JP2002082428A - Alkali developable photosensitive paste composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste composition for conductor/dielectric formation having high resolution even in a large film thickness and capable of forming a fine pattern. SOLUTION: The alkali developable paste composition contains (a) 40-97 pts.wt. inorganic powder, (b) 0.5-30 pts.wt. carboxyl-containing photosensitive resin binder, (d) 0.5-30 pts.wt. photoreactive monomer, (e) 0.2-20 pts.wt. photopolymerization initiator and (f) 1-30 pts.wt. organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductor and dielectric material which can be suitably formed by a photolithography method and which is adapted to a higher density and finer line in the field of electronic materials. About. More specifically, the present invention relates to a method for forming a conductor / conductor on a circuit board or the like.
An object of the present invention is to provide a conductor and a dielectric forming material that enable formation of a fine pattern with a high film thickness, which has not been realized conventionally, when forming a dielectric pattern.

[0002]

2. Description of the Related Art Conventionally, a paste using a metal powder such as Ag or Cu or a powder having a high hiding power such as black glass has been used for forming a conductor and a dielectric pattern on a substrate. However, when such a paste is used, in forming a pattern by photolithography, if the film thickness after firing is as high as 20 μm or more, it is inevitable that the resolution becomes insufficient.

For example, in the invention described in Japanese Patent Application Laid-Open No. 05-67405, a glycidyl methacrylate adduct is used as a binder, and only a phenyl ketone initiator is used as a photopolymerization initiator. When an initiator having an absorption wavelength is used, it is very difficult to form a pattern in a system having a high film thickness and a strong hiding power.

In Japanese Patent Application Laid-Open No. 11-43501, a photopolymerization initiator containing 2,4,6
The examples disclose the use of a combination of trimethylbenzoyldiphenylphosphine oxide and dimethylbenzyl ketal. In this case, although there is an advantage that it can be developed with water, it is not possible to obtain a high resolution as in the case of alkali etching.

[0005]

As described above, no conductor / dielectric forming material has been proposed so far that high resolution can be obtained even with a large film thickness and a fine pattern can be formed. The present invention has been made in view of such circumstances, and aims to provide a composition capable of initiating high-efficiency photopolymerization, which has never been seen before, by blending a specific photosensitive binder system in a predetermined amount. I do.

[0006]

In order to achieve the above object, the present invention has been studied as follows: a) 40 to 97 parts by weight of an inorganic powder; b) 0.5 of a photosensitive binder resin containing a carboxyl group. ~
Alkaline development type paste composition comprising 30 parts by weight, c) 0.5 to 30 parts by weight of a photoreactive monomer, d) 0.2 to 20 parts by weight of a photopolymerization initiator, and e) 1 to 30 parts by weight of an organic solvent. By using
The present inventors have found that excellent line formation, that is, formation of fine patterns of conductors / dielectrics is possible even when applied with a high film thickness on a substrate, and have completed the present invention.

The carboxyl group-containing photosensitive binder resin (b) preferably has the following chemical formula I:

[0008]

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[In the formula (I), R ₁ may be the same or different, and include a hydrogen atom, a C1-C4 alkyl group, -OCR ₂
COOH (R ₂ represents an alkyl group, a phenyl group or cyclohexyl group _{C2~C4), - C 3 H 6} OH,
-C ₂ H ₄ OH or an -COCH _3, at least 0.1 moles of -OCR ₂ COO per glucose unit
H]], a carboxyl group-containing cellulose derivative, a methacryloyloxyethyl isocyanate adduct of the carboxyl group-containing cellulose derivative, or a glycidyl methacrylate adduct of the carboxyl group-containing cellulose derivative. Further, as the carboxyl group-containing photosensitive binder resin (b), the following chemical formula II:

[0010]

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[In the formula II, R ₃ is a hydrogen atom or C
It represents H _3, which may be the same or different, R ₄
Represents a C1 to C18 alkyl group, a phenyl group or an arylalkyl group, and l, m and n each represent an integer of 1 or more].
Alternatively, a resin having a carboxyl group and a methacryloyl group in which glycidyl (meth) acrylate is added to a compound represented by the formula II is also preferable. The use of these binder resins is particularly preferred in that the inorganic powder can be formed into a fine pattern with a high film thickness.

In the above-mentioned alkaline developing paste composition, the photopolymerization initiator (d) may be one containing an acylphosphine oxide group alone, or one containing an acylphosphine oxide group and one containing a phenylketone group. An initiator can be used as a combination system. Since this system has a wide light absorption wavelength band and a high quantum yield, it can be efficiently cured to a deep portion even in the case of a high film thickness, and as a result, a good resolution can be obtained.

Further, as the inorganic powder (a), A
When at least one selected from the group consisting of metal powders of u, Ag, Cu, Pd, Pt, Ni, Al, W, Mo and Mn is selected, a paste composition for forming a conductor can be obtained. And Si, Pb, B, Z
one or more of oxides of n, Al, Ca, Mg and Ba;
Alternatively, when at least one or more kinds of glass powder containing one or more of such metal oxides as a constituent component is selected,
It can be a paste composition for forming a dielectric layer. And as the inorganic powder, Au, Ag, C
at least one selected from the group consisting of metal powders of u, Pd, Pt, Ni, Al, W, Mo and Mn, and Si, Pb, B, Zn, Al, Ca, Mg and B
It may be used in combination with at least one glass powder containing one or more oxides of a or one or more of these metal oxides as a constituent.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION First, each component to be blended in the paste composition of the present invention will be described.

(A) Inorganic powder An inorganic powder is an essential component for forming a conductor layer and / or a dielectric layer, and various conventionally known ones can be used.

(A-1) The formation of a conductor layer is indispensable for maintaining circuit continuity. For this reason, Au, Ag, Cu,
A conductive powder that is at least one member of the group consisting of Pd, Pt, Ni, Al, W, Mo, and Mn can be used, and generally, for example, Ag-Pd, Ag -Pt, Ag-Pt-Pd, Mo
-Two or more kinds such as Mn may be used in combination.

(A-2) In order to form a dielectric layer,
In order to obtain adhesion between the conductor and the substrate after firing,
oxides of i, Pb, B, Zn, Al, Ca, Mg, Ba
Is preferably used. For the same purpose, B_TwoO_Three・ B
i_TwoO_ThreeSystem, PbO ・ B_TwoO_ThreeSystem, PbO ・ SiO_TwoSystem, P
bOB_TwoO_Three・ SiO_TwoSystem, PbO ・ Al_TwoO_Three・ SiO _Two
System ・ ZnO ・ PbO ・ B_TwoO_ThreeSystem, ZnO ・ B_TwoO_ThreeSystem, C
aOB_TwoO_ThreeSystem, CaO ・ B_TwoO_Three・ SiO_TwoSystem, CaO
・ PbO ・ SiO_TwoSystem, CaO ・ PbO ・ B_TwoO_Three・ Si
O_TwoSystem, MgO ・ B_TwoO_ThreeSystem, MgO ・ B_TwoO_Three・ SiO_Two
System, MgO / PbO / SiO_TwoSystem, MgO / PbO / B_Two
O_Three・ SiO_TwoOne or two types of glass frit
Powders derived from glass containing more than one kind may be used.

(A-3) Further, the conductive powder of (a-1) is used in combination with the metal oxide or glass described in (a-2) to conduct the conductor to the substrate while ensuring conduction. The fixation may be strengthened.

If necessary, an appropriate amount of a metal oxide, silicide, Bi ₂ O ₃ , or the like shown as a conductive powder can also be used in combination.

The above-mentioned inorganic powder, when formed into a paste, has a viscosity suitable for printing, blade coating, and the like; and, in order to make the line width approximately 20 μm, the particle size is 20 μm.
It is preferably not more than μm. Therefore, those having an average particle size of 0.1 to 15 μm and a maximum particle size of 20 μm or less can be suitably used.

If the amount of the inorganic powder is too small, the conductor layer and / or the dielectric layer cannot be properly formed in a pattern, which hinders the etching. Since it may be possible, the ratio is preferably adjusted to the above-mentioned ratio.

(B) Carboxyl group-containing binder resin The binder resin as the second component of the paste composition of the present invention is an alkali-soluble photosensitive resin containing a carboxyl group. This resin has the property of being alkali-soluble when uncured, and has the property of insolubilizing only the photocured portion with alkali, and can be suitably used as a binder resin for forming a pattern by a photolithography method. High contrast ratio.

The molecular weight of the binder resin is 1000
It is desirable that the molecular weight is from 100,000 to 100,000 from the viewpoint of etching properties and workability. When the molecular weight is less than 1,000, the viscosity of the obtained paste composition becomes too low, so that printability and the like are inferior. In addition, the molecular weight is 100,000
When the value exceeds, the binder ability is too high, so that the etching property at the time of alkali etching is inferior.

Preferred as such photosensitive binder resin are: (b-1) Chemical formula I:

[0025]

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[In the formula (I), R ₁ may be the same or different, and includes a hydrogen atom, a C1-C4 alkyl group, -OCR ₂
COOH (R ₂ represents an alkyl group, a phenyl group or cyclohexyl group _{C2~C4), - C 3 H 6} OH,
-C ₂ H ₄ OH or an -COCH _3, at least 0.1 moles of -OCR ₂ COO per glucose unit
A binder resin which is a methacryloyloxyethyl isocyanate adduct of a carboxyl group-containing cellulose derivative or a glycidyl (meth) acrylate adduct of the same derivative; (b-2) Chemical formula II:

[0027]

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[In the formula II, R ₃ is a hydrogen atom or C
It represents H _3, which may be the same or different, R ₄
Represents a C1 to C18 alkyl group, a phenyl group or an arylalkyl group, and l, m and n each represent an integer of 1 or more.] Wherein a methacrylic acid-methacrylate copolymer binder resin (in which a comonomer And (b-3) a binder resin containing a carboxyl group and a methacryloyl group, which is a glycidyl methacrylate adduct of the copolymer binder resin described in (b-3) and (b-2). is there.

In the above (b-1), the carboxylic acid derivative of cellulose represented by the chemical formula I contains 0.1 to 1.0 mol of —OH groups per glucose unit, and at least 0.1 mol per glucose unit. Preferably, those containing 0.1 to 1.0 mol of -COOH groups can be suitably used.

The amount of -OH group is 0.1 per glucose unit.
If the amount is less than 1 mol, the resolution may be poor because the ratio of the polymerizable group introduced with glycidyl (meth) acrylate or methacryloyloxyethyl isocyanate is too low. On the other hand, if the amount of -OH groups exceeds 1.0 mol per glucose unit, the cured film becomes too hard, resulting in poor etching properties. And -COOH
When the group is less than 0.1 per glucose unit, the solubility in an alkaline aqueous solution is low and the etching property is poor. When the -COOH group exceeds 1.0 mol per glucose unit, the water resistance of the cured film is reduced. Therefore, the resolution is inferior.

The amount of glycidyl (meth) acrylate added to the carboxylic acid derivative of cellulose represented by the chemical formula I is preferably from 0.3 mol to 2.0 mol per 1 mol of -OH group. When the glycidyl (meth) acrylate addition amount is less than 0.3 mol per mol of -OH group, the resolution is inferior because the ratio of the polymerizable group introduced is low, while the glycidyl (meth) acrylate addition amount is-.
If it exceeds 2.0 moles per mole of OH group, the cured film becomes too hard, resulting in poor etching properties.

The addition amount of methacryloyloxyethyl isocyanate to the carboxylic acid derivative of cellulose represented by the chemical formula I is 0.2 to 0.2 mol per mol of --OH group.
Preferably it is 1.0 mole. When the addition amount of methacryloyloxyethyl isocyanate is less than 0.2 mol per 1 mol of -OH group, the ratio of the polymerizable group to be introduced is too low, so that the resolution is inferior. If it exceeds 0 mol, the film becomes too hard when cured, resulting in poor etching properties with an aqueous alkali solution.

In the above (b-2), the (meth) acrylic acid- (meth) acrylate copolymer binder resin represented by the chemical formula II comprises (meth) acrylic acid,
It is a copolymer with a C18 alkyl or arylalkyl (meth) acrylate. In Formula II:
l is preferably from 0 to 30, m is preferably from 5 to 95, and n is preferably from 5 to 70, and those having the above-mentioned molecular weight are suitably used.

The addition amount of the glycidyl methacrylate adduct of the (meth) acrylic acid- (meth) acrylate copolymer binder resin represented by the chemical formula II in the above (b-3) is included in the above copolymer. The amount is preferably 0.05 to 1.00 mol equivalent per 1 mol of the carboxyl group, in view of the balance between the solubility of the uncured portion in an aqueous alkaline solution and the curability by light.

The amount of the binder resin described in detail above is
If the amount is too small, the pattern formation becomes difficult due to poor etching, and if the amount is too large, the etching property is impaired and good resolution cannot be obtained.

(C) Photoreactive monomer In the paste composition of the present invention, the alkali-soluble photosensitive binder resin is diluted to adjust the viscosity and, at the same time, to adjust the physical properties of the cured portion. Add a functional monomer.

The photoreactive monomer used here is, for example, the following chemical formula III:

[0038]

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Wherein R ₅ is H or a methyl group, R ₆ is a C2-C9 alkyl group, a polyethylene oxide group having a molecular weight of 44-1000, a polypropylene oxide group having a molecular weight of 56-1000, or

[0040]

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Wherein n represents an integer of 1 to 10, and R ₇ represents H or a methyl group, and the following chemical formula IV:

[0042]

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[Wherein, R ₈ represents H or a methyl group, R ₉ represents a C1-C18 alkyl group, a C7-C26 arylalkyl group, or a C8-C18 alkylaryl group]
And the like, and any of those used as ordinary ultraviolet curable resin compositions can be used.

For example, C1-C18 alkyl (meth) acrylate, C1-C8 alcohol ethylene oxide derivative (meth) acrylate, C1-C1
8, (alkyl) phenol ethylene oxide derivative (meth) acrylate, C2-C9 diol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, bisphenol A ethylene oxide derivative di (meth) acrylate, bisphenol A propylene oxide derivative di (meth) acrylate, with the following chemical formula:

[0045]

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Wherein R ₁₀ -R ₁₂ may be the same or different and represent H or a methyl group; m, l and o each represent an integer of 0 or more;
It is 10. A trimethylolpropane derivative (meth) acrylate, preferably trimethylolpropane tri (meth) acrylate, trimethylolpropaneethylene oxide derivative tri (meth) acrylate and trimethylolpropaneprolene oxide derivative tri (meth) acrylate, The following chemical formula:

[0047]

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[Wherein, R _{13 to} R ₁₅ may be the same or different and each represents H or a methyl group; p, q and r each represent an integer of 0 or more;
It is 10. Glycerin derivative (meth) acrylate, preferably glycerin ethylene oxide derivative tri (meth) acrylate and glycerin prolene oxide derivative tri (meth) acrylate, and the following chemical formula:

[0049]

Embedded image

[Wherein R _{16 to} R ₁₈ may be the same or different and represent H or a methyl group, and R ₁₉ represents H or a (meth) acryloyl group. ],
Examples thereof include, but are not limited to, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.

(D) Photopolymerization Initiator The photopolymerization initiator (d) is a component added to initiate polymerization for curing the exposed portion.

In particular, in a system having a high hiding power as in the present invention, rather than a system having a high absorbance coefficient, a system capable of efficiently generating radicals from absorbed light energy, in other words, a photopolymer having a high quantum yield. An initiator is required.

Examples of such a photopolymerization initiator include a compound containing an acylphosphine oxide group alone or a combination of a compound containing an acylphosphine oxide group and a compound containing a phenylketone group.

Compounds containing an acylphosphine oxide group include benzoyldiphenylphosphine oxide, methylbenzoyldiphenylphosphine oxide,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dichlorobenzoyl) 4
-Propylphenylphosphine oxide, bis (2,
4,6-trimethylbenzoyl) -phenylphosphine oxide and derivatives thereof.

Compounds containing a phenyl ketone group include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-
Hydroxy-2-methyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-
Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-12-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone-1
And the like.

If necessary, aminobenzoic acids,
An appropriate amount of a sensitizing aid such as a dye may be used in combination.

If the addition amount of the photoinitiator is too small or too large, the usability of the paste composition may be impaired and the paste composition may become difficult to be put to practical use. Is preferred.

(E) Organic solvent To improve the handling of the paste composition of the present invention as a paste, terpineol,
Dihydroterpineol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol,
Alternatively, organic solvents such as acetates, pentanediol alkyl ethers, dibutyl phthalate, γ-butyrolactone, and aromatic, alcohol, ester, and ketone solvents are added.

If the addition amount is too small, the viscosity of the paste composition becomes too high, resulting in inferior usability. If the addition amount is too large, on the other hand, the viscosity becomes low, making line formation difficult, and in particular, ensuring a sufficient film thickness. It is inconvenient because it may be difficult, and there is a possibility that non-negligible distortion may be caused by drying after coating on the substrate. Therefore, it is preferable to adjust the ratio to the above-mentioned ratio.

Further, a thermal polymerization inhibitor, an antioxidant, a stabilizer and the like known in the art may be appropriately added as long as the characteristics of the paste composition of the present invention are not impaired.

In order to produce the paste composition of the present invention, the components described above may be blended and kneaded using a roll or the like in a conventional manner to form a paste.

The method of using such a paste composition is substantially the same as the method of using a conventional photosensitive conductive paste. That is, the paste composition of the present invention is applied on a sintered ceramic substrate or a green sheet, coated with a pattern mask, exposed to light to cure a predetermined portion, and then immersed in an alkali developing solution for etching. In this way, a fine pattern can be developed even with a high film thickness,
The desired fine pattern formation with high resolution can be achieved.

[0063]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are merely examples, and are not intended to limit the present invention.

[Synthesis Example 1] Synthesis of alkali-soluble photosensitive binder resin Hydroquinone was charged in a 1 L flask equipped with a stirrer, a condenser, an air inlet tube and a thermometer in an amount of 0.005.
g, carboxylic acid-modified cellulose derivative (see Table 1, hydroxypropyl methylcellulose phthalate,
90.0 g of Shin-Etsu Chemical Co., Ltd., trade name: HPMCP) and 210.0 g of butyl carbitol acetate were charged.
The temperature was raised to 0 ° C. to dissolve. While introducing air, 16.1 g of glycidyl methacrylate was charged and the temperature was raised to 90 ° C. Then, stirring was continued at 90 to 95 ° C. for 5 hours. The completion of the reaction was confirmed by the disappearance of the absorption at 820 cm ^-1 attributed to the oxirane ring by IR spectrum.

[Synthesis Example 2] Synthesis of alkali-soluble photosensitive binder resin In a 1 L flask equipped with a stirrer, a condenser, an air inlet tube, and a thermometer, 0.005 g of hydroquinone was added to a carboxylic acid-modified cellulose derivative (Table 1). Reference, hydroxypropyl methylcellulose hexahydrophthalate,
90.0 from Shin-Etsu Chemical Co., Ltd., trade name: HPMCHHP)
g and butyl carbitol acetate (210.0 g) were charged and dissolved by heating to 70 ° C. While introducing air, methacrylloyloxyethyl isocyanate is added to 1
1.0 g was charged and the temperature was raised to 90 ° C. Then, stirring was continued at 90 to 95 ° C. for 5 hours. The end of the reaction
Free-NCO was determined by chemical titration according to a standard method to obtain -NC.
It was confirmed that O was 0.1 mmol / g or less.

[Synthesis Example 3] Synthesis of alkali-soluble photosensitive binder resin In a 1 L flask equipped with a stirrer, a condenser, an air introduction tube, and a thermometer, 0.005 g of hydroquinone was added to a carboxylic acid-modified cellulose derivative (Table 1). Reference, 90.0 g of hydroxypropyl methylcellulose acetate phthalate, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: HPMCAP) and 210.0 g of butyl carbitol acetate were charged.
The temperature was raised to 0 ° C. to dissolve. While introducing air, 13.9 g of glycidyl methacrylate was charged and the temperature was raised to 90 ° C. Then, stirring was continued at 90 to 95 ° C. for 5 hours. The completion of the reaction was confirmed by the disappearance of the absorption at 820 cm ^-1 attributed to the oxirane ring by IR spectrum.

[0067]

[Table 1]

The alkali-soluble photosensitive binder resins obtained in Synthesis Examples 1 to 3, carboxyl group-containing cellulose derivatives shown in Table 1, or: methyl methacrylate-methacrylic acid-butyl acrylate =
Using a 65/25/10 mol% copolymer or: methacryloyloxyethyl isocyanate of hydroxypropylcellulose (manufactured by Hercules, trade name: KULCEL) as a binder resin, a dielectric paste composition or a conductor paste composition ( (Shown in Tables 2 and 3 respectively).

The components blended in each paste composition are as follows. (A) inorganic powders _{A: ZnO · PbO · B 2} O 3 based glass frit (manufactured by Asahi Glass Co., Ltd., trade name: ASF-1550), B: PbO · B 2 O 3 · SiO 2 based glass frit (Nippon Electric Glass Co. Ltd., trade name: GA-9), or _{C: CaO · PbO · B 2} O 3 · SiO 2 type glass frit (manufactured by Asahi glass Co., Ltd., trade name: YFT-061) (c) photoactive monomer TMPTMA (trimethylolpropane Propane trimethacrylate, manufactured by Daiichi Kogyo Seiyaku, New Frontier NF Bisomer TMPTMA), PEM-200 (polyethylene glycol 200 dimethacrylate, manufactured by Daiichi Kogyo Seiyaku, New Frontier NF Bisomer PEM-20)
0) and TEGDMA (triethylene glycol dimethacrylate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., New Frontier NF Bisomer TEGDMA) (d) Photopolymerization initiator As acylphosphine oxide-based photopolymerization initiator A, I: benzoyldiphenylphosphine oxide, II : Methylbenzoyldiphenylphosphine oxide, III: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, IV: bis (2,6-dichlorobenzoyl) 4-propylphenylphosphine oxide, or V: bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide Phenyl ketone group-containing (acetophenone) photopolymerization initiator B, VI: 2-hydroxy-1-phenylpropan-1-one, VII: 1-hydroxy- Clohexyl-phenyl ketone, VIII: 2,2-dimethoxy-1,2-diphenylethanone, IX: 2-methyl-1-1 [4- (methylthio) phenyl] -2-morpholinopropanone-1, or X: 2-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone-1 (e) Organic solvent α-terpineol.

Examples 1 to 5 Production of Dielectric Paste and Formation of Dielectric Layer After premixing each component having the composition shown in Table 2, the mixture was kneaded with a three-roll ceramic roll manufactured by EXAKT to form a paste. .

The obtained paste was solid-printed on a glass substrate using a # 325 mesh stainless screen and then dried at 80 ° C. for 10 minutes five times to obtain a dry film thickness of 100 μm. Thereupon, a chrome mask 10 shown in FIG. 1 was placed, and exposure was performed with 800 mJ of parallel light. The chrome mask 10 shown in FIG. 1 has a line width W and a gap width G of 50 as shown in the partial enlarged view of FIG.
A first region 1 of μm and a second region 2 of 75 μm are formed. Then 0.5
After being immersed in a 2% by weight aqueous solution of Na ₂ CO ₃ for 2 minutes, it was showered and developed. Further, firing was performed in a belt conveyor type firing furnace at a peak temperature of 600 ° C. for 10 minutes in air.
The film thickness after firing was 60 μm.

For the sample thus obtained, the pattern at line / gap: 75/75 μm (FIG. 2, first area 1) and 50/50 μm (FIG. 2, second area) was magnified by × 80. Line formation was evaluated by observation with a microscope. The evaluation of the line formability is as follows: ": The whole is patterned, the unexposed portions are completely etched, and there are no defects such as disconnection and short-circuit lines;
Δ: The whole is patterned, but the etching of the unexposed portion is insufficient and there is a defect such as a disconnection or a short circuit; and ×: The etching cannot be performed or the whole is dissolved and cannot be developed. "

[0073]

[Table 2]

As is clear from Table 2, according to the paste composition of the present invention, a high-thickness dielectric layer could be formed with preferable line forming properties.

Examples 6 to 10 Production of Conductive Paste and Formation of Conductive Layer Each component having the composition shown in Table 3 was preliminarily mixed and kneaded with a three-roll ceramic roll manufactured by EXAKT to form a paste. As the inorganic powder, a powder derived from glass frit and a metal powder were used in combination.

The obtained paste was solid printed on an alumina substrate and dried at 80 ° C. for 10 minutes three times by using a # 325 mesh stainless screen to make the dry film thickness 60 μm. Thereupon, a chrome mask shown in FIG. 1 was placed, and exposure was performed with 800 mJ of parallel light. Then 0.5
After being immersed in a 2% by weight aqueous solution of Na ₂ CO ₃ for 2 minutes, it was showered and developed.

Further, in a belt conveyor type firing furnace, A
The g-containing paste composition was baked in air, and the Cu-containing paste composition and the Ni-containing paste composition were baked in N ₂ at a peak temperature of 850 ° C. for 10 minutes. Next, the shape of the obtained sample was observed, and the line formability was evaluated in the same manner as described in Examples 1 to 5 above. The thickness after firing was 30 μm.

As Comparative Example 1, a similar paste composition was prepared using hydroxypropylcellulose methacryloyloxyethyl isocyanate without using a carboxyl group-containing binder resin, and an attempt was made to form a conductor layer.

[0079]

[Table 3]

As is clear from Table 3, according to the paste composition of the present invention, a high-thickness dielectric layer could be formed with preferable line forming properties. On the other hand, Comparative Example 1
According to the results, the line formability was poor.

[0081]

As described above, according to the present invention,
In forming a conductor / dielectric pattern on a circuit board or the like, alkali etching can be achieved with high resolution even at a film thickness of 20 μm or more based on the initiation of highly efficient photopolymerization,
Thus, a conductor / dielectric forming material capable of realizing fine pattern line formation is provided.

[Brief description of the drawings]

FIG. 1 is a plan view showing the shape of a chromium mask used when applying a paste composition according to the present invention.

FIG. 2 is a partially enlarged view of the chrome mask shown in FIG.

[Description of Signs] 1 ... first area 2 ... second area 10 ... chrome mask

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 291/00 C08F 291/00 5G301 G03F 7/029 G03F 7/029 5G303 7/038 501 501/03/501 501 H01B 1/22 H01B 1/22 A 3/00 3/00 A H05K 1/09 H05K 1/09 DF term (reference) 2H025 AA01 AA02 AA19 AB17 AC01 AD01 BC13 BC42 BC81 BC83 BC86 CA02 CA35 CC08 CC09 CC20 FA17 FA29 4E351 BB01 BB31 CC11 DD04 DD05 DD06 DD10 DD17 DD19 DD20 DD31 DD52 EE02 EE03 EE11 EE13 EE25 EE26 GG01 4J011 PA03 PA07 PA15 PA53 PA65 PA68 PA69 PB08 PB40 PC02 QA03 QB02 QB03 QB16 QB28 SA02 SA14 BA02 BA01 BA01 A02 BA01 DB30 DB36 GA07 4J027 AA01 AA02 AC03 AC04 AC06 AH00 BA24 CA12 CA20 CB10 CC05 CD10 5G301 DA03 DA04 DA05 DA06 DA08 DA09 DA10 DA11 DA12 DA14 DA33 DA34 DA35 DA36 DA42 DD01 5G303 AA05 AA08 AB20 BA12 CA01 CA03 CA09 CB01 CB02 CB03 CB06 CB17 CB25 CB30 CB38 CC01 CD01 CD04

Claims (7)

[Claims] 1. An alkaline developing paste composition comprising: a) 40 to 97 parts by weight of an inorganic powder; b) 0.5 to 0.5 parts by weight of a carboxyl group-containing photosensitive binder resin.
A paste composition comprising 30 parts by weight, c) 0.5 to 30 parts by weight of a photoreactive monomer, d) 0.2 to 20 parts by weight of a photopolymerization initiator, and e) 1 to 30 parts by weight of an organic solvent. 2. The carboxyl group-containing photosensitive binder resin has the following chemical formula I: [In formula I, R ₁ may be the same or different and include a hydrogen atom, a C1-C4 alkyl group, —OCR ₂ COOH (R ₂
Represents an alkyl group, a phenyl group or cyclohexyl group _{C2~C4), - C 3 H 6} OH, -C 2 H 4 OH or an -COCH _3, of at least 0.1 mol per glucose unit -OCR ₂ COOH], the carboxyl group-containing cellulose derivative, a methacryloyloxyethyl isocyanate adduct of the carboxyl group-containing cellulose derivative, or a glycidyl methacrylate adduct of the carboxyl group-containing cellulose derivative. 3. The carboxyl group-containing photosensitive binder resin has the following chemical formula II: [In formula II, R ₃ represents a hydrogen atom or CH ₃ , which may be the same or different, and R ₄ is
Wherein glycidyl (meth) acrylate is added to a carboxyl group-containing acrylic resin represented by the formula (1) or a compound represented by the formula (II), wherein l, m and n each represent an integer of 1 or more. The paste composition according to claim 1, which is a resin containing a carboxyl group and a methacryloyl group. 4. The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator is an initiator containing an acylphosphine oxide group alone, or a combination of an initiator containing an acylphosphine oxide group and an initiator containing a phenylketone group. The paste composition according to any one of the above. 5. The method according to claim 1, wherein the inorganic powder is Au, Ag, Cu, P
The paste composition according to any one of claims 1 to 4, wherein the paste composition is at least one selected from the group consisting of metal powders of d, Pt, Ni, Al, W, Mo, and Mn. 6. The method according to claim 1, wherein the inorganic powder is Si, Pb, B, Z.
one or more of oxides of n, Al, Ca, Mg and Ba;
5. The paste composition according to claim 1, wherein the paste composition is at least one kind of glass powder containing at least one kind of these metal oxides as a component. 7. The method according to claim 1, wherein the inorganic powder is Au, Ag, Cu, P
at least one selected from the group consisting of metal powders of d, Pt, Ni, Al, W, Mo and Mn;
A combination with at least one glass powder containing at least one of oxides of i, Pb, B, Zn, Al, Ca, Mg and Ba or at least one of these metal oxides as a constituent. 5. The paste composition according to any one of 1 to 4.