JPH0834096A - Ceramics green sheet and formation of pattern thereon - Google Patents

Abstract

PURPOSE:To form a pattern on a ceramics green sheet using photosensitive paste by providing a photo-set layer of a photosensitive resin compsn. on a ceramics green sheet substrate. CONSTITUTION:A photosensitive resin compsn. is used in the formation of the photo-set layer on a ceramics green sheet substrate. The photosensitive layer composed of the photosensitive resin compsn. is a layer becoming insoluble by the irradiation with active light. As an example of the photosensitive resin compsn., a compsn. prepared by mixing a functional monomer or oligomer having one or more unsaturated group in one molecule thereof with a proper polymer binder is designated. As a result of the sufficient curing of the photosensitive resin compsn. layer with ultraviolet rays, the chemical resistance or solvent resistance of a sheet is enhanced and the reaction with an org. solvent in photosensitive paste is almost eliminated and an undeveloped part is perfectly removed. By this constitution, a good pattern can be formed on the sheet using photosensitive paste.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramics green sheet suitably used for forming a fired ceramics substrate and the like and a method for forming a pattern on the ceramics green sheet. Ceramics
The green sheet is a green sheet made of a ceramic that is suitable for use in high-density mounting in which semiconductor elements are mounted and interconnected with each other, and particularly for a multilayer ceramic board. , A green sheet effective for forming a fine circuit pattern on the surface and inner layer electrodes of a ceramic multilayer substrate.

[0002]

2. Description of the Related Art Multilayer ceramic substrates are mainly manufactured by a green sheet laminating method. The green sheet laminating method is a method of printing a conductor and laminating a large number of green sheets that have been subjected to via hole processing, thermocompression-bonding, and then simultaneously firing to form a multilayer substrate.

Conventional ceramics green sheets are
Japanese Unexamined Patent Publication No. 1-232797 and Japanese Unexamined Patent Publication No. 2-14145
As described in Japanese Patent Publication No. 8, usually, a ceramic powder, an organic binder, a plasticizer, a solvent, and a dispersant, if necessary, are appropriately blended and mixed to form a slurry, and the obtained slurry is a doctor blade method. The green sheet is formed by a known method such as. The obtained green sheet is processed into a desired shape by a cutter or a punching die, and then a via hole or through hole (hereinafter referred to as a via hole) is provided on the green sheet by a die or laser using a punch die. Drilling with. Then, the green sheet is filled with a conductive paste in the via holes by a normal screen printing method.

Further, in JP-A-63-64953 and JP-A-2-204356, a composition containing a ceramic raw material, an ultraviolet curable liquid compound and a photopolymerization initiator is irradiated with ultraviolet rays to be cured. Green sheets containing a bisazide compound have been proposed as ceramics green sheets and glass ceramic green sheets.

On the other hand, in order to form a conductor pattern on a conventional green sheet, a screen printing method using a conductive paste has been used. In this method, L (line width) is used.
It is difficult to form a fine pattern of / S (width interval) = 100 μm / 100 μm or less. Therefore, JP-A-63-26
As described in JP-A-5979, JP-A-5-67405 and JP-A-5-204151, there has been proposed a photosensitive conductive paste capable of forming a fine conductor pattern by using a photolithography method. ing. This photosensitive conductive paste comprises a paste of a composition containing conductive powder such as copper, gold, tungsten or silver, a photosensitive resin, a photoinitiator and a solvent. The film obtained by applying the paste to the ceramic substrate after firing the paste by the screen printing method is dried, and then the exposed portion is cured by irradiating with ultraviolet rays using a photomask having a circuit pattern. Next, a non-cured portion of the unexposed portion is removed using a developing solution to form a pattern. However, when attempting to form a conductor pattern using a photosensitive conductive paste on a conventional green sheet that has not been fired, the organic solvent contained in the conductive paste is poor because the green sheet has poor chemical resistance and dissolution resistance. And the polymer binder in the green sheet react with each other, and it is very difficult to remove the unexposed portion during development.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a ceramic green sheet and a pattern on the ceramic green sheet, which can form a good pattern by a photolithography method using a photosensitive paste on the ceramic green sheet. To provide a method of forming.

[0007]

The object of the present invention is as follows.
A ceramics green sheet characterized by providing a layer obtained by photo-curing a photosensitive resin composition on a ceramics green sheet substrate, and applying a photosensitive paste on the ceramics green sheet, drying, selective exposure,
It is achieved by a method of forming a pattern on a ceramic green sheet, which is characterized by developing.

Known ceramics green sheets can be used as the ceramics green sheet substrate in the present invention. That is, usually, a ceramic powder, an organic binder, a plasticizer, a solvent and, if necessary, a dispersant and the like are appropriately blended, and then mixed to form a slurry, and the slurry is formed into a sheet by a known method such as a doctor blade method. It is what

Usually, the thickness of the ceramic green sheet is about 50 to 250 μm.

The ceramic powder contained in the ceramic green sheet substrate is not particularly limited, and any known ceramic insulating raw material for low temperature or high temperature firing can be applied. 850-1000 for low temperature
For high temperature and high temperature, it is a ceramic insulating material that can be sintered at 1400 to 1650 ° C.

Examples of the ceramic powder used in the present invention include ceramic powder alone, glass-ceramic composite system, and crystallized glass.

Examples of the ceramic powder used alone include alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ).
₂ ), magnesia (MgO), beryllia (BeO), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (5SiO ₂ .2Al ₂ O ₃ .2MgO), spinel (MgO.Al ₂ O ₃ ), forsterite (2MgO
・ SiO ₂ ), anorthite (CaO ・ Al ₂ O ₃・ 2)
SiO ₂ ), Sergian (BaO ・ Al ₂ O ₃・ 2Si
Powders of O ₂ ), silica (SiO ₂ ), aluminum nitride (AlN) and the like, or ceramic powder for low temperature firing are mentioned. The purity of these ceramic powders is preferably 90% by weight or more.

Examples of the glass-ceramic composite system include, for example, glass composition powder containing SiO ₂ , Al ₂ O ₃ , CaO, B ₂ O ₃ and optionally MgO and TiO ₂ , and alumina, zirconia, magnesia. , Beryllia, mullite, cordierite, spinel, forsterite, anorthite, cergian, silica, and at least one inorganic filler powder selected from the group consisting of aluminum nitride. SiO ₂ more preferably ceramic powder in terms of oxide title 30-70 wt% Al ₂ O ₃ 5~25 wt% CaO 5 to 25 wt% MgO 0 wt% B ₂ O ₃ 3~50 wt% TiO ₂ In the composition range of 0 to 15% by weight, 40 to 60% by weight of glass composition powder with a total amount of 95% by weight or more, and alumina, zirconia, magnesia, beryllia, mullite, cordierite, spinel, forsterite, anorthite, sergian. , A raw material mixture with 60 to 40% by weight of at least one inorganic filler powder selected from the group consisting of silica and aluminum nitride. That is, SiO ₂ , Al ₂ O ₃ , CaO, Mg
The composition range of O, B ₂ O ₃ , and TiO ₂ is the ratio in the glass composition powder, and the total amount of these components is 9 in the glass powder.
It is preferably 5% by weight or more.

Specific examples of the glass-ceramic composite system include SiO ₂ —B ₂ O ₃ system glass and PbO—SiO ₂
-Al ₂ O ₃ -B ₂ O ₃ based glass, CaO-SiO ₂ -
Etc. Al ₂ O ₃ -B ₂ O ₃ based glass, Al ₂ O _3, quartz (SiO _2), ZrO _2, is plus a ceramic component such as cordierite and the like.

A specific example of the crystallized glass is MgO--
Al ₂ O ₃ -SiO ₂ system and _{Li 2 O-Al 2 O 3} -Si
O ₂ type crystallized glass or the like is used. The crystallized glass is obtained by adding B ₂ O ₃ and a nucleating substance to MgO—Al ₂ O ₃ —SiO ₂ and firing it at 900 to 1000 ° C. to precipitate cordierite crystals to increase the strength or L.
_{i 2 O-Al 2 O 3} -SiO 2 in B ₂ O ₃ and nucleating agent was added, to precipitate a spodumene, it is also used similarly those aimed at strengthening.

As the photosensitive resin composition used for preparing the photocurable layer on the ceramic green sheet substrate of the present invention, a conventionally known photocurable resin composition can be applied. The photosensitive layer composed of these photocurable resin compositions is a layer which is insolubilized by irradiation with active rays. Examples of the photocurable resin composition are (1) a mixture of a functional monomer or oligomer having one or more unsaturated groups in one molecule with a suitable polymer binder. (2) A mixture of a photosensitive compound such as an aromatic diazo compound, an aromatic azide compound or an organic halogen compound with a suitable polymer binder. (3) A photosensitive polymer obtained by pendant to an existing polymer with a photosensitive group, or a modified product thereof. (4) A so-called diazo resin such as a condensation product of a diazo amine and formaldehyde. And so on.

A particularly preferred photocurable resin composition contains an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or molecular end, a photoreactive compound and a photopolymerization initiator. The acrylic copolymer is produced by adding an ethylenically unsaturated group to a side chain or a molecular end of an acrylic copolymer formed by copolymerizing an unsaturated carboxylic acid and an ethylenically unsaturated compound. can do. Preferred is one having a carboxyl group and an ethylenically unsaturated group in the side chain.

Specific examples of unsaturated carboxylic acids include:
Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. On the other hand, specific examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and n-butyl acrylate. Butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, isobutyl methacrylate, tert-butyl acrylate,
tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, styrene, p-
Examples include, but are not limited to, methylstyrene, o-methylstyrene, m-methylstyrene, and the like. A copolymer having good thermal decomposability can be obtained by including at least methyl methacrylate from the above ethylenically unsaturated compounds as the main polymerization component of these acrylic main chain polymers.

Examples of the ethylenically unsaturated group at the side chain or the terminal of the molecule include vinyl group, allyl group, acryl group and methacryl group. As a method of adding such a side chain to the acrylic copolymer, a method of making an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an acrylic acid chloride compound with a carboxyl group in the acrylic copolymer is available. is there.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether and isocrotonic acid glycidyl ether. . Examples of acrylic acid chloride compounds include acrylic acid chloride, methacrylic acid chloride, allyl chloride and the like. The addition amount of these ethylenically unsaturated compounds or acrylic acid chloride compounds is preferably 0.05 to 1 molar equivalent, more preferably 0.1 to 0.8, based on the carboxyl groups in the acrylic copolymer. It is a molar equivalent. If the addition amount of the ethylenically unsaturated compound is less than 0.05 equivalent, the photosensitive property becomes poor and it becomes difficult to form a pattern. When the addition amount is larger than 1 molar equivalent, the solubility of the developer in the unexposed area is lowered and the hardness of the coating film is lowered.

A non-photosensitive polymer may be contained in these photocurable resin compositions. As the non-photosensitive polymer, polyvinyl alcohol, polyvinyl butyral,
Examples thereof include a methacrylic acid ester copolymer, an acrylic acid ester copolymer, an acrylic acid ester-methacrylic acid ester copolymer, a methylstyrene polymer, and a butyl methacrylate resin.

The photoreactive compound is a carbon having photoreactivity.
A compound containing a carbon unsaturated bond, and specific examples thereof include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl. Acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, iso Octyl acrylate, lauryl acrylate, 2-
Methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allyl or cyclohexyl diacrylate, bisphenol A diacrylate,
1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxy or cyclohexyl diacrylate, neopentyl Glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate,
Examples thereof include triglycerol diacrylate, trimethylolpropane triacrylate, and those obtained by replacing the above acrylate with methacrylate, γ-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. In the present invention, these may be used alone or in combination of two or more.

The acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or at the terminal of the molecule is usually 0.1 to 10 times by weight of the photoreactive compound,
It is preferably used in an amount of 0.5 to 5 times. If the amount of the acrylic copolymer is too small, the viscosity of the slurry becomes small,
The uniformity of dispersion in the slurry may be reduced.
On the other hand, if the amount of the acrylic copolymer is too large, the solubility of the unexposed area in the developer becomes poor.

As a concrete example of the photopolymerization initiator,
Benzophenone, methyl o-benzoylbenzoate, 4,
4-bis (dimethylamine) benzophenone, 4,4-
Bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,
2-diethoxyacetophenone, 2,2-dimethoxy-
2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl dimethyl ketanol, benzyl-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone. , Methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6
-Bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2-
(O-Methoxycarbonyl) oxime, 1-phenyl-
Propanedion-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-Ethoxycarbonyl) oxime, 1-phenyl-
3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler-ketone, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone,
4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoin peroxide and eosin, methylene blue, and other photoreducible dyes. And a reducing agent such as ascorbic acid or triethanolamine. In the present invention, these may be used alone or in combination of two or more.

The photopolymerization initiator is contained in an amount of 5 to 30% by weight based on the sum of the acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or molecular end and the photoreactive compound.
Is added, and more preferably from 2 to 25% by weight. If the amount of the photopolymerization initiator is too small, the photosensitivity becomes poor and the photocuring becomes insufficient. Further, if the amount of the photopolymerization initiator is too large, photocuring proceeds only in the surface layer of the photosensitive resin composition, and a uniform photocured film cannot be obtained.

The composition of such a photosensitive resin composition is preferably selected within the following range. (A) Acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or molecular end; 4
0 to 90% by weight (b) photoreactive compound; 60 to 10% by weight (c) photopolymerization initiator; 5 to 30% by weight based on the sum of (a) and (b)

More preferably in the above, the compositions of the components (a) and (b) are 50 to 80% by weight and 50% by weight, respectively.
It is preferable to select it in the range of 20% by weight. Within this range, the photo-curing function is sufficiently exhibited during exposure to ultraviolet light, and chemical resistance and dissolution resistance during subsequent development are improved, which is preferable. Further, in the above, when the photoreactive compound of the component (b) exceeds 60% by weight, especially when the binder which is the photosensitive resin composition is evaporated in a nitrogen gas neutral atmosphere or a hydrogen gas atmosphere, debinding property is exhibited. Decrease, causing problems such as insulation resistance and strength deterioration. If it is less than 10% by weight, the sensitivity is lowered, and there is a problem that a large amount of exposure is required for photocuring.

If desired, stabilizers, sensitizers, plasticizers, defoamers, dispersants, organic or inorganic precipitation inhibitors, etc. may be added to the photosensitive resin composition.

The sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone,
2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone,
4,4, -bis (diethylamino) -benzophenone,
4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene)- Isonaphthothiazole, 1,3- ^ bis (4
-Dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone,
3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N
-Phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 3-phenyl-5-benzoylthio-tetrazoleazole, 1-phenyl-5-ethoxycarbonylthio- Examples include tetrazole. In the present invention, these may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. When the sensitizer is added to the photosensitive resin composition of the present invention, the addition amount is the sum of the acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or molecular end and the photoreactive compound. On the other hand, it is usually 0.1 to 30% by weight, more preferably 0.5 to 15% by weight. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed area may be too small.

Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol and glycerin.

Such a photosensitive resin composition is prepared by dissolving an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at a side chain or a molecular end and a photopolymerization initiator in a photoreactive compound. can do. When the acrylic copolymer having an ethylenically unsaturated group at the side chain or the molecular end and the photopolymerization initiator are not dissolved in the photoreactive compound or when it is desired to adjust the viscosity of the solution, the acrylic copolymer, the photopolymer A solvent such as an organic solvent or water in which the mixed solution of the polymerization initiator and the photoreactive compound can be dissolved may be added. The solvent used at this time may be any solvent that can dissolve the mixture of the acrylic copolymer, the photopolymerization initiator and the photoreactive compound. For example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, etc., and one or more of them are contained. An organic solvent mixture is used.

Further, if necessary, an organic solvent, a stabilizer, a sensitizer, a plasticizer, an antifoaming agent, a dispersant, an organic or inorganic suspending agent are added, and the mixture is stirred with a homogenizer or the like for example 12 Mix for ~ 48 hours to make a slurry. Further, if air bubbles remain in the slurry, it becomes a defect after the sheet is formed, so it is preferable to remove the air bubbles by using a vacuum degassing machine.

The slurry is applied onto the ceramic green sheet substrate by a known method such as dip coating, screen printing, squeegee, dispenser or roller. The viscosity of the slurry varies depending on the coating method, but it is 1,000 to 50,000 cps (centipoise).
It is preferable that it is, and if it is in this range, control of the coating film thickness becomes easy.

The photosensitive resin composition is used to
After forming the coating film on the green sheet substrate, the photomask is used to irradiate the entire surface with ultraviolet rays or selectively,
The coating film is photo-cured. A low-pressure mercury lamp, a high-pressure mercury lamp, a halogen lamp, and a germicidal lamp are suitable as a light source for the ultraviolet rays used for exposure. Of these, an ultra-high pressure mercury lamp is preferable. The photo-curing conditions vary depending on the thickness of the coating film,
The range of 50 to 5000 mJ / cm ² is preferable. Within this range, photo-curing is sufficiently achieved and chemical resistance and solubility are improved.

The film thickness of the layer obtained by photocuring the photosensitive resin composition is preferably 3 to 50 μm. More preferably 5
˜30 μm. If the film thickness is less than 3 μm, the irregularities of the ceramic green sheet are usually several μm or more, so that they cannot be completely applied to the gaps of the ceramic powder.
As a result, the photo-cured layer becomes less dense, and the solvent in the photosensitive paste reacts with the binder in the green sheet, resulting in poor development and pattern formation. On the other hand, when the film thickness exceeds 50 μm, it may take time to burn the green sheet to remove (remove the binder) the photosensitive resin composition, or carbon may remain after baking in an inert atmosphere. It may cause insulation failure. Further, in the case of a ceramic multilayer substrate, if the binder is not completely removed from the photosensitive resin composition layer, the conductor embedded in the via hole may not be able to be conducted, or the adhesion between the conductor film and the ceramic substrate may be poor. Occurs.

By providing the surface layer of the layer obtained by effectively curing the photosensitive resin composition with ultraviolet rays in this way, the chemical resistance and dissolution resistance of the green sheet are greatly improved, and the photosensitivity of the photosensitive conductive paste or the like is improved. It becomes possible to avoid the reaction between the organic solvent contained in the paste and the polymer binder in the green sheet. As a result, it becomes possible to form a fine pattern by removing the uncured portion of the unexposed portion using the developing solution.

In this way, a pattern is formed by a photolithography method using a photosensitive paste on the ceramic green sheet in which a layer obtained by photo-curing a photosensitive resin composition is provided on the ceramic green sheet substrate. As the photosensitive paste, a photosensitive conductive paste, a photosensitive resistor paste, a photosensitive dielectric paste, a photosensitive insulating paste or the like is used. Each contains a conductive powder, a resistor powder, a dielectric powder, an insulator powder, and a photosensitive resin composition.

As the conductor powder, Cu, Au, Ag,
Examples thereof include metals such as Pd, Pt, W, Mn, Ni and Mo or alloys containing these.

As the Cu-based conductor powder, for example, Cu
(97-70) -Ag (3-30), Cu (95-6
0) -Ni (5-40), Cu (90-70) -Ag
(5-20) -Cr (3-15) (above () is weight%
Represents The same applies hereinafter) and mixed binary or ternary mixed metal powders are used. Among these, Cu-Ag powder is preferable, and among them, a powder in which the surface of Cu is coated with 3 to 30% by weight of Ag is particularly preferable because it can suppress the oxidation of Cu.

As the Au, Ag, Pd, Pt-based conductor powder, for example, Ag (30-97) -Pd (70-3),
Ag (40-70) -Pd (60-10) -Pt (5-
20), Ag (30-80) -Pd (60-10) -C
r (5-15), Pt (20-40) -Au (60-4
0) -Pd (20), Au (75-80) -Pt (25
-20), Au (60-80) -Pd (40-20),
Ag (40-95) -Pt (60-5), Pt (60-
90) -Rh (40-10) and other binary or ternary mixed noble metal powders are preferably used. Among the above, those to which Cr or Rh is added are particularly preferable in that the high temperature characteristics can be improved.

As the W, Mo and Mn type conductive powder,
W, W (92-98) -TiB ₂ (8-2), W (92
-98) -ZrB ₂ (2-8), W- (92-98)-
TiB ₂ (1-7) -ZrB ₂ (1-7), W (95-
60) -TiN (5-60), W (90-60) -Ti
N (5-35) -TiO ₂ (2-10), W (90-6
0) -TiN (5-35) -TiO ₂ (2-10) -N
i (1-10), W (99.7-97) -AlN (0.
3-3), W (10-90) -Mo (90-10), W
(92-98) -Al ₂ Y ₂ O ₃ (8-2), Mo, M
o (92-98) -TiB ₂ (8-2), Mo (92-
98) -ZrB ₂ (8-2), Mo (92-8) -Ti
B ₂ (1-7) -ZrB ₂ (1-7), Mo-TiN,
Mo (90-60) -TiN (5-35) -TiO
₂ (2-10), Mo (90-60) -TiN (5-3
_{5) -TiO 2 (2-10) -Ni} (1-10), Mo
(99.7-97) -AlN (0.3-3), Mn (5
0-90) -Mo (10-50), Mo (60-90)
_{-Mn (40-10) -SiO 2 (0-20} ), W (3
A binary or ternary mixed metal powder such as 0-90) -Mo (30-70) -Mn (3-30) is used. Among the above, TiB ₂ , ZrB ₂ , TiN, AlN,
The one to which Ni or TiO ₂ is added is particularly preferable because it has the effect of improving the adhesive strength between the conductor film and the alumina substrate and reducing the resistance of the conductor film.

As the resistor powder, RuO ₂ and RuO _{2 are used.}
System, glass powder containing Al powder and B ₂ O ₃ , A
1 powder, glass powder containing transition metal powder and B ₂ O ₃ , In ₂ O ₃ system-glass powder, RuO ₂ -glass powder, LaB ₆ -glass powder, SnO ₂ additive-glass powder, silicide-glass powder, NiO and Li ₂ O ₃ -B ₂ O
Examples thereof include glass powders composed of _3- SiO ₂ -RO (R is a kind selected from Mg, Ca, Sr and Ba). , RuO ₂ are amorphous and crystalline, or CdBiRu ₂ O called a pyrochlore compound.
₇ , BiRu ₂ O ₇ , BaRuO ₅ , LaRuO ₃ , S
It may be rRuO ₃ , CaRuO ₃ , Ba ₂ RuO ₄ , or the like. The RuO _{2 system,} RuO 2 -SiO ₂ can be used.

The glass powder containing Al powder and B ₂ O ₃ includes 4 to 15% by weight of Al and 96 to 85% by weight of glass powder containing B ₂ O ₃ . B ₂
The glass powder containing O _3, B ₂ O ₃ -BaO
_{-SiO 2 -TaiO 5 -Al 2 O 3} -CaO-MgO
System, etc. MoSi ₂ , AlSi ₂ ,
A metal silicide such as WSi ₂ or TiSi ₂ may be included.

As the Al powder, the transition metal powder and the glass powder containing B ₂ O ₃ , the above Al powder and B are used.
_In addition to the glass powder containing ₂ O ₃ , Nb, V, W,
It contains a transition metal powder such as Mo, Zr, Ti and Ni.

In ₂ O ₃ system-glass powder is 30-80
An example thereof is one composed of a wt% In ₂ O ₃ system and 70 to 20 wt% of glass powder. As an In ₂ O ₃ system,
ITO (In ₂ O ₃ doped with Sn), In ₂
Examples thereof include SnO ₃ + SnO ₂ doped with O ₃ and Sb. Further, as the glass powder, SiO ₂ --Al ₂
For example, O ₃ —MgO—ZnO—B ₂ O ₃ —BaO system. Of these, the SiO ₂ —B ₂ O ₃ system is preferable because it can be sintered at a low temperature.

RuO ₂ -Glass powder, LaO ₆ -Glass powder, SnO ₂ -added product-Glass powder or system hydride-
The total amount of glass powder used for the glass powder is 90 to 3
The composition is 0% by weight, Al ₂ O _{3 is} 10 to 30% by weight,
B ₂ O ₃ 6 to 30 wt%, SiO ₂ 10 to 45 wt%,
CaO5~40 wt%, a ZnO15~50 wt%, RuO ₂ of the balance 10 to 70 wt%, LaB _6, S
It is a product added with nO ₂ or a silicide.

Examples of the dielectric powder include a lead-based powder and a barium titanate-based powder. Most of the dielectric powders, except for TiO ₂ , are of the ABO ₃ type, which is called a perovkite structure. It has the feature that it can always be controlled to be constant with the stoichiometric ratio.

The lead-based powder includes lead titanate PbTiO ₃ , lead zincate PbZnO ₃ , and lead ferrate PbFe.
O ₃ , lead magnesium oxide PbMgO ₃ , lead niobate Pb
ZbO ₃ , lead nickelate PbNiO ₃ , lead zirconate P
At least one dielectric compound selected from the group consisting of bZrO ₃ , a composite perovskite-based dielectric, and a titanium oxide TiO ₂ group may be mentioned, and a typical dielectric powder is Pb (Fe _X W _(1-X) ). O ₃ -Pb (Fe _Y N
_{b (1-Y)) O} 3, PbTiO 3 -Pb (Mg X Nb (1-X
_{)) O 3, Pb (Zn} X Nb (1-X)) O 3 -BaTiO
_{3, Pb (Zn X Nb (} 1 -X)) O 3 -Pb (Fe Y W
_{(1-Y)) O 3} -Pb (Fe Z Nb (1-Z)) O 3, Pb
_{(Zn X Nb (1-X} )) O 3 -PbTiO 3 -BaTiO
_{3, Pb (Mg X W (} 1 -X)) O 3 -PbTiO 3 -Pb
_{ZrO 3, Pb (Mg X Nb} (1-X)) O 3 -PbTiO
_{3 -Pb (Mg Y W (1} -Y)) O 3, Pb (Mg X W
_{(1-X)) O 3} -Pb (Zr Y TiO (1-Y)) O 3 + Zn
_{O, Pb (Mg X Nb (} 1-X)) O 3 -PbTiO 3 -P
_{bO, Pb (Fe X Nb (} 1-X)) O 3 -Pb (Mg Y N
_{b (1-Y)) O} 3, (1-Z) PbTiO 3 -Z (La 2
O ₃ ), such as binary and ternary compound perovskite compounds, (Pb _X Ba _(1-X) ) ZrO ₃ , Sr _X Pb
_(1-X) TiO ₃ , PLZT {(Pb _(1-X) La _X ) (Z
r _Y Ti _Z ) _{(1-X / 4)} O ₃ } and the like.

For the powder based on barium titanate, (Ba _X Sr _(1-X) ) (Sn _Y Ti _(1-Y) ) O ₃ ,
_{Ba (Ti X Sn (1-} X)) O 3, Ba X Sr (1-X) Ti
_{O 3, BaTiO 3 -CaZrO 3,} BaTiO 3 -B
i ₄ Ti ₃ O ₁₂ , (Ba _X Ca _(1-X) ) (Zr _Y TiO
Binary or ternary compounds such as _(1-Y) ) O ₃ may be mentioned.

As the insulating powder, the same insulating powder as the ceramic powder used for the ceramic green sheet substrate is preferably used.

When a pattern is formed by the photolithography method using the above-mentioned photosensitive dielectric paste and photosensitive insulator paste, an ultraviolet (UV) light absorber is added to the paste composition in order to cure it effectively with ultraviolet rays. It is preferable to add. By adding a light absorber having a high ultraviolet absorption effect, a pattern having a high resolution and a via hole can be formed.

That is, with only the dielectric powder or the insulating powder, the ultraviolet rays are scattered by these powders and photo-cured to an excessive portion, and even if it is developed, almost no via hole or pattern can be formed, or a good one is obtained. I can't. As a result of diligent investigations by the present inventors regarding this cause, scattered ultraviolet light is absorbed or weakened and wraps around to a light-shielded portion by an exposure mask, and the light reaches the lower part of the dielectric film or the insulating film. It turned out that it could not be cured. Therefore, by adding the ultraviolet light absorber, it is possible to prevent the scattered light from wrapping around, prevent the photosensitive resin in the mask portion from hardening, and form a pattern corresponding to the exposure mask. In addition, light can be transmitted to the lower part of the dielectric film or the insulating film without being absorbed, and the function of photocuring can be sufficiently satisfied, and a highly accurate via hole can be formed.

As an ultraviolet absorber, 350 to 450 nm
Organic dyes having a high UV absorbance in the wavelength range of are preferably used. As the organic dye, various dyes having high absorbance can be used. As the organic dye, an azo dye, an aminoketone dye, a xanthene dye, a quinoline dye, an aminoketone dye, an anthraquinone dye, or the like can be used. Among these, azo dyes are particularly preferable. Even when added as a light absorber, the organic dye is preferable because it does not remain in the substrate after baking because it evaporates at the time of baking and thus the insulation resistance is not reduced by the light absorbing agent.

Typical examples of azo dyes include:
Sudan Blue (C ₂₂ H ₁₈ N ₂ O
₂ = 342.4), Sudan R (C ₁₇ H ₁₄ N ₂ O ₂ = 27
8.31), Sudan _{II (C 18 H 14 N 2} O = 276.3
4), Sudan III (C ₂₂ H ₁₆ N ₄ O = 352.4), Sudan IV (C ₂₄ H ₂₀ N ₄ O = 380.45), Oil Orange SS (Oil Orange SS, CH ₃ C ₆ H)
₄ N: NC ₁₀ H ₆ OH = 262.31) Oil Violet (C ₂₄ H ₂₁ N ₅ = 379.
46), Oil Yellow OB (Oil Yellow)
_{OB, CH 3 C 4 H 4} N: NC 10 H 4 NH 2 = 261.
33) and the like, but a dye capable of absorbing at 250 to 520 nm can be used.

The amount of organic dye added is L (line width) / S
(Width interval) = 30 μm / 30 μm A fine pattern can be formed, and the circularity of the via hole is high, and the difference in hole diameter between the upper and lower portions after forming the via hole is small. The amount is preferably 0.05 to 2% by weight with respect to the dielectric powder or the insulating powder. If it is less than 0.05% by weight, the effect of adding an ultraviolet absorber is reduced, and if it exceeds 2% by weight, when the amount of the absorber is too large and it is irradiated with ultraviolet rays, it is absorbed by the powder until it reaches the lower part, which is sufficient. It is not preferable because the pattern resolution cannot be obtained or the formation of via holes becomes defective.

The method of adding the ultraviolet light absorber composed of an organic dye is preferably as follows. That is, a solution in which an organic dye is previously dissolved in an organic solvent is prepared. Next, the dielectric powder or the insulating powder is mixed in the organic solvent and dried with stirring. By this method, a so-called capsule-shaped dielectric powder or insulating powder in which the surface of each powder is uniformly coated with an organic dye film can be produced.

In the present invention, there is a preferred range of integrated value of absorbance (wavelength measurement range; 350 to 450 nm).
The integrated value of absorbance is measured in a powder state, and is measured for an organic dye or a powder whose surface is coated with an organic dye.

In the present invention, the absorbance is defined as follows. That is, using a commercially available spectrophotometer, light is applied to a measurement sample in an integrating sphere, and the light reflected there is collected and detected. Further, except for the light detected by the integrating sphere, all the light is regarded as absorbed light and is calculated from the following formula.

The light intensity of the control light was set to Ir (Ir is the BaSO ₃ of the same material as the material coated on the inner surface of the integrating sphere, and the light intensity by reflection was measured before measuring the absorbance of the sample. Data) When the light intensity of light incident on the sample is I and the light intensity of the absorbed light after hitting the sample is Io, the light intensity of the reflected light from the sample is represented by (I-Io), and the absorbance is as follows. (1) is defined. In the above, the unit of light intensity is W / cm ² . Absorbance _{= -log ((I-I 0} ) / Ir) (1)

The absorbance is measured as follows.

1. The powder to which the light absorber is added is molded with a press into a size of 10 to 30 mm in diameter and 3 to 5 mm in thickness.

2. Next, a spectrophotometer is used to attach a powder molding to the attachment port of the reflecting sample of the integrating sphere, and the absorbance due to the reflected light is measured in the wavelength range of 200 to 650 nm. A graph as shown in FIG. 1 is obtained. The vertical axis represents the absorbance of the formula (1), and the horizontal axis represents the measurement wavelength.

3. Next, in FIG. 1, the wavelength range of 350 to 450 nm is divided into 10 intervals of 10 nm, and the area of each interval is obtained. The area is calculated as follows.

For example, the absorbance at 350 nm is 0.75, the absorbance at 360 nm is 0.80, the absorbance at 370 nm is 0.85, the absorbance at 440 nm is 0.60, the absorbance at 450 nm is As 0.55, 350-
The area of 360 nm is regarded as a trapezoid and calculated as follows. , Area A = (0.75 + 0.80) × 10/2 = 7.75 Similarly, Area B is Area B = (0.80 + 0.85) × 10/2 = 8.25. J = (0.60 + 0.55) × 10/2 = 5.75. The integrated value S of the area of 10 sections is obtained as follows. S = A + B + C + ... + J The area S was defined as the integrated value of the absorbance at 350 to 450 nm. In the present invention, the preferable range of the above integrated value of the absorbance is 20 to 100, and the more preferable range is 30 to 70. If the integrated value of the absorbance is less than 20, the light is scattered by the dielectric powder or the insulating powder during the exposure to ultraviolet light to cure the unexposed portion, and thus the pattern having a high resolution and the via having the roundness are formed. Holes cannot be formed. If the absorbance exceeds 100, the light is absorbed by the powder before reaching the film below the film formed of the dielectric or insulating paste, and the light cannot be cured. As a result, peeling occurs during development, making it difficult to form patterns and via holes.

As the photosensitive resin composition in the photosensitive paste, known ones can be used, but the particularly preferable one is
It contains the above-mentioned acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at the side chain or molecular end, a photoreactive compound and a photopolymerization initiator. When the photosensitive resin composition having this composition is used, a fine pattern of L (line width) / S (width interval) = 20 μm / 20 μm can be formed by photolithography.

In order to form a pattern or via hole on the ceramic green sheet of the present invention using the photosensitive paste, first, the green sheet is applied by the usual screen printing method or spin coating method. Next, a photomask having a circuit pattern is used to irradiate ultraviolet rays to expose the photosensitive paste, and the photosensitive paste is photocured. Then, the unexposed portion is removed with a developing solution to obtain a fine pattern or via hole as a mask.

As a light source of ultraviolet rays used for exposure,
For example, a low pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, a germicidal lamp, etc. can be used. Among these, the ultra-high pressure mercury lamp is preferable. Although the exposure conditions vary depending on the thickness of the coating film of the photosensitive resin, it is preferable to perform the exposure for 1 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 5 to 100 mW / cm ² .

After exposure, development is performed using a developing solution. In this case, dipping or spraying is used. As the developer, an organic solvent in which the mixture of the acrylic copolymer having an ethylenically unsaturated group at the side chain or molecular end, the photoreactive compound and the photopolymerization initiator can be dissolved can be used. Further, water may be added to the organic solvent within the range in which the dissolving power is not lost. When the side chain of the acrylic copolymer has a carboxyl group, it can be developed with an aqueous alkali solution. As the alkaline aqueous solution, a metallic alkaline aqueous solution such as sodium hydroxide or calcium hydroxide aqueous solution can be used, but it is preferable to use the organic alkaline aqueous solution because the alkaline component can be easily removed during firing. Specific examples of the organic alkali include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.01
-5% by weight, more preferably 0.1-1% by weight.
If the alkali concentration is too low, the unexposed area is not removed, and if the alkali concentration is too high, it causes peeling of the exposed area.
It is also not good because it may cause corrosion.

When a conductor is embedded in the via hole of the green sheet, a green sheet in which a via hole is formed with a carbide drill is used. The embedding method is copper,
Filling with silver, silver-palladium, tungsten, molybdenum, or gold conductor paste to form a conductor for interlayer connection for wiring in the via hole. The embedding of the conductive paste in the via holes of the green sheet is repeated for each number of layers.

Thus, a predetermined conductor, resistor, dielectric or insulator pattern is printed on the surface of the green sheet. Also, a guide hole is drilled in the same manner as forming a via hole. Next, the required number of sheets are stacked using the guide holes, and at a temperature of 90 to 130 ° C, 50 to 200k.
Bonding is performed at a pressure of g / cm ² to produce a sheet made of a multilayer substrate.

Next, the above-mentioned sheet is fired in a firing furnace to prepare a ceramic multilayer substrate having conductors and patterns of conductors and the like formed in via holes. The firing atmosphere and temperature differ depending on the type of ceramic substrate and conductor. In the case of a low-temperature firing multilayer substrate made of ceramics or glass / ceramics, the insulating layer is fired at a temperature of 850 to 1000 ° C. for several hours. Alumina, aluminum nitride, and mullite substrates are fired at a temperature of 1450 to 1600 ° C. for several hours. Cu, W, Mo, W-Mo, Mn
-For a conductor such as Mo, it is fired in a neutral atmosphere such as nitrogen or a reducing atmosphere containing hydrogen. Acrylic copolymer having ethylenically unsaturated group at side chain or molecular end contained in photosensitive paste and ceramics green sheet during firing, photoreactive polymerizable compound, non-photosensitive resin binder, organic dye, plasticizer Alternatively, an atmosphere that allows the oxidation and evaporation of organic substances such as a solvent may be used. As such, when the conductor is Cu, W, Mo, W-Mo, or Mn-Mo, it contains 3 to 100 ppm of oxygen, and the rest can be fired in an atmosphere controlled by a neutral gas such as nitrogen or argon or steam. The firing temperature is such that the organic binder is completely oxidized and evaporated at 300 to 600 ° C. for 5 minutes to several hours, and then at 850 to 1600 ° C. for several hours to prepare a ceramic multilayer substrate.

The amount of carbon remaining in the multilayer substrate after firing is 2
It should be 50 ppm or less. Otherwise, problems such as a decrease in porosity of the multilayer substrate, a decrease in strength, an increase in dielectric constant, an increase in dielectric loss, an increase in leak current or a decrease in insulation resistance occur. The residual carbon amount is 100 ppm or less,
It is more preferably 50 ppm or less.

[0073]

The present invention will be described below in detail with reference to examples. In the following description, all concentrations are expressed in weight% unless otherwise specified.

Examples 1 to 9 <Preparation of ceramics green sheet substrate> Alumina sheet; Aluminum oxide (Al ₂ O ₃ ) 9
2%, silicic acid anhydride (SiO ₂ ) 5%, magnesium oxide and calcium oxide 1.5% each were mixed in a wet process using an attritor to obtain an average particle diameter of 1.8 μm.
It was mixed and pulverized until it reached m. To 100 parts of this mixed powder, 13 parts of an acrylic resin as a binder, a solvent, a plasticizer, and a dispersant, 22 parts of a mixed solvent of toluene and isopropyl alcohol (IPA), 3.1 parts of dibutyl phthalate (DBP), and a cationic dispersion. After 1.2 parts of the agent was added and thoroughly mixed with stirring, the mixture was degassed in a vacuum to obtain a viscosity of 1500c.
Using the slurry adjusted to p, a ceramics green sheet substrate having a thickness of 200 μm was produced by the doctor blade method.

Aluminum nitride sheet; specific surface area 3 m ² / g
Add 3% of yttrium oxide, 1% of aluminum oxide and 1% of calcium carbonate (CaCO ₃ ) as a sintering aid to the aluminum nitride (AlN) powder, and the average particle size becomes 2.0 μm with an attritor. Were mixed and crushed. To 100 parts of this mixed powder, 10 parts of acrylic resin, 26 parts of 1,1,1-trichloroethane, 19 parts of n-butanol, 15 parts of tetrachloroethylene, and 5 parts of dibutyl phthalate were further added as a binder, a solvent and a plasticizer component. In addition, after sufficiently mixing, vacuum degassing was performed, and the slurry adjusted to a viscosity of 2000 cp was used to prepare a ceramics green sheet substrate having a thickness of 200 μm by the doctor blade method.

Glass-ceramics green sheet: The composition of the glass-ceramics powder is 96% pure alumina powder 50% and borosilicate glass 50%. The glass composition is SiO ₂ ; 70%, BaO; 3%, Al ₂ O
₃ ; 7%, B ₂ O ₃ ; 18%, Na ₂ O; 2%.
As the glass powder, a powder having an average particle diameter of 2.2 μm and a specific surface area of 1.5 m ² / g, which had been finely powdered by an attritor, was used. Next, 100 parts of this powder was further mixed with polyvinyl butyral 12 as a binder, a solvent, a plasticizer, and a dispersant.
Parts, 22 parts of a mixed solvent of toluene, methyl ethyl ketone and isopropyl alcohol, 3.1 parts of a plasticizer and 1.2 parts of a cationic dispersant, and thoroughly mixed, and then vacuum degassed, and a slurry having a viscosity adjusted to 1500 cp was doctored. A ceramic green sheet substrate having a thickness of 200 μm was produced by the blade method.

<Preparation of Photosensitive Resin Composition Slurry> A. Polymer binder 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (S
Polymer in which 0.4 equivalent (corresponding to 40%) of glycidyl methacrylate (GMA) is added to the carboxyl group (MAA) of the copolymer of t).

B. Monomer (photoreactive compound) Trimethylol / Propane / Triacrylate

C. Solvent γ-butyrolactone

D. Photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2
20% each of morpholinopropanone-1 and 2,4-diethylthioxanthone were added to the total amount of polymer and monomer.

E. Preparation of organic vehicle Mix solvent and polymer binder and stir 1
All polymer binders were homogeneously dissolved by heating to 20 ° C. Then, the solution was cooled to room temperature, and a photopolymerization initiator was added and dissolved. Then, this solution was filtered using a 400-mesh filter to prepare an organic vehicle.

F. Preparation of Slurry A slurry was prepared by adding a photoreactive compound and a photopolymerization initiator to the above organic vehicle so as to have a predetermined composition,
It was prepared by wet mixing for 12 hours with an attritor. Further, the mixture was defoamed with a vacuum stirrer for 16 hours to prepare a slurry.
The viscosity of the prepared slurry was 3500 cps when measured with a Brookfield viscometer (model; RVDV-II +) at a rotation speed of 50 rpm. The slurry composition is shown in Table 1.

<Formation of Photosensitive Resin Composition Layer> A. Coating film formation A coating film was formed on the ceramic green sheet substrate of alumina, aluminum nitride, and glass-ceramics prepared above by using the slurry of the photosensitive resin composition. Spin coating on each green sheet (MIKAS
Spin coater made by A, 1H-DX) rotation speed 1500-4
It was carried out under the condition of 000 rpm. The thickness of the coating film is shown in Table 1.

B. Exposure Exposure amount from the top of the coating film prepared above is 1500 mJ
The film was exposed to ultraviolet light at a dose of 1 cm ² / cm ² and cured.

<Formation of Conductor Pattern> A fine pattern was formed with a photosensitive conductive paste on a green sheet of alumina, aluminum nitride and glass-ceramic having a layer obtained by photo-curing the film of the above-mentioned photosensitive resin composition. The production of the photosensitive conductive paste and the pattern formation by this paste were performed by the following method. Among the above green sheets, a photosensitive tungsten paste was used for the alumina and aluminum nitride green sheets, and a photosensitive copper paste was used for the glass-ceramics green sheet.

A. Preparation of Photosensitive Conductive Paste 1-1 Conductive Powder Tungsten Powder; Polyhedral Average Particle Diameter 3.5 μm
m, a powder having a specific surface area of 0.15 m ² / g. Copper powder; a polyhedral powder having an average particle diameter of 4.1 μm and a specific surface area of 0.32 m ² / g. 89% of each of the above conductive powders was added as a paste composition.

1-2 Polymer 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (S
Polymer in which 0.4 equivalent (corresponding to 40%) of glycidyl methacrylate (GMA) is added to the carboxyl group (MAA) of the copolymer of t). 6% of polymer was added.

1-3 Monomer 3% of trimethylol propane triacrylate was added.

1-4 Glass Frit Calcium oxide (5.0), zinc oxide (28.1), boron oxide (25.0), silicon dioxide (22.8), sodium oxide (8.8), zirconium oxide (4.
5) and 0.7% of glass frit having a composition containing alumina (5.8) was added.

1-5 Copper Oxide Powder 0.3% of CuO powder having a particle diameter of 0.6 μm was added.

1-6 Solvent γ-butyrolactone

1-7 Photopolymerization Initiator 2-Methyl-1- [4- (methylthio) phenyl] -2
1.8% of morpholinopropanone-1 and 2,4-diethylthioxanthone were added (20% each relative to the sum of polymer and monomer).

1-8 Plasticizer 0.6% dibutyl phthalate (DBP) was added (10% of polymer). 1-9 Sensitizer 2% of 2,4-diethylthioxanthone was added (the same ratio as the photopolymerization initiator).

1-10 Photopolymerization Accelerator p-Dimethylaminobenzoic Acid Ethyl Ester (EPA)
2% was added (the same ratio as the photopolymerization initiator).

1-11 Preparation of Organic Vehicle A solvent and a polymer binder are mixed and stirred for 8 hours.
All polymer binders were homogeneously dissolved by heating to 0 ° C. Then, the solution was cooled to room temperature, and a photopolymerization initiator was added and dissolved. The solution was then passed through a 400 mesh filter and filtered.

1-12 Stabilization Treatment After dissolving 10% of benzotriazole in copper powder of the above conductive powder with methyl acetate, it was immersed in a solution for 12 hours so that the copper powder could be sufficiently immersed. After the immersion, it was dried in a draft at 20 to 25 ° C. to evaporate the solvent to prepare a triazole-treated copper powder.

1-13 Preparation of Conductive Paste A conductive powder, a monomer, a copper oxide powder, a plasticizer, a sensitizer, a photopolymerization accelerator, and a glass frit are added to the above organic vehicle so as to have a predetermined composition, and 3 This roller was mixed and dispersed to prepare a paste.

B. Printing The above paste was solidly printed in a size of 70 mm square on a 100 mm square green sheet on which a photo-cured layer of the photosensitive resin composition had been formed, using a 250-mesh polyester screen, and then 40 ° C. at 80 ° C. Hold for minutes to dry. The thickness of the coating film after drying was about 20 μm.
Printing was performed in a room protected from ultraviolet rays.

C. Exposure and development The coating film prepared above is 5 μm in the range of 10 to 60 μm.
Using a chrome mask on which fine patterns of intervals were formed, ultraviolet exposure was performed from the upper surface with an ultrahigh pressure mercury lamp with an output of 500 mJ / cm ² . Next, it was immersed in a 0.5% by weight aqueous solution of monoethanolamine maintained at 25 ° C. for development, and then the portion which had not been photocured was washed with water using a spray.

D. Oxygen 50ppm of the coating film printed on the firing green sheet
The binder was evaporated by holding it in an atmosphere (the balance: nitrogen) containing it for 1 hour at 500 ° C., and then sintered to obtain a ceramic substrate. Glass-ceramic sheet is 900 ℃
It was held for 1 hour. Alumina and aluminum nitride green sheets are fired in H ₂ (hydrogen) gas and N ₂ (nitrogen) gas atmosphere at 500 ° C. for 2 hours, and after binder removal, held at temperatures of 1500 and 1600 ° C. for 1 hour, respectively. And sintered to obtain a ceramic substrate.

E. Evaluation The resolution, film thickness and specific resistance of the conductor film after firing were measured and evaluated. The resolution is 20-40 by observing the conductor film with a microscope.
The finest line spacing was determined as the line spacing at which the μm lines were straight and did not overlap and reproducibility was obtained. The film thickness was measured with a micrometer. The specific resistance was measured by the 4-terminal method. The rate of occurrence of wire breakage of the conductor film was evaluated by the presence or absence of conduction by resistance measurement. Table 1 shows the results.

When a ceramics green sheet provided with a layer obtained by photocuring a photosensitive resin composition on a ceramics green sheet substrate as described above is used, a line width / width is obtained by a photolithography method using a photosensitive conductive paste. A circuit pattern having a fine pattern with a distance of 30 μm / 30 μm or less and low resistance can be obtained. Further, a conductor film pattern that does not cause disconnection even after firing can be obtained. As a result, it is possible to further reduce the size and increase the density of the ceramic multilayer substrate.

Comparative Example 1 An attempt was made to form a conductor pattern on the alumina green sheet substrate produced in Example 1 by using the photosensitive copper paste of Example. However, if the exposure condition is 100,500,1
3,000, 3000 mJ / cm ² and developing conditions were also examined by changing the concentration of the monoethanolamine aqueous solution to 0.2, 0.5 and 1% by weight. No pattern could be formed.

Comparative Example 2 A non-photosensitive resin composition layer was formed on the alumina green sheet substrate prepared in Example 1. That is, as the resin, polyvinyl butyral, polyacryl and polyacetal are contained in an amount of 15% by weight, 20% by weight, 2%
A slurry obtained by dissolving 5 wt% γ-butyrolactone and making it uniform was applied by a spin coater and dried at 80 ° C. for 20 minutes to form a coating film layer made of a resin composition. The thickness of the coating film layer was 20 μm. Next, an attempt was made to form a conductor pattern using the photosensitive tungsten paste prepared in the example, but in any of the cases, it is difficult to remove the unexposed portion during development because the solvent of the photosensitive tungsten paste reacts with the resin. However, a fine pattern could not be formed.

Examples 10 to 11 <Formation of Insulating Layer Via Holes> Fine via holes were formed with a photosensitive insulating paste on a glass-ceramic green sheet having a layer obtained by photo-curing the film of the above-mentioned photosensitive resin composition. Preparation of the photosensitive insulating paste and formation of via holes by this paste were performed by the following method.

A. Insulating powder Cordierite powder; spherical average particle size 2.1 μm,
A powder having a specific surface area of 1.97 m ² / g, a dielectric constant of 6.1 and a coefficient of thermal expansion of 2.9 × 10 ^-6 / ° C was used. Insulating powder; spherical average particle diameter 2.5 μm, specific surface area 1.5 m ² / g, dielectric constant 5.4, thermal expansion coefficient 3.7 × 1
A powder with 0 ^-6 / ° C was used.

89% of each of the above-mentioned insulating powders was added as a paste composition.

B. UV absorber Organic dye; Azo dye; Sudan, chemical formula: C _{2 4} H ₂ ON ₄ O, molecular weight: 380.45.

C. Polymer Binder 40% methacrylic acid (MAA), 30% methylmethacrylate (MMA) and 30% styrene (S
Polymer in which 0.4 equivalent (corresponding to 40%) of glycidyl methacrylate (GMA) is added to the carboxyl group (MAA) of the copolymer consisting of t). The acid value of the polymer was 100. 6% of polymer was added.

D. Monomer trimethylol propane triacrylate was added at 3%.

E. Solvent γ-butyrolactone F. A photopolymerization initiator α-aminoacetophenone was added in an amount of 1.8% (20% based on the total amount of the polymer and the monomer).

G. 0.6% of plasticizer dibutyl phthalate (DBP) was added (10% of polymer).

H. Sensitizer 2,4-diethylthioxanthone (1.8%) was added (the same ratio as the photopolymerization initiator).

I. Sensitization aid p-Dimethylaminobenzoic acid ethyl ester (EPA)
2% was added (the same ratio as the photopolymerization initiator).

<Production of Insulating Paste> A. Preparation of Organic Vehicle A solvent and a polymer binder were mixed so as to form a 50% solution, and heated to 120 ° C. with stirring to uniformly dissolve all polymer binders. Then, the solution was cooled to room temperature, and a photopolymerization initiator, a sensitizer and a sensitization aid were added and dissolved. The solution was then filtered through a 400 mesh filter.

B. Preparation of Powder with Added Light Absorber A predetermined amount of an organic dye was weighed, a dispersant was added to a solution dissolved in isopropyl alcohol (IPA), and the mixture was uniformly stirred with a homogenizer. Next, a predetermined amount of insulator powder was added to this solution, and the mixture was homogeneously dispersed and mixed, and then dried at a temperature of 150 to 200 ° C. using a rotary evaporator to evaporate IPA. Thus, a powder in which the surface of the insulating powder was uniformly coated with the organic dye film (so-called capsule treatment) was produced. The results of measurement of the integrated value of the absorbance of the powder are summarized in Table 2.

C. Insulating paste preparation To prepare the paste, add a photoreactive compound, a light absorber-added powder (insulating powder encapsulated with an organic dye), a thickener and a plasticizer to the above-mentioned organic vehicle so as to have a predetermined composition, It was prepared by mixing and dispersing with three rollers. The prepared composition is shown in Table 2.

D. Printing The above paste was solid-printed in a size of 70 mm square on a green sheet on which a photo-cured layer (layer thickness: 5 μm) of a photosensitive resin composition was formed using a 320-mesh stainless screen. And kept at 80 ° C for 40 minutes to dry. The thickness of the coating film after drying was about 50 μm. Printing was performed in a room protected from ultraviolet rays.

E. Exposure and Development The coating film prepared above was exposed to ultraviolet rays from an upper surface using an ultrahigh pressure mercury lamp with an output of 1000 mJ / cm ² using a chrome mask having 5000 fine via holes of 5000 to 100 μmφ. Next, monoethano kept at 25 ° C
It was immersed in a 0.5% by weight aqueous solution of luamine for development, and then the unexposed area was washed with water using a sprayer.

F. Evaluation The cross section of the via hole of the green sheet after development was observed with a microscope, and the via hole diameters of the upper and lower parts were observed. A cross section having a straight portion without a via barrel and a via hole having no difference in hole diameter were uniformly formed.

Example 12 <Resistor pattern formation> A fine pattern was formed with a photosensitive resistor paste on a glass-ceramic green sheet having a layer obtained by photo-curing the film of the above-mentioned photosensitive resin composition. The production of the photosensitive resistor paste and the pattern formation by this paste were carried out by the following method.

A. Resistor powder RuO ₂ powder; a powder having a spherical average particle diameter of 2.5 μm and a specific surface area of 1.8 m ² / g was used.

The paste composition of the resistor powder is 8
8% was added.

B. UV absorber Organic dye; Azo dye; Sudan, chemical formula: C _{2 4} H ₂ ON ₄ O, molecular weight: 380.45.

C. Polymer Binder 40% methacrylic acid (MAA), 30% methylmethacrylate (MMA) and 30% styrene (S
Polymer in which 0.4 equivalent (corresponding to 40%) of glycidyl methacrylate (GMA) is added to the carboxyl group (MAA) of the copolymer consisting of t). The acid value of the polymer was 100. 6% of polymer was added.

D. Monomer trimethylol propane triacrylate was added at 3%.

E. Solvent γ-butyrolactone F. A photopolymerization initiator α-aminoacetophenone was added in an amount of 1.8% (20% based on the total amount of the polymer and the monomer).

G. 0.6% of plasticizer dibutyl phthalate (DBP) was added (10% of polymer).

H. Sensitizer 2,4-diethylthioxanthone (1.8%) was added (the same ratio as the photopolymerization initiator).

I. Sensitization aid p-Dimethylaminobenzoic acid ethyl ester (EPA)
2% was added (the same ratio as the photopolymerization initiator).

<Production of Resistor Paste> A. Preparation of Organic Vehicle A solvent and a polymer binder were mixed so as to form a 50% solution, and heated to 120 ° C. with stirring to uniformly dissolve all polymer binders. Then, the solution was cooled to room temperature, and a photopolymerization initiator, a sensitizer and a sensitization aid were added and dissolved. The solution was then filtered through a 400 mesh filter.

B. Preparation of Powder with Added Light Absorber A predetermined amount of an organic dye was weighed, a dispersant was added to a solution dissolved in isopropyl alcohol (IPA), and the mixture was uniformly stirred with a homogenizer. Then, a predetermined amount of resistor powder was added to this solution, and the solution was uniformly dispersed and mixed, and then dried at a temperature of 150 to 200 ° C. using a rotary evaporator to evaporate IPA. Thus, a powder in which the surface of the resistor powder was uniformly coated with the organic dye film (so-called capsule treatment) was produced. The results of measurement of the integrated value of the absorbance of the powder are summarized in Table 2.

C. Resistor paste preparation A mixture of the above organic vehicle powder with a light absorber added (resistor powder encapsulated with an organic dye), monomer, plasticizer, sensitizer, sensitization aid and solvent should be in the specified composition. And was mixed and dispersed uniformly with three rollers to prepare one kind of paste. The composition of the paste is shown in Table 2.

D. Printing The above paste was solid-printed in a size of 70 mm square on a green sheet on which a photo-cured layer (layer thickness: 5 μm) of a photosensitive resin composition was formed using a 320-mesh stainless screen. And kept at 80 ° C for 40 minutes to dry. The thickness of the coating film after drying was about 30 μm. Printing was performed in a room protected from ultraviolet rays.

E. Exposure, development The coating film prepared above is 30 μm in the range of 30 to 50 μm.
Using a chrome mask on which a fine pattern with m intervals was formed, ultraviolet exposure was performed from the top surface with an ultrahigh pressure mercury lamp with an output of 500 mJ / cm ² . Next, it is immersed in a 0.5% by weight aqueous solution of monoethanolamine maintained at 25 ° C. for development,
After that, the unexposed portion was washed with water using a sprayer.

F. Evaluation When the pattern resolution of the green sheet after development was observed with a microscope, reproducibility was obtained without lines of 25 to 40 μm being straight lines and overlapping.

Example 13 <Formation of Dielectric Layer Via Holes> Fine via holes were formed with a photosensitive dielectric paste on a glass-ceramic green sheet having a layer obtained by photo-curing the film of the above-mentioned photosensitive resin composition. Preparation of the photosensitive dielectric paste and formation of via holes by this paste were performed by the following method.

A. Dielectric powder BaTiO ₃ powder; spherical powder having an average particle diameter of 3.0 μm and specific surface area of 1.2 m ² / g was used. 88% was added as the paste composition of the dielectric powder.

B. Organic dyes Benzophenone dyes; Ubinal D-50, chemical formula;
C ₁₃ H ₁₀ O _5, molecular weight: 246. C. Polymer 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (S
Polymer in which 0.4 equivalent (corresponding to 40%) of glycidyl methacrylate (GMA) is added to the carboxyl group (MAA) of the copolymer consisting of t). The acid value of the polymer was 100. 6% of polymer was added.

D. Monomer trimethylol propane triacrylate was added at 3%.

E. Solvent γ-butyrolactone F. A photopolymerization initiator α-aminoacetophenone was added in an amount of 1.8% (20% based on the total amount of the polymer and the monomer).

G. 0.6% of plasticizer dibutyl phthalate (DBP) was added (10% of polymer). H. Sensitizer 2,4-diethylthioxanthone (1.8%) was added (the same ratio as the photopolymerization initiator).

I. Sensitization aid p-Dimethylaminobenzoic acid ethyl ester (EPA)
2% was added (the same ratio as the photopolymerization initiator).

<Production of Dielectric Paste> A. Preparation of Organic Vehicle A solvent and a polymer binder were mixed so as to form a 50% solution, and heated to 120 ° C. with stirring to uniformly dissolve all polymer binders. Then, the solution was cooled to room temperature, and a photopolymerization initiator, a sensitizer and a sensitization aid were added and dissolved. The solution was then filtered through a 400 mesh filter.

B. Preparation of Powder with Added Light Absorber A predetermined amount of an organic dye was weighed, a dispersant was added to a solution dissolved in isopropyl alcohol (IPA), and the mixture was uniformly stirred with a homogenizer. Next, a predetermined amount of dielectric powder was added to this solution, and the mixture was uniformly dispersed and mixed, and then dried using a rotary evaporator at a temperature of 150 to 200 ° C. to evaporate IPA. Thus, a powder in which the surface of the dielectric powder was uniformly coated with the organic dye film (so-called capsule treatment) was produced. The results of measurement of the integrated value of the absorbance of the powder are summarized in Table 2.

C. Preparation of dielectric paste To prepare the paste, add a photoreactive compound, a powder with a light absorber added (dielectric powder encapsulated with an organic dye), a thickener and a plasticizer to the above organic vehicle so as to have a predetermined composition. It was prepared by mixing and dispersing with three rollers. The prepared composition is shown in Table 2.

D. Printing 70 mm on the green sheet on which the photo-cured layer (layer thickness: 10 μm) of the photosensitive resin composition has been formed by using the above-mentioned paste using a 320-mesh stainless screen.
Solid printing was performed on the size of the corner, and the product was kept at 80 ° C. for 40 minutes and dried. The thickness of the coating film after drying was about 50 μm. Printing was performed in a room protected from ultraviolet rays.

E. Exposure and development The coating film prepared above was exposed to ultraviolet rays from an upper surface of the coating film using a chromium mask having 5,000 fine via holes of 5000 μm square with an ultrahigh pressure mercury lamp having an output of 1000 mJ / cm ² . Next, it was immersed in a 0.5% by weight aqueous solution of monoethanolamine held at 25 ° C. for development, and then the unexposed portion was washed with water using a sprayer.

F. Evaluation The cross section of the via hole of the green sheet after development was observed with a microscope, and the via hole diameters of the upper and lower parts were observed. A cross section having a straight portion without a via barrel and a via hole having no difference in hole diameter were uniformly formed.

[0150]

[Table 1]

[Table 2]

[0151]

EFFECTS OF THE INVENTION Even when a pattern is formed on a conventional ceramics green sheet by using a photosensitive paste, the organic polymer, plasticizer, solvent or various additives contained in the green sheet before firing and the photosensitive paste are used. The organic solvent contained reacted with each other, and the exposed portion could hardly be removed during development, and pattern formation was difficult (Comparative Example 1). Even if a non-photosensitive resin composition layer is formed on a conventional ceramics green sheet and a pattern is formed using a photosensitive paste, the resin composition reacts with the organic solvent in the paste, making pattern formation difficult. Was (Comparative Example 2).

In the present invention, since a layer obtained by photocuring a photosensitive resin composition is formed on a ceramic green sheet, a good pattern can be formed on the sheet by using a photosensitive paste. This is because the ultraviolet curing of the photosensitive resin composition layer is sufficient, the chemical resistance and solvent resistance of the sheet are improved, the reaction with the organic solvent in the photosensitive paste is almost eliminated, and the unexposed portion is removed. Is completely based on.

Since the pattern can be formed on the ceramic green sheet by using the photosensitive paste as described above, fine conductors, resistors, dielectrics and insulator patterns of L / S = 20 μm / 20 μm and via holes of 50 μmφ are formed. It is possible to form a conductor pattern having a low resistance and an inner layer conductor of the ceramic multilayer substrate can be formed. As a result, it is possible to further reduce the size and increase the density of the ceramic multilayer substrate.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between measurement wavelength and absorbance.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03F 7/027 501 H05K 1/09 3/00 J 3/46 H 6921-4E S 6921-4E

Claims (16)

[Claims] 1. A ceramic green sheet comprising a ceramic green sheet substrate and a layer obtained by photocuring a photosensitive resin composition on a substrate. 2. A photosensitive resin composition comprising an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group at a side chain or a molecular end, a photoreactive compound and a photopolymerization initiator. The ceramic according to claim 1.
Green sheet. 3. The ceramic green sheet according to claim 1, wherein the film thickness of the layer obtained by photocuring the photosensitive resin composition is 3 to 50 μm. 4. A pattern is formed on the ceramic green sheet according to any one of claims 1 to 3, characterized in that a photosensitive paste is applied, dried, selectively exposed and developed on the ceramic green sheet. How to form. 5. The photosensitive paste according to claim 4, wherein the photosensitive paste is at least one selected from the group consisting of a photosensitive conductive paste, a photosensitive resistor paste, a photosensitive dielectric paste and a photosensitive insulating paste. A method of forming a pattern on a ceramic green sheet. 6. The method for forming a pattern on a ceramic green sheet according to claim 5, wherein the photosensitive conductive paste contains a conductor powder and a photosensitive resin composition. 7. The method for forming a pattern on a ceramic green sheet according to claim 5, wherein the photosensitive resistor paste contains a resistor powder and a photosensitive resin composition. 8. The method for forming a pattern on a ceramic green sheet according to claim 5, wherein the photosensitive dielectric paste contains a dielectric powder and a photosensitive resin composition. 9. The method for forming a pattern on a ceramic green sheet according to claim 8, wherein the photosensitive dielectric paste further contains an ultraviolet absorber. 10. The method for forming a pattern on a ceramic green sheet according to claim 9, wherein the dielectric powder is coated with an ultraviolet absorber. 11. The method for forming a pattern on a ceramic green sheet according to claim 5, wherein the photosensitive insulating paste is an insulator powder and a photosensitive resin composition. 12. The method for forming a pattern on a ceramic green sheet according to claim 11, wherein the photosensitive insulating paste contains an ultraviolet absorber. 13. The method for forming a pattern on a ceramic green sheet according to claim 12, wherein an insulator powder is coated with the ultraviolet light absorber. 14. The method for forming a pattern on a ceramic green sheet according to claim 9, wherein the ultraviolet absorber is an organic dye. 15. The method for forming a pattern on a ceramic green sheet according to claim 14, wherein the organic dye is an azo dye. 16. A UV absorbing light agent having a wavelength of 350 to 450 nm.
13. The method for forming a pattern on a ceramic green sheet according to claim 9 or 12, wherein the integrated value of the absorbance at 20 to 100 is 20 to 100.