller than the force F ₅ to try to reach equilibrium (FIG. 2 (a)), collapsed equilibrium F ₅ and F _6, the paste composition 5 (not shown) would become the droplets Phenomenon occurs.

Therefore, in order to form the pattern 2 (the coated material of the paste composition 5) on the support 1 and transfer the pattern 2 to the transfer target 3, the conditions of F ₁ <F ₂ and F ₅ <F ₆₀ are satisfied. You need to meet the requirements.

The more the surface treatment of the support 1 is performed (the stronger the surface treatment), the smaller the adhesive force F ₁ between the support 1 and the pattern 2 becomes, and the more the paste composition 5 is applied. There contact angle θ force F ₅ to try to reach equilibrium (FIG. 2 (a)) increases.

[0048] Further, F ₆₀ is derived from the viscosity of the paste composition 5, the low shear viscosity tends to be large higher during drying.

That is, a pattern is formed on a support
To transfer to the transfer object, surface treatment of the support and paste
The low shear viscosity of the composition when dry₁<F₂And F₅
<F ₆₀What is necessary is just to make it. And for that
Has a contact angle with respect to the paste composition within a predetermined range.
Although there is a method using a support for pattern formation, the present invention
The contact angle to the paste composition is 30 degrees or more
And usually uses F₁<
F₂, F₅> F₆₀Low shear viscosity when dry
Using a paste composition having a viscosity of 30 Pa · s or more
By doing, F₅<F₆₀Can meet the requirements of
It will work.

As described above, according to the pattern forming method using the pattern forming support and the paste composition of the present invention, the shape of the formed pattern is changed on the support during drying (when the temperature is raised). Can be reliably held, and by transferring this pattern, a uniform pattern can be formed on a transfer target such as a ceramic green sheet.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a support for pattern formation (hereinafter simply referred to as "support") used in the present invention will be described. Examples of the pattern forming support that can be suitably used in the present invention include, for example,
Film-like supports such as polyester films, polypropylene films, nylon films, and polystyrene films are exemplified.

As the surface treatment method of the pattern forming support, for example, a method of applying a release agent on the support or a method of performing a corona treatment is suitably used.

As the release agent, waxes such as silicone wax, paraffin wax, amide wax, Teflon (registered trademark) wax, carnauba wax, polyethylene wax, amino-modified, epoxy-modified, OH
Modification, COOH modification, catalyst curing type, light curing type, heat curing type silicone oil, silicone resin, fluorine resin, melamine resin, polyolefin resin, polyester resin,
Epoxy resins and the like are preferably used. By performing these surface treatments, it is possible to control the contact angle of the support with the paste composition.

As a surface treatment method in the present invention, for example, in a polystyrene film obtained by mixing syndiotactic polystyrene and rubber and forming a film, the mixing ratio of syndiotactic polystyrene and rubber is adjusted. It is possible to use a changing method, and this method can also control the contact angle of the support with the paste composition.

Since the paste composition has a high viscosity,
Measuring the contact angle of the support with the paste composition using the paste composition itself requires a considerable amount of time. However, insoluble components (such as inorganic powder) in the paste composition do not affect the contact angle of the support with the paste composition. Therefore, in order to measure the contact angle of the support with the paste composition, the contact angle of the support with respect to the paste composition whose viscosity has been reduced by removing insoluble components may be measured.

The contact angle of the support with the paste composition in the present invention was 20 ° C., and insoluble matter was removed from the paste composition using an automatic contact angle meter CA-Z manufactured by Kyowa Interface Science Co., Ltd. Put 5 μl on the support
(Microliter) It is the value of the contact angle measured when dropped.

By using a support in which the contact angle with the paste composition is controlled to 30 degrees or more by performing the surface treatment, in the pattern formation by the screen printing method, even in the drying step involving the temperature rise of the paste composition, The pattern shape can be maintained. Further, even when the photosensitive paste is used, it is possible to prevent the pattern shape from changing in the drying step, and to maintain a predetermined pattern shape.

Next, the paste composition used in the present invention will be described. The paste composition used in the present invention is obtained by kneading or mixing an inorganic powder, an organic binder, an organic solvent, and the like using a three-roll mill or the like. As the inorganic powder in the paste composition of the present invention, conductive metal powder, ceramic powder,
Glass powder or the like can be used.

In the paste composition used in the present invention, gold, silver, copper, platinum, aluminum, and the like can be used as the conductive metal powder which can be suitably used as the inorganic powder.
Examples thereof include simple metal powders such as palladium, nickel, molybdenum, and tungsten, alloy powders of the above metals, and base metal powders such as copper coated with a noble metal such as silver.

In the paste composition used in the present invention, ceramic powders usable as inorganic powders include insulating ceramic powders such as Al ₂ O _{3, and the} like.
Dielectric ceramic powder such as BaTiO ₃ , ferrite powder such as nickel zinc ferrite, nickel zinc copper ferrite, RuO ₂ , Pb ₂ Ru ₂ O ₇ , Mn · Co
・ High resistance ceramic powder such as Ni composite oxide, PZ
And a piezoelectric ceramic powder such as T.

The paste composition used in the present invention is
Glass powder that can be used as an inorganic powder
For example, SiO₂-PbO-based, SiO₂-ZnO-based, S
iO ₂-B₂O₃System, SiO₂-K₂O-based, SiO₂−
Na₂O-based, SiO₂-PbO-B₂O₃System, SiO₂
-ZnO-B₂O₃System, SiO₂-Bi₂O₃-B₂O
₃System, SiO₂-K₂OB₂O₃System, SiO₂-Na
₂OB₂O₃And the like.

The organic binder in the paste composition used in the present invention includes cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate and cellulose butyrate, polyvinyl alcohol and polyvinyl acetate. And vinyl resins such as polyvinyl butyral, polyvinyl acetal and polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, polyimide resins and polyester resins. .

Examples of the organic solvent in the paste composition used in the present invention include anones such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, methylene chloride, 3-methoxybutyl acetate, and ethylene glycol monoester. Alkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene Glycol monoalkyl ether acetates, ethylene glycol, diethylene glycol Lumpur, propylene glycol, dipropylene glycol, glycols such as pentamethylene glycol, alpha-terpineol or the like terpenes such as β- terpineol and the like. For convenience in use, an organic solvent having a boiling point of 150 ° C. or higher is desirable.

The paste composition used in the present invention includes a thixotropic agent, an anti-gelling agent, an antifoaming agent,
Plasticizers, dispersants, dyes, pigments, surfactants, polymerization inhibitors, release agents and the like can be added as appropriate.

The thixotropic agent that can be added to the paste composition is generally a “thickening / sagging / settling inhibitor”, a “sagging / settling inhibitor”, a “pigment wetting / dispersion / sedimentation agent”. It is possible to use what is called `` inhibitors '', and as `` thickening, sagging and sedimentation inhibitors '', vegetable polymerized oils, polyether-ester surfactants, hydrogenated castor oils, Examples thereof include a mixture of hydrogenated castor oil and amide, and a fatty acid amide wax.

Further, as the “sagging / settling preventing agent”,
It is possible to use special fatty acid type, sulfate ester type / anionic type surfactant, polyethylene oxide type, a mixture of polyethylene oxide type and amide type, etc. Polycarboxylic acid, amine salt of high molecular weight polyester, polyether / ester type anionic surfactant, long chain amine salt of high molecular weight polycarboxylic acid, salt of long chain polyaminoamide and high molecular weight polyester, long chain polyaminoamide And a salt of phosphoric acid, a specially modified polyamide, a phosphate ester surfactant, an amide amine salt of a high molecular polyester acid, and the like.

In addition, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose,
Sodium alginate, casein, sodium caseinate, xanthan gum, polyvinyl alcohol, modified polyether warren, polyacrylate, polymethacrylate, montmoronite, aluminum stearate, zinc stearate, aluminum octylate, dextrin fatty acid ester, Dibenzylidene sorbitol, vegetable oil-based polymerized oil, surface-treated calcium carbonate, organic bentonite, silica, titania, zirconia, fine powder of alumina and the like can be used as the thixotropic agent.

The low shear viscosity during drying, that is, the viscosity at a shear rate of 4 s ^-1 at the drying temperature of the paste composition that can be used in the present invention depends on the amount of the thixotropic agent added and the amount of the organic solvent. It is possible to control. The drying temperature of the paste composition used in the present invention is usually 50 to 150 ° C., and can be freely changed according to the heat-resistant temperature of the support for pattern formation. In addition, the shear rate 4 at the drying temperature in the present invention.
The viscosity at s ^-1 (low shear viscosity when dry) was determined by Carri-Me
d., Ltd. (Dorking, Surrey, England) CSL series stress controlled rheometer at a drying temperature of the paste composition, measured using a cone of 2 cmφ and 1 °, and a viscosity at a shear rate of 4 s ⁻¹ . It is.

In the present invention, by setting the low shear viscosity of the paste composition when dried to 30 Pa · s or more,
Even on a patterning support having a contact angle to the paste composition of 30 degrees or more, in the case of the screen printing method, the pattern shape can be maintained during drying, and in the case of the photosensitive paste method, the pattern shape can be maintained during drying. The photosensitive paste coating can remain uniform.

Examples of the plasticizer that can be added to the paste composition used in the present invention include normal alkyl phthalates such as dimethyl phthalate, di-n-octyl phthalate and bis-2-ethylhexyl phthalate; Phthalic acid esters such as 2-ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalethyl glycolate, butyl phthalyl butyl glycolate, tri-2-ethylhexyl trimellitate, tri-n-alkyltrimethyl phthalate Trimellitates such as melitate, triisononyl trimellitate, and triisodecyl trimellitate, dimethyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate Dibutyl glycol adipate,
Di-2-ethylhexyl acetate, dimethyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n-butyl citrate, acetyl Fatty acid dibasic acid esters such as tributyl citrate, glycol derivatives such as polyethylene glycol benzoate, triethylene glycol di- (2-ethylhexoate) and polyglycol ether; glycerin such as glycerol triacetate and glycerol diacetyl monolaurate Derivatives, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., low molecular weight polyether having a molecular weight of 300 to 3000, low molecular weight poly-α-styrene, low molecular weight polystyrene Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2
Orthophosphates such as ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc., and methyl acetyl ricinolate Ricinoleic acid esters, such as poly-1,3-butanediol adipate, polyesters such as epoxidized soybean oil, epoxidized esters, and acetic acid esters such as glycerin triacetate and 2-ethylhexyl acetate.

In the paste composition used in the present invention, when a polyvalent metal component such as copper, boron and lead is contained in the inorganic powder, it reacts with acidic functional groups in the organic binder to cause gelation. May occur. In order to prevent the reaction between the polyvalent metal component in the inorganic additive component and the acidic functional group in the organic binder, it is effective to add one or more of the following three types of additives. (1) Anion-adsorbing substance (2) Alcohol with boiling point of 178 ° C or higher (3) Fatty acid amide

As the anion-adsorbing substance of the above (1),
It may be in the form of inorganic fine particles or organic fine particles. As the inorganic fine particles, hydroxyapatite, hydrotalcite, zirconium phosphate, hydrous antimony oxide, and the like are preferable. In addition, as organic fine particles,
An anion exchange resin can be used.For example, (a) a copolymer of divinylbenzene and acrylate, methacrylate or acrylonitrile is
Primary, secondary, tertiary or tertiary or tertiary or quaternary amino groups introduced as an ion exchange group; (b) a copolymer of trivinylbenzene and acrylate, methacrylate or acrylonitrile; What introduced a quaternary or quaternary amino group as an ion-exchange group, (c) trimethylolpropane trimethacrylic acid ester, and a copolymer of acrylate, methacrylate or acrylonitrile as a base,
A primary, secondary, tertiary or quaternary amino group introduced as an ion exchange group, (d) a copolymer of ethylene glycol dimethacrylate and acrylate, methacrylate or acrylonitrile as a parent, Those obtained by introducing a secondary, tertiary or quaternary amino group as an ion-exchange group are exemplified.

As the alcohol having a boiling point of 178 ° C. or higher in (2), any of monohydric and polyhydric alcohols can be used. As a monohydric alcohol,
1-octyl alcohol, 2-octyl alcohol, nonyl alcohol, decyl alcohol, 1-methylcyclohexanol, trimethylcyclohexanol, ethylene glycol monoacetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monovinyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol isoamyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, trimethylhexanol, tetrahydro Furfuryl alcohol, cresol, butyl lactate, benzyl alcohol, hydroxyethyl acrylate, phenethyl alcohol, mercaptobutanol, hydroxyethyl methacrylate, hydroxyethyl piperazine, cyclohexanone oxime, hydroxymethoxyallyl benzene, hydroxymeth Shi benzaldehyde, hydroxymethyl piperazine, hydroxypropionitrile, hydroxyacetophenone Na futon, hydroxybenzaldehyde,
Hydroxyacetophenone, hydroxybenzimidazole, phenylphenol, hydroxybenzoic acid, hydroxybenzophenone, benzoin, thymol, hydroxymethoxybenzoic acid, hydroxymethylbenzoic acid, hydroxymethylpyrone, hydroxynaphthoic acid, hydroxynaphthoquinone, hydroxynorbornenedicarboximide, hydroxyphenyl Examples include acetic acid, hydroxyphenylglycine, hydroxyphthalimide, neopentylglycol hydroxypivalate, hydroxypropiophenone, hydroxystearic acid, hydroxysuccinimide, hydroxytoluic acid, pentaerythritol diacrylate monostearate or a mixture thereof.

The polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, tetramethylene glycol,
Pentamethylene glycol, butenediol, hexamethylene glycol, heptanediol, octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, hexanetriol, heptanetriol, threitol, erythritol, Examples include arabitol, xylitol, ribitol, adonitol, glucitol, mannitol, iditol, talitol, galactitol, malitol, perseitol, bolemitol and the like.

Further, the fatty acid amide of the above (3) includes:
Examples thereof include acetic amide, butyric amide, propionic amide, valeric amide, hexanoic amide, heptyl amide, octanoic amide, decanoic amide, nonanoic amide, stearic amide, oleic amide, and erucamide.

As the photosensitive organic component added to make the paste composition used in the present invention into a photosensitive paste, a known photopolymerizable compound or photo-modified compound can be used. For example, (1) a monomer or oligomer having a reactive functional group such as an unsaturated group,
A mixture with a photoradical generator such as an aromatic carbonyl compound, (2) a so-called diazo resin such as a condensate of an aromatic bisazide and formaldehyde, and (3) an addition polymerizable compound such as an epoxy compound and a diallyl iodonium salt. Examples thereof include a mixture with a photoacid generator, and (4) a naphthoquinonediazide compound. Among them, particularly desirable is a mixture of a monomer or oligomer containing a reactive functional group such as an unsaturated group and a photoradical generator such as an aromatic carbonyl compound.

Further, it is preferable that the organic binder contains an acrylic copolymer having a carboxyl group in a side chain since a pattern can be formed with an aqueous developing solution such as an aqueous alkaline solution. The photosensitive paste used in the present invention may be either a negative type or a positive type. Further, the organic binder may be made water-soluble so that it can be developed with water.

A monomer containing the above reactive functional group
As the oligomer, hexanediol triacrylate, tripropylene glycol triacrylate, trimethylolpropane triacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, Caprolactone acrylate, ethoxylated nonylphenol acrylate, 1,
3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, ethoxylated bisphenol A
Diacrylate, propoxylated neopentyl glycol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, Pentaerythritol tetraacrylate,
Ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, ethoxylated pentaerythritol tetraacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol di Methacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, isocyanuric acid EO-modified diacrylate, ethoxylated paracumylphenol acrylate, ethylhexyl carbitol acrylate, N-
Vinyl-2-pyrrolidone, isobornyl acrylate,
Examples include polypropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol pentaacrylate, dipentaethythritol hexaacrylate, and the like.

Further, as the above-mentioned photo-radical generator,
Benzyl, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl dimethyl ketal, 2-n-butoxy-4-dimethylamino Benzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,
4-diisopropylthioxanthone, isopropylthioxanthone, 2-dimethylaminoethylbenzoate,
Ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3′-dimethyl-4-methoxybenzophenone, 2,4-dimethylthioxanthone, 1- (4-dodecylphenyl) -2-hydroxy-
2-methylpropan-1-one, 2,2-dimethoxy-
1,2-diphenylethan-1-one, hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2
-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, methylbenzoyl formate, 1-phenyl-1,2-propanedione-2- (o
-Ethoxycarbonyl) oxime, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
1-butanone, bis (2,6-dimethoxybenzoyl)
-2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like.

The acrylic copolymer having a carboxyl group in the side chain to be contained in the organic binder can be produced, for example, by copolymerizing an unsaturated carboxylic acid and an ethylenically unsaturated compound. As unsaturated carboxylic acids, acrylic acid, methacrylic acid,
Maleic acid, fumaric acid, vinyl acetic acid and anhydrides thereof are exemplified. Examples of the ethylenically unsaturated compound include acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, and fumarate esters such as monoethyl fumarate. Further, as the acrylic copolymer having a carboxyl group in the side chain, a copolymer having an unsaturated bond introduced in the following form may be used. (1) An acrylic copolymer obtained by adding an acrylic monomer having a functional group such as an epoxy group, which can react with the carboxyl group in the side chain of the acrylic copolymer. (2) After reacting an unsaturated monocarboxylic acid with an acrylic copolymer in which an epoxy group is introduced instead of a carboxyl group in a side chain, a saturated or unsaturated polycarboxylic anhydride was further introduced. thing.

Next, the transfer object used in the present invention will be described. As the transfer object used in the present invention, a fired substrate such as an alumina fired substrate, a glass substrate, a printed substrate, a ceramic green sheet, or the like can be used.

The ceramic green sheets include, for example, inorganic powders composed of ceramic powder and / or glass powder,
A slurry obtained by mixing a plasticizer, an organic binder, an organic solvent, and the like is formed on a sheet by a doctor blade method or the like, and dried at a temperature of 50 to 150 ° C.

The ceramic powder constituting the ceramic green sheet includes, for example, insulating ceramic powder such as Al ₂ O ₃ , dielectric ceramic powder such as BaTiO _3, and ferrite based powder such as nickel zinc ferrite and nickel zinc copper ferrite. Powder, RuO ₂ , Pb ₂
It is possible to use a high-resistance ceramic powder such as Ru ₂ O ₇ or a composite oxide of Mn, Co, and Ni, and a piezoelectric ceramic powder such as PZT.

In the ceramic green sheet,
The glass powder that can be used is SiO 2₂−P
bO system, SiO₂-ZnO-based, SiO₂-B₂O₃system,
SiO₂-K₂O-based, SiO₂-Na₂O-based, SiO₂
-PbO-B₂O₃System, SiO₂-ZnO-B₂O
₃System, SiO₂-Bi₂O₃-B₂O₃System, SiO₂−
K ₂OB₂O₃System, SiO₂-Na₂OB₂O₃system
And the like.

The inorganic powder constituting the ceramic green sheet desirably contains crystallized glass powder or glass-ceramic powder. By sintering the ceramic green sheet at a low temperature as described above, it is possible to perform simultaneous sintering with a conductor layer made of a low melting point metal such as silver or copper having a small specific resistance.

[0086] Examples of the plasticizer that can be used for the ceramic green sheet include the same plasticizers that can be added to the paste composition used in the present invention.

The organic binder that can be used for the ceramic green sheet includes the same organic binders that can be used for the paste composition used in the present invention.

Examples of the organic solvent that can be used for the ceramic green sheet include the same organic solvents that can be used for the paste composition used in the present invention. Unlike, for convenience of use, the boiling point does not matter.

Further, the ceramic green sheet may further contain a photosensitive organic component similar to that which can be added to the paste composition to form a photosensitive ceramic green sheet. Also, if necessary,
It is also possible to add an antistatic agent, an antifoaming agent and the like.

The transfer object is made of ceramic powder and / or
Alternatively, in the case of a ceramic green sheet obtained by forming a slurry containing an inorganic powder containing a glass powder, an organic binder, and a plasticizer into a sheet, the volume ratio of the organic binder to the inorganic powder is determined by the amount of the organic binder / By using the inorganic particles having an amount of 0.25 (volume ratio), the degreasing property when firing the ceramic green sheet can be improved. Also, the degreasing property when firing the ceramic green sheet can be enhanced by setting the volume ratio of the plasticizer and the inorganic powder in the ceramic green sheet to the amount of the plasticizer / the amount of the inorganic powder ≦ 0.15 (volume ratio). Can be.

Here, the amount of organic binder / the amount of inorganic particles ≦
When using a ceramic green sheet in which 0.25 (volume ratio) or plasticizer amount / inorganic powder amount ≦ 0.15 (volume ratio), the pattern is transferred from the binder-forming support to the ceramic green sheet. In this case, the adhesive strength between the pattern forming support and the ceramic green sheet is increased, and the ceramic green sheet may be broken when the pattern forming support is peeled off. However, when the support for pattern formation of the present invention is used, the amount of the organic binder / the amount of the inorganic particles ≦ 0.25 (volume ratio) or the amount of the plasticizer / the amount of the inorganic powder ≦ 0.15 (volume ratio). Even if a ceramic green sheet is used, the adhesion between the pattern forming support and the ceramic green sheet does not become too strong, and the pattern forming support can be peeled without breaking the ceramic green sheet. it can.

Next, the pattern forming method of the present invention will be described. Examples of the method for forming a pattern on the pattern forming support of the present invention using the paste composition of the present invention include methods such as a screen printing method and a photosensitive paste method. In addition, the pattern forming support is provided with a concave portion having a shape corresponding to the shape of the pattern to be formed,
A method of filling the concave portion with the paste composition using a squeegee or the like, or forming a convex pattern on a pattern forming support using a photoresist or the like, and applying the paste composition to a portion where the pattern is not formed. It is also possible to adopt a filling method or the like.

Hereinafter, a pattern forming method using the photosensitive paste method will be specifically described with reference to FIGS. 3 (a), 3 (b) and 3 (c).

(1) First, as shown in FIG. 3A, a photosensitive paste is applied to the pattern forming support 1 by a method such as spin coater, screen printing, or doctor blade method.
1 and dried at a temperature of 50 to 150 ° C. for 10 minutes to 2 hours to form a coating film 12 of a photosensitive paste.

(2) Next, as shown in FIG. 3B, the coating film 12 on the pattern-forming support 11 is activated by a high-pressure mercury lamp or the like through a mask 15 on which a desired pattern is drawn. A light beam is irradiated at an exposure amount of about ²⁰ to 5000 mJ / cm ² to expose the coating film 12 in a predetermined pattern. Thereby, the light-irradiated portions (exposed portions) 13a and 13a
3b is cured and becomes a region that is not developed by a later development process.

(3) Then, the coating film 12 composed of the exposed portions 13a and 13b and the unexposed portions 12a, 12b and 12c is
A general-purpose aqueous developer such as an aqueous sodium carbonate solution is applied by a method such as a spray shower. As a result, the unexposed portions 12a, 12b, and 12c are dissolved (developed) in the aqueous developer, and the patterns 13a and 13b are formed on the pattern forming support 11 as shown in FIG. You.

Next, a method of transferring the patterns 13a and 13b formed on the pattern forming support 11 to the transfer target 16 will be described with reference to FIGS. 4 (a) and 4 (b).

(1) First, as shown in FIG. 4 (a), the patterns 13a and 13b on the support 11 are formed by using a general hot press under the conditions of 1 to 200 MPa and 50 to 150 ° C. The thermal transfer is performed on the object 16 over a period of 5 seconds to 5 minutes.

(2) Then, as shown in FIG. 4B, the support 11 is peeled from the transfer target 16. Thus, patterns 13a and 13b are formed on the transfer target 16.

[Circuit Board (Chip Coil) According to Embodiment] Next, a circuit board manufactured through a step of forming a predetermined pattern by the pattern forming method of the present invention will be described. Here, a chip coil will be described as an example of the circuit board with reference to FIGS.

As shown in FIG. 6, the chip coil 21 (FIG. 5) has internal electrodes 24a, 24b, 24c and 24c.
The external electrodes 23a, 23b (FIG. 5) are formed on the side surfaces of a laminate (laminated substrate) 22 (FIG. 5) in which insulator layers 22a, 22b, 22c, 22d, and 22e made of alumina or the like on which the respective layers d are formed are sequentially laminated. ) Is provided.

That is, inside the laminated substrate 22, the internal electrodes 24a, 24b, 24c
And 24d are provided between the insulator layer 22a and the insulator layer 22b, between the insulator layer 22b and the insulator layer 22c, between the insulator layer 22c and the insulator layer 22d, and between the insulator layer 22d and the insulator layer 22e. Insulator layer 22a-insulator layer 2
The internal electrodes 24a provided between the electrodes 2b are external electrodes 23a.
In FIG. 5, an internal electrode 24d provided between the insulator layer 22d and the insulator layer 22e is connected to an external electrode 23b (FIG. 5).

Further, the insulator layer 22a-insulator layer 22b
The internal electrode 24a provided therebetween is connected to the insulator layer 2 via a via hole (not shown) formed in the insulator layer 22b.
2b and the internal electrode 24b provided between the insulator layer 22c. Similarly, the internal electrode 24b and the internal electrode 24c, and the internal electrode 24c and the internal electrode 24d are electrically connected to the insulator layer 22c. , 22d via a via hole (not shown).

Next, a method of manufacturing the chip coil 21 will be described. (1) First, using a photosensitive conductor paste using a conductive powder as an inorganic powder, the pattern forming method of the present invention is performed by a photosensitive paste method, and an insulator layer (insulating substrate) 22a such as alumina is formed. A desired conductor pattern is formed thereon. Next, after degreasing, for example, at 850 ° C. in air.
For about one hour to form a spiral internal electrode 24a.
To form

(2) Next, using a photosensitive insulating paste using glass powder as the inorganic powder, the pattern forming method of the present invention is carried out by the photosensitive paste method, and the insulating material on which the internal electrode 24a is formed is formed. An insulator paste layer is formed on the substrate 22a. A via hole pattern having a diameter of, for example, 50 μm is formed on the insulating paste layer by a photosensitive paste method. Further, baking is performed at a predetermined temperature in the atmosphere to form an insulator layer 22b having a through hole for a via hole (not shown).

(3) Then, a conductive paste is filled into the through-hole for via hole and dried to form a via hole (not shown) for connecting one end of the internal electrode 24a and one end of the internal electrode 24b. 1) In the internal electrode 24a
The spiral internal electrode 24b is formed by a method similar to the method of forming the above.

(4) Next, in the same manner,
c, internal electrode 24c, insulator layer 22d, internal electrode 24d
To form Then, by forming a protective insulator layer 22e and further providing external electrodes 23a and 23b, a chip coil 21 having a structure in which an internal electrode and an insulator layer are laminated as shown in FIG. 5 is obtained. Can be

According to the above-described manufacturing method, the internal electrodes 24
Since a, 24b, 24c and 24d are formed by the pattern forming method of the present invention using the photosensitive paste method, a uniform and fine conductor pattern can be formed. Also, the insulator layers 22b, 22c, 22
Since the pattern forming method of the present invention is used to form d and 22e, a uniform insulator layer can be formed. Further, since the through-holes for via holes are formed in the insulator paste layer using the photosensitive paste method, fine via holes can be efficiently formed.

As described above, according to the pattern forming method of the present invention, a uniform conductor pattern and an insulating layer can be formed, so that it is possible to cope with a high-speed signal of a circuit board. Further, since the photosensitive paste method is used, a fine pattern and a via hole can be formed, so that the circuit board can be downsized.

The pattern forming method of the present invention is not limited to a chip coil, but may be a high-frequency circuit electronic component such as a chip capacitor or a chip LC filter, or a high-frequency module (for example, a VCO (Voltage Controlled Osc)).
It can be applied to a high-frequency circuit board such as an illator or a PLL (Phase Locked Loop).

[Ceramic Multilayer Substrate According to Embodiment]
Next, a ceramic multilayer substrate formed by using the pattern forming method of the present invention will be described with reference to FIG.

The ceramic multilayer substrate 31 shown in FIG. 7 has insulating layers 32a, 32b, 32c, 32d, and 32e.
And a multilayer circuit board formed by laminating dielectric layers 33a and 33b. Further, inside the ceramic multilayer substrate 31, a capacitor pattern, a coil pattern, a strip line, and the like are formed by the inner layer conductor patterns 34a, 34b, 34c and the via holes 35. further,
A semiconductor IC is provided on one main surface of the ceramic multilayer substrate 31.
37, a chip component 38 such as a chip capacitor, a thick film resistor 39, etc. are provided.
And the inner layer conductor patterns 34a, 34b, 34c, etc.

Next, a method of manufacturing the ceramic multilayer substrate 31 will be described. First, by performing a pattern forming method of the present invention by a photosensitive paste method using a photosensitive conductive paste using a conductive powder as an inorganic powder, an insulating ceramic green sheet and a dielectric ceramic green on which a desired pattern is formed. Make a sheet.

Next, the ceramic green sheets on which the conductor patterns and the via holes are formed are stacked, pressed and fired at a predetermined temperature. Further, similarly, after the pattern forming method of the present invention is performed by the photosensitive paste method to form the surface conductor pattern 36, the chip component 3 is formed.
8. The semiconductor IC 37 is mounted, and the thick film resistor 39 is printed. Thus, a ceramic multilayer substrate 31 having a structure as shown in FIG. 7 is obtained.

According to the above-described manufacturing method, the pattern forming method of the present invention using the photosensitive paste method is used to form the inner conductor patterns 34a, 34b, 34c and the surface conductor pattern 36. A uniform and fine conductor pattern can be formed.

Further, according to the pattern forming method of the present invention, since a uniform pattern can be formed on the ceramic green sheet, it is possible to cope with a high-speed signal of the ceramic multilayer substrate. Furthermore, since a fine pattern can be formed by using the photosensitive paste method, the size of the ceramic multilayer substrate can be reduced.

The ceramic multilayer substrate is not limited to high-frequency circuit electronic components such as a chip capacitor and a chip LC filter.
ageControlled Oscillator) and PLL (Phase Locked L)
oop) etc.).

[0118]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, and the features thereof will be described more specifically.

After the following raw materials were mixed, they were kneaded using a three-roll mill to prepare a photosensitive conductor paste. <Organic binder> Copolymer having a copolymerization ratio of methacrylic acid / methyl methacrylate of 25/75 by weight (weight average molecular weight = 50,000): 3.2 g <Conductive material> Silver powder: 40.0 g <Reaction Functional Group-Containing Monomer> Ethoxylated trimethylolpropane triacrylate:
3.2 g <photopolymerization initiator> 2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropan-1-one: 0.3 g 2,4-diethylthioxanthone: 0.1 g 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone: 0.2 g <organic Solvent> Ethyl carbitol acetate: 4.0 g

Next, a composition obtained by removing the silver powder from the composition of the photosensitive conductor paste was mixed and stirred to prepare a transparent photosensitive varnish having no insoluble matter.

Next, borosilicate glass powder 37.3
g, 24.9 g of alumina powder, 6.2 g of an acrylic organic binder, 5.0 g of di-n-octyl phthalate, 3.1 g of ethanol, and 0.5 g of toluene, and a slurry obtained by a doctor blade method. It is formed into a sheet and dried at 100 ° C.
A μm ceramic green sheet (ceramic green sheet 1) was obtained. Ratio of organic binder and inorganic particles in ceramic green sheet (organic binder amount /
The amount of inorganic particles) is 0.30 (volume ratio), and the ratio of plasticizer to inorganic particles (plasticizer amount / inorganic particle amount) is 0.24 (volume ratio).
It is.

Next, a polyester film A not particularly subjected to surface treatment and polyester films B to L subjected to surface treatment by coating with a silicone resin were prepared. The strength of the surface treatment of the polyester films B to L is changed by a known method.

Next, the photosensitive conductive paste was applied to the polyester films A to L by a doctor blade method, and then dried at 50 ° C. for 1 hour, and the coatability of the photosensitive conductive paste on the polyester films A to L was reduced. Was examined. The results are shown in Table 1 together with the contact angles of the polyester films A to L with the photosensitive varnish.

[0124]

[Table 1]

[0125] In Table 1, those marked with “○” in the column of paste applicability indicate that the photosensitive conductive paste was dried in a uniform state without being formed into droplets during drying. It was good. In addition, those marked with “x” in the column of paste applicability were those in which the photosensitive conductive paste became droplets during drying, became non-uniform, and had poor paste applicability. . In addition, the contact angle of the polyester film A without surface treatment is too low,
It could not be measured.

Table 1 shows that when polyester films A to G having a contact angle to the photosensitive varnish of less than 30 degrees as shown in Nos. 1 to 7 were used, the paste coatability was good. .8 to 12, polyester film H having a contact angle with photosensitive varnish of 30 degrees or more
It can be seen that when L was used, the paste coatability was poor.

On the other hand, a composition obtained by adding Dispalon 305 (manufactured by Kusumoto Kasei) as a thixotropic agent to the composition of the above-mentioned photosensitive conductor paste (photosensitive conductor paste 1) was prepared. To obtain photosensitive pastes 2 to 5. Then, the photosensitive conductive paste 2-5, at 50 ° C., the viscosity was measured at a shear rate of ^{4s -1} (dry low shear viscosity).

Next, the photosensitive conductive pastes 2 to 5 are applied to the polyester films H to L by a doctor blade method, and then dried at 50 ° C. for 1 hour to form the photosensitive conductive pastes on the polyester films H to L. The coatability of 2 to 5 was measured. Table 2 shows the photosensitive conductor pastes 2 to 5 together with the added amount of Disparon 305 and the low shear viscosity when dried.
Shown in

[0129]

[Table 2]

[0130] In Table 2, "O" in the column of paste applicability indicates that the photosensitive conductive paste did not form droplets during drying, but was dried in a uniform state.
Indicates that the photosensitive conductive paste did not completely become droplets during drying, but also generated non-uniform portions. Further, “x” indicates that the photosensitive conductive paste became droplets during drying, resulting in an uneven state. In addition,
Dispalon 305 is insoluble in the photosensitive varnish and does not affect the contact angle of the polyester film with the photosensitive conductive paste.

As shown in Table 2, when a photosensitive conductive paste having a low low shear viscosity of 30 Pa · s or more is used as in the case of photosensitive conductive pastes 4 and 5, the photosensitive conductive paste applied material is kept in its original form. It can be seen that, since the resistance force to be applied is strong, even on a polyester film having a contact angle of 30 degrees or more with the photosensitive conductive paste 1, it is dried uniformly. On the other hand, in the case of the photosensitive conductor paste having a low low shear viscosity of less than 30 Pa · s as in the case of the photosensitive conductor pastes 2 and 3, the resistance to keep the applied material of the photosensitive conductor paste in the original shape is weak. Therefore, it can be seen that the polyester film having a contact angle of 30 degrees or more with the photosensitive conductive paste 1 is dried unevenly.

Further, a conductive pattern is formed on the polyester film H by using the photosensitive conductive pastes 4 and 5, transferred and laminated on a ceramic green sheet having via holes formed, and then subjected to degreasing and firing. As a result, a ceramic multilayer substrate having a conductor pattern was obtained.

The above-mentioned ceramic green sheet 1
In the composition of the above, the amount of acrylic organic binder and di-n-
By changing the amount of octyl phthalate, the ceramic green sheets 2 to 7 having different ratios of organic binder and inorganic particles (organic binder amount / inorganic particle amount) and different ratios of plasticizer and inorganic particles (plasticizer amount / inorganic particle amount) Produced.

Next, using the polyester films F and G, polyester films 1 and 2 with a conductor pattern were produced.

Next, using the polyester films H and I, polyester films 3 and 4 with a conductor pattern were produced.

Next, the polyester films 1 to 4 with a conductor pattern are superimposed on the ceramic green sheets 2 to 7 and hot-pressed under the conditions of 10 MPa and 60 ° C. for 1 minute. Was thermally transferred onto the ceramic green sheets 2 to 7. The state of the ceramic green sheet at the time of peeling the polyester film at that time is indicated by ceramic green sheet 2
Table 3 shows the ratio of the organic binder to the inorganic particles (the amount of the organic binder / the amount of the inorganic particles) and the ratio of the plasticizer to the inorganic particles (the amount of the plasticizer / the amount of the inorganic particles).

[0137]

[Table 3]

In Table 3, "O" indicates that the ceramic green sheet was not damaged when the polyester film was peeled off, and "X" indicates that the ceramic green sheet was broken when the polyester film was peeled off. Show.

As shown in Table 3, when a polyester film having a contact angle with a photosensitive varnish of 30 ° or more was used, such as polyester films 3 and 4 with a conductor pattern, the amount of organic binder / the amount of inorganic particles was Even when a ceramic green sheet with ≦ 0.25 (volume ratio) or plasticizer amount / inorganic particle amount ≦ 0.15 (volume ratio) is used, the adhesion of the polyester film to the ceramic green sheet is small. The conductor pattern was completely transferred onto the ceramic green sheet without breaking the ceramic green sheet when the polyester film was peeled off. On the other hand, when a polyester film having a contact angle with respect to the photosensitive varnish of less than 30 degrees, such as the polyester films 1 and 2 with a conductor pattern, is used, the amount of organic binder / the amount of inorganic particles ≦ 0.25 (volume Ratio) or a plasticizer amount / inorganic particle amount ≦ 0.15 (volume ratio), the ceramic green sheet is damaged when the polyester film is peeled off because the adhesion of the polyester film to the ceramic green sheet is large. It was confirmed that it would.

Next, using ceramic green sheets 4 to 7 in which conductor patterns were transferred from polyester films 3 and 4 with conductor patterns, a ceramic green sheet having no conductor pattern was formed,
The layers were laminated by pressing under hydrostatic pressure for 1 minute under the conditions of Pa and 60 ° C., and after degreasing, they were baked in air under the temperature condition of 900 ° C. In each case, L / S = 15/20 (μm), thickness 8
A ceramic multilayer substrate with a conductor pattern of μm was obtained.

The present invention is not limited to the above embodiments and examples, and various applications and modifications can be made within the scope of the invention.

[0142]

As described above, the pattern forming support of the present invention (claim 1) is subjected to a surface treatment so that the contact angle with the paste composition becomes 30 degrees or more. Even when a paste composition having a large low shear viscosity is used, it is possible to reliably form a predetermined pattern on the surface of the pattern forming support, and to form a pattern formed on the pattern forming support. Can be reliably transferred onto a transfer target, and a uniform pattern having high shape accuracy and dimensional accuracy and a large film thickness can be formed.

The paste composition of the present invention (Claim 2) is a paste composition used for forming a pattern on the pattern forming support of the present invention, and has a shear rate of 4 s at a drying temperature. Viscosity at ^-1 is 30
Since it is configured so as to be Pa · s or more, it becomes possible to keep the pattern in a desired shape even in the drying step, so that a predetermined pattern is reliably formed on the surface of the pattern forming support. And the pattern formed on the pattern-forming support can be reliably transferred onto the object to be transferred. A large pattern can be formed.

Further, since the paste composition of the present invention (claim 3) contains a photosensitive organic component, it is uniform, has high shape accuracy and dimensional accuracy, and has a large film thickness by the photosensitive paste method. A pattern can be efficiently formed.

The pattern forming method of the present invention (Claim 4) uses the paste composition of the present invention (Claim 2 or 3) on the pattern forming support of the present invention (Claim 1). After the predetermined pattern is formed, the pattern formed on the pattern-forming support is transferred onto the transfer-receiving body, so that the pattern formed on the pattern-forming support is transferred onto the transfer-receiving body. It is possible to surely form a uniform, high-precision and dimensional accuracy and large-thickness pattern.

In the case where a photosensitive paste containing a photosensitive organic component is used as the paste composition, a uniform pattern having high shape and dimensional accuracy and a large film thickness can be formed by the photosensitive paste method. It can be formed efficiently.

Further, in the step of forming a predetermined pattern on the pattern forming support as in the pattern forming method of the fifth aspect, the photosensitive paste is applied on the pattern forming support after being applied. Expose the photosensitive paste,
When development is performed, a fine pattern can be efficiently formed on the support.

Further, as in the case of the pattern forming method of the present invention, the object to be transferred is formed into a sheet shape by slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder and a plasticizer. In the case of a ceramic green sheet, a ceramic green sheet having a predetermined pattern disposed on its surface can be reliably formed. By using the ceramic green sheet, a circuit board, a ceramic multilayer board, or the like can be formed. Can be efficiently manufactured.

Further, as in the pattern forming method of the present invention, a ceramic green sheet having a volume ratio of organic binder / inorganic powder of organic binder / inorganic particle ≦ 0.25 (volume ratio) is used. In this case, the degreasing property when firing the ceramic green sheet can be improved.

Further, as in the pattern forming method of the present invention, the ceramic green sheet is such that the volume ratio of the plasticizer and the inorganic powder is such that the amount of the plasticizer / the amount of the inorganic powder ≦ 0.15 (volume ratio). Also in this case, as in the case of the pattern forming method of claim 7, the degreasing property when firing the ceramic green sheet can be improved.

Further, as in the method for manufacturing a circuit board according to the present invention (claim 9), a predetermined pattern is formed on a substrate by the pattern forming method according to any one of claims 4 to 8. In this case, it is possible to reliably manufacture a circuit board which is uniform and has a pattern with high shape accuracy and dimensional accuracy and a large film thickness, and which can sufficiently cope with high-speed signal transmission and high-density wiring.

Further, like the method of manufacturing a ceramic multilayer substrate according to the present invention (claim 10), ceramic green sheets having a predetermined pattern formed by the pattern forming method according to any one of claims 4 to 8 are laminated. By manufacturing a ceramic multilayer substrate through a firing process, a ceramic that is uniform, has high shape and dimensional accuracy, has a pattern with a large film thickness, and can sufficiently respond to high-speed signaling and high-density wiring A multilayer substrate can be reliably manufactured.

The circuit board according to the present invention (claim 11) is manufactured by the method according to claim 9 and has a uniform pattern with high shape precision and dimensional precision and a large film thickness. As a result, it is possible to realize characteristics that can sufficiently cope with high-speed signal transmission and high-density wiring.

The ceramic multilayer substrate of the present invention (claim 12) is manufactured by the method of claim 10 and is uniform, has high shape precision and high dimensional precision, and
Since a pattern having a large film thickness is provided, it is possible to realize characteristics that can sufficiently cope with high-speed signal transmission and high-density wiring.

[Brief description of the drawings]

 .

FIG. 1 is a schematic view showing a mechanism for transferring a pattern from a pattern formation support to a transfer target.

FIGS. 2A and 2B are schematic views showing a mechanism for forming a pattern on a pattern forming support in the present invention.

FIGS. 3A, 3B and 3C are schematic sectional views showing a pattern forming method according to an embodiment of the present invention.

FIGS. 4A and 4B are schematic sectional views showing a pattern forming method according to an embodiment of the present invention.

FIG. 5 is a schematic diagram showing a circuit board (chip coil) according to an embodiment of the present invention.

FIG. 6 is an exploded perspective view showing a configuration of a circuit board (chip coil) according to one embodiment of the present invention.

FIG. 7 is a schematic sectional view showing a ceramic multilayer substrate according to one embodiment of the present invention.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 support 2 pattern 3 transfer object (ceramic green sheet) 4 droplet 5 paste composition θ contact angle F ₁ adhesive force between support and pattern F ₂ adhesive force between pattern and transfer object F ₃ support Adhesive force between body and ceramic green sheet F ₄ Tensile strength of ceramic green sheet F ₅ Force to reach equilibrium at contact angle θ F ₆ Resistance to maintain original shape γ Surface of _L droplet (liquid) Tension γ _S Surface tension of support γ Interfacial tension between _SL droplet (liquid) and support F ₆₀ Upper limit of resistance F ₆ 11 Support for pattern formation 12 Coating with photosensitive paste 12a, 12b, 12C Unexposed Units 13a, 13b Exposure unit (pattern) 15 Mask 16 Transfer object 21 Chip coil 22 Laminated body (laminated substrate) 22a, 22b, 22c, 22d, 22e Insulator layer 23 a, 23b External electrode 24a, 24b, 24c, 24d Internal electrode 31 Ceramic multilayer substrate 32a, 32b, 32c, 32d, 32e Insulator layer 33a, 33b Dielectric layer 34a, 34b, 34c Inner layer conductor pattern 35 Via hole 36 Surface conductor pattern 37 Semiconductor IC 38 Chip component 39 Thick film resistor

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H05K 3/46 H05K 3/46 TF term (Reference) 2H025 AA02 AA03 AB15 AC01 AD01 BJ06 DA33 FA29 FA35 2H096 AA26 BA05 CA05 HA07 HA30 5E343 AA23 BB24 BB72 BB76 DD02 DD03 DD56 DD62 DD76 EE42 EE52 EE58 GG08 5E346 AA15 AA32 CC16 CC32 DD13 DD44 EE21 HH26

Claims (12)

[Claims] 1. A method comprising the steps of: forming a predetermined pattern on a support using a paste composition; and transferring the pattern formed on the support onto an object to be transferred. A support for forming a pattern, which has been subjected to a surface treatment so that a contact angle with respect to a paste composition is 30 degrees or more. 2. A paste composition used for forming a pattern on the pattern forming support according to claim 1, wherein the viscosity at a shear rate of 4 s ^{-1 at} a drying temperature is 30 Pa · s or more. A paste composition comprising: 3. A paste composition used for forming a pattern on the pattern-forming support according to claim 1, wherein the paste composition contains a photosensitive organic component. Paste composition. 4. A step of forming a predetermined pattern on the pattern forming support according to claim 1 using the paste composition according to claim 2 or 3, and forming the predetermined pattern on the pattern forming support. Transferring the pattern onto an object to be transferred. 5. The step of forming a predetermined pattern on the pattern forming support, the step of applying a paste containing a photosensitive organic component (photosensitive paste) on the pattern forming support. 5. The pattern forming method according to claim 4, further comprising: exposing and developing a photosensitive paste applied on the pattern forming support to form a predetermined pattern. 6. A ceramic green sheet formed by molding a slurry containing an inorganic powder containing a ceramic powder and / or a glass powder, an organic binder, and a plasticizer into a sheet. The pattern forming method according to claim 4 or 5, wherein: 7. The ceramic green sheet wherein the transferred body is formed by molding a slurry containing an inorganic powder containing ceramic powder and / or glass powder, an organic binder, and a plasticizer into a sheet shape, 7. The pattern forming method according to claim 6, wherein the volume ratio of the organic binder and the inorganic powder is such that the amount of the organic binder / the amount of the inorganic particles ≦ 0.25 (volume ratio). 8. A ceramic green sheet in which the object to be transferred is formed by molding a slurry containing an inorganic powder containing ceramic powder and / or glass powder, an organic binder, and a plasticizer into a sheet, 8. The pattern forming method according to claim 6, wherein the volume ratio of the plasticizer and the inorganic powder is such that the amount of the plasticizer / the amount of the inorganic powder ≦ 0.15 (volume ratio). 9. A method of manufacturing a circuit board, comprising a step of forming a predetermined pattern on a substrate by the pattern forming method according to claim 4. 10. A method of manufacturing a ceramic multilayer substrate, comprising a step of laminating and firing ceramic green sheets on which a predetermined pattern has been formed by the pattern forming method according to claim 4. . 11. A circuit board manufactured by the method for manufacturing a circuit board according to claim 9. 12. A ceramic multilayer substrate manufactured by the method for manufacturing a ceramic multilayer substrate according to claim 10.