JP3334428B2 - Organic binder for ceramic molding, its production method and use using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of so-called ceramics such as alumina from the viewpoints of low pollution, resource saving, disaster prevention safety and safety and health, that is, the production of molded articles made of ceramic precursors and green sheets. In particular, the present invention relates to an organic binder for ceramics which is water-based and has excellent binder removal properties.

[0002]

[Prior art]

(A) Conventionally, organic binders such as polyvinyl butyral resin and polyacrylate resin have been generally used as a binder for ceramics. This binder is dissolved or dispersed in an organic solvent such as an alcohol, a ketone, a chlorinated solvent, or an aromatic solvent, mixed with a ceramic fine powder, kneaded for a long time in a ball mill or the like, dispersed and slip-shaped. Eggplant After defoaming, a method of casting a sheet having a certain thickness on a base material such as a polyester film by a doctor blade method or the like, and drying by heating to form a green sheet is employed.

(B) As a water-soluble binder for ceramics, JP-A-56-76405 discloses a water-soluble polyvinyl acetal having a degree of acetalization of 10 mol% or less.
JP-A-64-29408 as a cold water-soluble polyvinyl acetal having a degree of acetalization of 10 to 30 mol%, and JP-A-59-29139 as a modified polyvinyl alcohol having a hydrophobic group or a specific ionic hydrophilic group in its side chain as an aqueous organic binder.
This is known from, for example, Japanese Patent Application No. 156959.

(C) As water-soluble poly (meth) acrylate ester-based binders, Japanese Patent Publication No. 1-35333, Japanese Patent Publication No. 44668/1994, and Japanese Patent Application Laid-Open No. 1-286555 are known. In these, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is neutralized (pH adjusted) with amines such as ammonia, trialkylamine such as trimethylamine, dimethylamino alcohol, and monoethanolamine. .

[0005] Also, (d) an emulsion binder obtained by emulsion polymerization of a vinyl monomer using a surfactant is used with (meth) acrylic acid and neutralized with ammonia (pH
JP-A-60-180955, JP-A-60-180956, and JP-A-61-180956.
No. 151060, Japanese Unexamined Patent Publication No. 1-28655,
JP-A-63-260855, which has a crosslinked structure
A gazette is known.

(E) (a) an α-olefin polymer, (b) a (meth) acrylate alone or (meth) acrylate monomer and a styrene monomer,
(C) JP-A-3-131604 using a system in which a swelled product comprising a polymerization initiator is dispersed in an aqueous medium containing a dispersant for polymerization (for example, a water-soluble polymer polyvinyl alcohol) and subjected to suspension polymerization, as a binder. Publications are known.

(F) JP-A-59-128266 discloses that (a) 100 parts by weight of a water-soluble polymer component
(B) Composite binders for ceramic molding containing 1 to 1000 parts by weight of a hydrophobic polymer component are known.

On the other hand, (g) JP-A-59-995,
JP-A-60-254697 discloses a method for manufacturing a multilayer ceramic circuit board substrate, in which a polymethacrylate resin is disclosed as a binder containing a thermally depolymerizable resin.

(H) Japanese Patent Application No. 5-306245 discloses that (a) a polymer of at least one vinyl monomer, (b) a water-soluble polymer, and (c) water or water and water-soluble polymer. Organic ceramic molding organic binders formed from organic solvents are known.

[0010]

However, (A)
In the binder, butyl alcohol, isopropyl alcohol, trichloroethylene, toluene and the like are used as organic solvents. However, explosiveness due to ignition, danger of fire, odors during molding and drying, especially halogen-based solvents have environmental problems due to evaporative gas and harm to the human body. In addition, there are many problems such as the necessity of installing waste gas treatment equipment, solvent recovery equipment and the like. The cases (b) and (c) are disadvantageous in that they are water-soluble and therefore have high hygroscopicity, causing variations in the characteristics of the ceramic green sheet. In the case of (d), the ceramic green sheet using the emulsion having a carboxyl group has drawbacks such as low tensile strength and poor glossiness and smoothness. In addition, since all the binders are inferior in debinding properties, there is a problem that the strength of the fired ceramic sheet and ceramic substrate is inferior. Also,
In the case of (e), the compatibility between the component (a) and the component (b) is poor, and the mechanical properties of the ceramic precursor composition are poor.
Further, since a polymer having low thermal decomposability such as an α-olefin polymer or polyvinyl alcohol is used, there are problems such as poor binder removal properties and inferior strength of fired ceramics, ceramic sheets and ceramic substrates.
In the case of (f), the hydrophobic polymer latex obtained by emulsion polymerization is added as a water-based dispersion to a water-soluble polymer solution dissolved in water. Because of the large number of molecules, it is important that the amount added is as small as possible in order to use a water-soluble polymer as a binder. In addition, when a large amount of water-soluble polymer is present, the green sheet easily absorbs moisture, so that there are large variations in mechanical properties and the like.
In addition, since the hydrophobic polymer latex obtained by emulsion polymerization contains a surfactant, the workability is poor, such as agglomeration depending on the type of the ceramic powder and generation of many bubbles at the time of defoaming.

On the other hand, in order to use the polymethacrylate ester resin used in (g) as an organic binder for ceramic molding, for example, a vapor such as a ketone solvent such as methyl ethyl ketone or an alcohol solvent such as butyl alcohol is used. Lack of fire safety due to use of organic solvent with high pressure. In (h), the amount of the water-soluble polymer for forming the green sheet into a multilayer is small, so that the adhesiveness between sheets is inferior, and the heat-decomposability of the water-soluble polymer compound described is not necessarily sufficient. In order to manufacture a multilayer wiring board of 100 cm ² or more and 30 or more layers of a low-temperature sinterable ceramic, it is necessary to have a material composition excellent in thermal decomposition. In addition, there is a problem that the defoaming time when producing a green sheet is prolonged.

[0012]

The present inventors have conducted intensive studies and have found that (A) at least one kind of 1) an alkylene oxide having an ethylene oxide content of 70% by weight or more is subjected to addition polymerization to obtain an average molecular weight. Is 30,00
0 or more water-soluble high molecular weight compound; 2) an organic compound having two active hydrogen groups having an ethylene oxide content of 7
A water-soluble high molecular weight compound having an average molecular weight of 30,000 or more obtained by addition polymerization of 0% by weight or more of an alkylene oxide; 3) an organic compound having two active hydrogen groups having an ethylene oxide content of 70% by weight or more; A reaction product of a polyhydroxyl compound having an average molecular weight of 1000 or more obtained by addition-polymerizing an alkylene oxide and a polycarboxylic acid or a lower alkyl ester thereof, wherein the ethylene oxide content is 68% by weight or more, and 1 to 30 parts by weight of a water-soluble high molecular weight compound having a degree of 4.5 to 21 and an average molecular weight of 30,000 or more is used as a dispersion stabilizer for polymerization, and in the presence of the component (A), (C) water or In water and a water-soluble organic solvent, (B) 100 parts by weight of at least one vinyl monomer is dispersed and polymerized with a radical polymerization initiator. Click molding organic binder - can be obtained. The obtained organic binder for ceramic molding is excellent in environmental friendliness, safety and debinding properties (thermal decomposition properties).
They have found that they are useful as aqueous ceramic organic binders, and have completed the present invention.

That is, according to the present invention, as a component of an organic binder for forming a ceramic which is excellent in environmental friendliness, safety and thermal decomposability, at least one kind of a vinyl monomer as component (B) is 100 parts by weight. , Preferably at least one or more (meth) acrylates (provided that the number of carbon atoms is 1)
(C) water or water in the presence of the above-mentioned component (A), the polymerization stabilizer, and 100 parts by weight of (C) an alkyl group having 1 to 12 carbon atoms or an ester of a cyclic alkyl group or an aryl group having 1 to 12 carbon atoms. And in a solution dispersed in a water-soluble organic solvent, an organic binder for ceramic molding is obtained by dispersion (co) polymerization (or suspension polymerization) with a radical polymerization initiator,
The above object is achieved.

(D) 100 parts by weight of ceramic powder,
A slurry of the ceramic precursor composition, which is a ceramic precursor composition comprising (E) 5 to 30 parts by weight of an organic binder for ceramic molding and, if necessary, (F) a dispersant and a plasticizer, A green sheet is obtained by coating the surface in a thin film form, the sheet is fixed to a jig, drilling is performed, the conductor is filled, and a conductor layer is formed in a pattern on the sheet. Number 1 from layer
The multilayer ceramic substrate is obtained by laminating and adhering to zero layers and sintering under predetermined conditions (a binder removing step, and then a step of reducing residual carbon), and the above object is achieved.

The ceramic powder as the component (D) is not particularly limited. However, when forming a green sheet which requires fine wiring and fine holes for high density, the average of the ceramic powder is used. It is desirable that the fine particles have a particle size of 20.0 microns or less.

The component (D) having an average particle diameter of 20.
100 parts by weight of a ceramic fine powder having a particle size of 0 micron or less, 5 to 30 parts by weight of the organic binder for ceramic molding (E), and a dispersant and a plasticizer (F) as required. A conductive layer is formed on the ceramic precursor composition in a pattern and filling up the layers, and thermocompression bonding is performed to form several to several tens of layers, followed by sintering (the binder removal process, The step of reducing the residual carbon) yields a multilayer ceramic substrate. In order to further increase the density, the green sheet layer
Component (D) having an average particle size of 10.0 microns or less.
100 parts by weight of the ceramic fine powder and the component (E),
A ceramic precursor composition comprising 5 to 30 parts by weight of the ceramic forming organic binder and, if necessary, component (F), a dispersant and a plasticizer; The above object is achieved by a method of manufacturing a multilayer wiring ceramic substrate obtained by sintering a laminate through the above method.

Hereinafter, the present invention will be described in detail.

The present invention is characterized in that 1 to 30 parts by weight of the polyethylene oxide resin as the component (A) and (C) water or water and a water-soluble organic solvent are used as the polymerization stabilizer (A). The polymer (B) is obtained by blending a polymer of 100 parts by weight of at least one kind of vinyl monomer.

That is, at least one or more (meth) acrylic acid esters (B) having a carbon number of 1 to
18 alkyl groups, an ester of a cyclic alkyl group or an aryl group having 1 to 12 carbon atoms);
In water or a mixture of water and a water-soluble organic solvent in which 1 to 30 parts by weight of the above water-soluble high molecular weight compound (A) is dissolved (based on 100 parts by weight of component (B)), a polymerization initiator is added. The present invention relates to an organic binder for ceramic molding characterized by being subjected to dispersion (co) polymerization (or suspension polymerization) in the presence thereof, and a method for producing the same.

The water-soluble high molecular weight compound used in the present invention is soluble in water. (A) used in the present invention
As the water-soluble high-molecular-weight compound as a component, 1) a water-soluble high-molecular-weight compound having an average molecular weight of 30,000 or more obtained by addition-polymerizing an alkylene oxide having an ethylene oxide content of 70% by weight or more; A water-soluble high molecular weight compound having an average molecular weight of 30,000 or more obtained by addition-polymerizing an alkylene oxide having an ethylene oxide content of 70% by weight or more to an organic compound having
3) A polyhydroxyl compound having an average molecular weight of 1000 or more obtained by addition-polymerizing an alkylene oxide having an ethylene oxide content of 70% by weight or more to an organic compound having two active hydrogen groups, a polyhydric carboxylic acid or a lower alkyl thereof. A water-soluble high molecular weight compound which is a reaction product with an ester and has an ethylene oxide content of 68% by weight or more, a degree of polymerization of 4.5 to 21, and an average molecular weight of 30,000 or more. The ethylene oxide content is 70% by weight or more, preferably 70 to 98% by weight,
More preferably, it is 75 to 95% by weight, and when the ethylene oxide content is less than 70% by weight, it becomes difficult to dissolve in water.

The alkylene oxide used as a component of the water-soluble high molecular weight compound includes, for example, ethylene oxide, propylene oxide, butylene oxide,
Styrene oxide and the like are used, and the amount of the styrene oxide is 0.05 to 20 parts by weight based on 100 parts by weight of the alkylene oxide.
The amount of the catalyst used in the addition polymerization reaction, which is a caustic alkali such as sodium hydroxide or potassium hydroxide, is preferably 0.01 to 100 parts by weight based on 100 parts by weight of the starting material and the alkylene oxide. A range of 1 part by weight is preferred. As a conventional method for synthesizing a high molecular weight polyalkylene oxide having an average molecular weight of 20,000 or more, for example, polyethylene oxide is polymerized on ylene oxide with a special catalyst such as diethyl zinc, strontium carbonate, triethyl aluminum, etc. Under polymerization conditions, for example, n-hexane, 1,4-dioxane, and n-heptane are used as solvents.

The organic compounds having two active hydrocarbon groups include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1.4-butanediol, 1,6- Hexanediol, neopentyl glycol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetraethylene glycol, and the like.
In addition, polyvalent carboxylic acid or lower alkyl ester thereof,
Malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, itaconic acid, or dimer acid, and anhydrides of these monoesters, dialkyl esters, or carboxylic acids, etc. Is mentioned.

The component (B) used in the present invention is a main component of an organic binder for forming a ceramic, and is used for bonding ceramic powders to each other. For example, methyl (meth) acrylate, ethyl (meth) acrylate , N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl ( (Meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, iso Runiru (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylate and the like. Of these components, from the viewpoint of thermal decomposability, methacrylate esters, further n-butyl methacrylate, tert-butyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-octyl methacrylate, and methyl methacrylate are preferred.

If necessary, at least one kind of a combination of (H) and a hydroxyl (meth) acrylate such as 2-hydroxypropyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate in the component (B). 3
It can be used in a range of 0% by weight or less. When the content exceeds 30% by weight, a stable dispersion (suspension) can be obtained by aggregation of polymer particles dispersed in the dispersion (suspension) during dispersion (suspension) polymerization. And cannot be put to practical use. Similarly, if necessary, in combination of at least one kind or more, ethylene monomers such as ethylene, isobutylene and methacrylonitrile, styrene monomers such as styrene (St) and α-methylstyrene (α-MSt), Unsaturated diester monomers such as maleic diester, fumaric diester, itaconic diester and citraconic diester can be used in an amount of 50% by weight or less. When the amount exceeds 50% by weight, when this copolymer is used as a binder to form a ceramic sintered body, the sintered body has low strength due to poor binder removal properties, and has a high dielectric constant. Can not. The purpose of copolymerizing the vinyl monomer with the component (B) is to improve the thermal decomposability and improve the mechanical properties.

Examples of the solvent used in the present invention include water, alcohols such as methanol, ethanol, propanol and isopropanol (IPA), and ethylene such as ethylene glycol methyl ether, ethylene glycol ethyl ether and ethylene glycol butyl ether (EM). Glycol derivatives, diethylene glycol methyl ether, diethylene glycol ethyl ether,
Diethylene glycol derivatives such as diethylene glycol butyl ether, propylene glycol methyl ether (PM), propylene glycol derivatives such as propylene glycol ethyl ether and propylene glycol butyl ether, acetate derivatives such as methyl acetate and ethyl acetate, methyl lactate and ethyl lactate (EL) Water-soluble solvents such as lactate derivatives and the like can be mentioned. It is selected from at least one or more of water or water and a water-soluble solvent. Further, an alcohol-based solvent that is hardly soluble in water may be partially added. When water and a water-soluble solvent are used, the mixing ratio is 100 to 50% by weight of water, 0 to 50% of a water-soluble solvent, preferably 95 to 70% by weight of water, and 5 to 30% by weight of a water-soluble organic solvent.

The function of the water-soluble organic solvent is as follows. If the water-soluble organic solvent is present during the dispersion polymerization, the polymer particles formed are liable to become fine particles, and the dispersion polymerization proceeds smoothly. Also, adhesion of the polymer to the polymerization vessel is small.

Examples of the polymerization initiator include, for example, 2,2′-
Azobis (isobutyronitrile) [AIBN), 2,
2′-azobis (2,4-dimethylvaleronitrile),
Azo compounds such as 2,2′-azobis (isobutylvaleronitrile), peroxides such as tert-butyl hydroperoxide (t-BHPO), benzoyl peroxide and t-butyl peroxide, ammonium persulfate (APS); A water-soluble polymerization initiator such as a persulfate such as potassium persulfate (KPS) can be used without any particular limitation.
The amount used is 0.0 to 100 parts by weight of the total amount of the monomers.
It is desirable to use 5 to 5 parts by weight. In addition, the molecular weight of the binder can be controlled by using a chain transfer agent such as tasharydecyl mercaptan, thioglycolic acid, α-methylstyrene oligomer, oxygen gas, or the like, if necessary.

This reaction depends on the type of polymerization catalyst,
Usually, it can be carried out at 40 to 90 ° C. Lower temperatures give higher molecular weight products and higher temperatures give lower molecular weight polymers.

The average molecular weight of the vinyl monomer polymer used as the binder in the present invention is 100,000 to 100.
10,000, preferably 200,000 to 550,000. If it is less than 100,000, the mechanical properties of the green sheet cannot be sufficiently obtained, and
If it exceeds 10,000, the fluidity of the binder resin becomes low, and it is difficult to obtain sufficient mechanical properties of the green sheet.

The particle size of the polymer obtained according to the present invention can be measured by an electron microscope, a microtrack method or the like.

When used as the organic binder for ceramics used in the present invention, the average particle size of the polymer (the center of the particle size distribution) is preferably 5 μm or less, more preferably 3.0 μm or less. In order to produce such a polymer particle size, it is preferable that the polyethylene oxide-based water-soluble polymer compound as the component (A) has an average molecular weight of 30,000 or more as a dispersion stabilizer for polymerization. Preferably, it is 100,000 to 400,000. The amount of the component (A) used is 1 to 30 parts by weight based on 100 parts by weight of the total amount of the vinyl monomer. Preferably 3 to 20 parts by weight, more preferably 3 to 15 parts by weight. In order to use an organic binder for ceramic molding in a glass ceramic for low-temperature sintering, a polyethylene oxide-based water-soluble polymer compound as the component (A) Is preferably used as little as possible, and preferably 1 to 9.5 parts by weight. When the amount of the component (A) is increased from about 10 to 30 parts by weight and the green sheet is multi-layered, the adhesion between the sheets is improved and the slurry which is a ceramic precursor composition is used. There are merits such as defoaming, dehydration or dehydration of water and shortening the time of a water-soluble organic solvent. If the amount of the component (A) is less than 1 part by weight, no dispersion occurs, or the polymer particles become large and blockage occurs due to adhesion between the particles. When the amount exceeds 30 parts by weight, the polymer composition comprising the component (A) and the polymer of the component (B) becomes difficult to be compatible with each other, so that the mechanical strength of the sheet is lowered and the binder is removed. Due to poor properties, the strength of the sintered body is low and the dielectric constant is high, so that it cannot be put to practical use.

Since the component (A) is a polymer, the appearance of the formed green sheet is much smoother than when a low-molecular surfactant is used, and the ceramic powder hardly falls off from the surface, and the green sheet is hardly removed. Less foaming during foaming and excellent workability. When a general water-soluble polymer compound is used,
This causes variations in the mechanical properties of the green sheet due to humidity and, consequently, lowers the accuracy of drilling. However, polyethylene oxide resin (melting point: 50 ° C. to 65 ° C.)
(C, average molecular weight of 100,000 to 1,000,000) was found to be less hygroscopic in the film form and hardly influenced by humidity even when used as a binder after being mixed with the polymer of component (B). In addition, it has been found that the performance of the aqueous organic binder obtained by the present invention is equal to or higher than that of a green sheet prepared from an organic solvent based on the same components. Further, a polymer obtained by copolymerizing less than 30% by weight of propylene oxide with ethylene oxide (A) than a single polyethylene oxide resin has excellent thermal decomposability and low residual carbon.

The function of the dispersion stabilizer for polymerization used in the present invention is to allow the fine particles of the polymer obtained from the vinyl monomer (B) by dispersion (suspension) polymerization to stably exist. Further, since the dispersant is a high molecular weight compound, it also functions as a part of an organic binder for ceramics. Therefore,
In the case of performing debinding at a low temperature, for example, in the case of a glass ceramic multilayer substrate, the dispersant for polymerization needs to have both excellent properties of thermal decomposition and moisture resistance.

The basic performance of the organic binder for ceramic used in the present invention is based on the mechanical properties (handling property) of the green sheet produced using the organic binder.
It is necessary to have good thermal decomposition properties (residual carbon during sintering should be small). For this purpose, it is better that the amount of the dispersant for polymerization is as small as possible.

Surfactants used as component (F) include, for example, anionic surfactants of higher alcohol sulfates such as sodium lauryl sulfate and ether type non-surfactants such as polyoxyethylene alkyl ether. Examples of the surfactant include an ionic surfactant, a carboxybetaine type, and an amphoteric surfactant of an aminocarboxylate, and the amount of the surfactant is 0.5 to 8 parts by weight, preferably 1 to 5 parts by weight. Particularly preferred surfactants are nonionic surfactants, and when the added amount of the surfactant is less than 0.5 part by weight, the dispersing effect is not good. If the amount is more than 8 parts by weight, there is a problem that foam is generated when used as a binder and the slurry is difficult to handle.

The plasticizer used together with the binder is basically one which is hardly azeotropic with water or an aqueous solvent.
In addition, it has good compatibility with the polymer obtained from the vinyl monomer. For example, dibutyl phthalate (abbreviated as DBP), di-2-ethylhexyl phthalate (DOP),
Diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diheptyl phthalate (DH
P), phthalic acid esters such as di-n-octyl phthalate (N-DOP) butylbenzyl phthalate (BBP), ethyl phthalyl ethyl glycolate, di-2-ethylhexyl adipate (DOA), dibutyl diglycol adipate (BXA), etc. Aliphatic ester, tripropylene glycol methyl ether (TPM), dipropylene glycol-n-butyl ether (DPnB),
Tripropylene glycol-n-butyl ether (TP
nB), propylene glycol phenyl ether (PP
h) and the like. Preferably, DOP, DINP, DIDP, DH
P, N-DOP is good. The above-mentioned plasticizer may be added according to each form, and is not particularly limited. That is, it is only necessary that the mechanical properties of the ceramic precursor composition formed by using the organic binder for ceramic are maintained and the handling properties are excellent. That is, the mechanical properties of the green sheet obtained by changing the amount of the plasticizer can be adjusted with the plasticizer. As a guide, the elongation is required to be about 5 to 25% in order to obtain the handling property and the perforation processing accuracy of the green sheet. The plasticizer may be added at the time of dispersion polymerization of the vinyl monomer or after the polymerization. Preferably, it is added during polymerization in order to prevent adhesion of polymer particles.

The organic binder for ceramic molding used in the present invention has a solid content of 30% by weight or less, 15% by weight or less.
Above. If it exceeds 50% by weight, the particle size of the component (B) becomes large, and if it is less than 15% by weight, the workability decreases.

In the method for producing the organic binder for ceramic molding used in the present invention, 100 parts by weight of the total amount of the monomer as the component (B) is added to (C) water or a mixture of water and a water-soluble organic solvent. ) Component 1 to 30 parts by weight (based on 100 parts by weight of the total amount of the vinyl monomer (B)) is dissolved, and the vinyl monomer (B) is vigorously stirred in the solution. The mixture is dispersed (suspended) and heated, polymerized or copolymerized in the presence of a polymerization catalyst with vigorous stirring.

The average of the ceramic powder used in the present invention
Particle size less than 20.0 microns, preferably 10 microns
Or less, more preferably 5 microns or less. Ceramic
As the powder, for example, Al_TwoO_Three, SiO_Two, 3Al_Two
O_Three・ SiO_Two, PbO, Al _TwoO_Three・ MgO, B_TwoO_Three, C
aO, BaO, ZrO_Two, ZnO, Na_TwoO, P_TwoO_Five, K
_TwoO, Li_TwoSelected from at least one or more of O, etc.
It is. More specifically, alumina (Al_TwoO_Three),
Anorthite (Anorthite, CaO, AlO,
2SiO_Two), Mullite (Mulli-te, 3Al)_TwoO
_Three・ 2SiO_Two), Cordierite
e, 2MgO.2Al_TwoO_Three・ 5SiO_Two), Spoju-
Men (Spodumene, Li_TwoO ・ Al_TwoO_Three・ Si
O_Two) At least one ceramic powder, SiO_Two
-B_TwoO_Three-Na_TwoO-based, SiO_Two-B_TwoO_Three-K_TwoO system, S
iO_Two-B_TwoO_Three−Li_TwoO-based, SiO_Two-B_TwoO_Three-Zn
O, at least one or more borosilicate glasses
Selected from glass ceramic powders. Also these gala
Amorphous that ceramics can be fired below the melting point of copper
Or, it is preferable to use crystalline glass ceramic and strong bending strength.
More preferably, after sintering, cristobalite (Cris
Components that are unlikely to produce tobalite) are preferred. This
The ceramic fine particles used are spherical, pulverized, etc.
You. If fine through-hole processing is required,
The average particle size of the ceramic powder for lean sheet is generally
10 microns or less, more preferably 5 microns or less
Good.

The ceramic raw material used in the present invention includes a high dielectric material such as BaTiO ₃ , a resistor material and the like, and is not particularly limited.

Examples of the dispersing aid for ceramics used in the present invention include salts of polyacrylic acid such as ammonium polyacrylic acid, phosphate esters (Phosphate).
ester), polyethylene glycol, polyvinyl-
2-pyrrolidone and copolymer, glycerol triole
(Glycerol trioleaste) and the like (Advases in ceramics,
Vol. 21, Ceramic Powder Sci
ence p537-547, 1987). 3,6
-Dimethyl-4-octyne-3,6-diol, 2,
4,7,9-Tetramethyl-5-decyne-4,7-diol, a nonionic surfactant such as a liquid to which ethylene oxide has been added (the number of moles of ethylene oxide added: 1.3, 3.5, 10, 30, weight%: 2
0, 40, 65, 85), 2,4,7,9, -tetramethyl-5-decyne-4,7-diol and polyoxyethylene alkylphenyl ether at high concentrations in ethylene glycol. Examples of the dissolved liquid nonionic surfactant and, if necessary, other surfactants include, for example, anionic surfactants of higher alcohol sulfates such as sodium lauryl sulfate, and polyoxyethylene alkyl ethers. And ether type nonionic surfactants such as polyoxyethylene polypropylene alkyl ether, carboxybetaine type and aminocarboxylate amphoteric surfactants.

The ceramic dispersing aid makes it difficult for the ceramic powders to agglomerate and facilitates the flow of the slurry. The ceramic dispersion aid is used by adding a ceramic powder to a solution dissolved or dispersed in a solvent (water, water and a water-soluble solvent). When used, wet mixing is performed for 1 to 5 hours using a ball mill, a predetermined amount of an organic binder for ceramic is added, and the ceramic precursor composition is further wet-mixed using a ball mill for at least 10 hours.
It may be performed for more than an hour.

The method for producing the ceramic precursor composition used in the present invention is as follows.
Parts by weight, 5 to 30 parts by weight of a (meth) acrylic resin dispersion liquid as a binder, which is a component (E), and, if necessary, a dispersant selected from various ceramic dispersion aids. The ceramic precursor composition is wet-mixed using a ball mill for at least 5 hours or more to form a slurry of the ceramic precursor composition. After a defoaming step, an extrusion molding method, an injection molding method, a doctor blade method, and a calendar roll are used. It is formed by a metal method or the like. The production method is not particularly limited.

The method for producing the ceramic used in the present invention is as follows.
It can be obtained by firing at a temperature of 50 to 1800 ° C. for at least 5 hours in air or in a non-reducing atmosphere.

The multilayer ceramic substrate used in the present invention is obtained by the following manufacturing method. (D) Component, ceramic fine powder 10 having an average particle size of 20.0 microns or less
0 parts by weight, 5 to 30 parts by weight of a (meth) acrylic resin suspension as a binder, which is the component (E), and if necessary, selected from various ceramic dispersants which are the component (F). The ceramic precursor composition comprising the obtained dispersant and ceramic powder is subjected to wet mixing using a ball mill for 5 to 50 hours to obtain a ceramic precursor composition slurry.
After a defoaming step, a green sheet is formed by a doctor blade method or the like at a casting temperature from room temperature to 120 ° C. In order to improve the mechanical properties of the green sheet obtained as required, the temperature is further increased to 100 to 120 ° C.
For 30 to 90 minutes. The obtained green sheet having a thickness of 0.05 to 2 mm is cut into a predetermined size (for example, 10 to 200 mm × 10 to 200 mm square), and a through hole is formed in a required layer and a predetermined position. Punch out.
The diameter of the through-hole is not limited, but can be as small as 40 microns. This punched grease
On the sheet, for example, W (melting point 3410 ° C.), Mo
(Melting point: 2620 ° C.), Ag (melting point: 961.9), Au
(Melting point 1064 ° C), Pt (melting point 1769 ° C), Pd
(Melting point 1554 ° C), Cu (melting point 1083.4 ° C), N
A conductor paste mainly composed of one or more conductors such as i (melting point 1453 ° C.) is printed at a predetermined position by a screen printing method. Thus, a predetermined circuit is formed on a green sheet on which a conductor is printed via a screen mask, and several to several tens of layers of the green sheet formed with the circuit are laminated, and a temperature of 80 to 150 ° C. Pressure 0.98 MPa to 29.
Hot press bonding is performed at 4 MPa (10 to 300 kgf / cm ² ). The obtained laminate is cut into a predetermined shape and size. The sintering temperature varies depending on the type of the above conductor (generally sintering at a temperature equal to or lower than the melting point of the conductor). Is obtained.

In order to manufacture a multilayer glass ceramic circuit board, at the time of firing, firing is performed at room temperature or 350 to 450 ° C. in the air or in a non-reducing atmosphere during the heating process.
After firing at 0 to 900 ° C. to remove the binder, the volume ratio of nitrogen, hydrogen (H ₂ ) and water vapor (H ₂ O) or nitrogen and water vapor is 10 to ⁷ to disperse residual carbon if necessary. 1
0 to ⁴ or nitrogen gas and water vapor (water vapor partial pressure 0.005
By sintering at 900 ° C. to the melting point of the above conductor under an atmosphere of (inert atmosphere controlled to 0.5 atm), a multilayer ceramic circuit board is obtained.

The ceramic forming organic binder obtained according to the present invention is composed of water alone or water and a water-soluble organic solvent. It can produce ceramic green sheets excellent in dispersibility, surface smoothness, density, elongation, and strength, low pollution,
This is advantageous from the viewpoint of resource saving. Further, by laminating and firing the green sheets, a multilayer ceramic substrate which is dense and excellent in surface smoothness and strength can be obtained.

By using the finely divided aqueous organic binder of the present invention, sintering can be performed at a temperature of 1000 ° C. or less,
A desired green sheet laminating method can easily form a glass ceramic substrate having a low dielectric constant, and can be used as a conductor such as Cu, Ni, Ni, Au, Ag, and Pd, which can be fired in a neutral or reducing atmosphere. Can be used, and the mounting density can be increased.

Further, the multilayer glass ceramic substrate according to the present invention can use an organic binder having excellent thermal decomposability, so that residual carbon after sintering can be reduced, and the mechanical strength and dielectric constant of the glass ceramic can be reduced. Since it is possible to use an aqueous organic binder that is excellent and has low moisture absorption, it is possible to put into practical use a multilayer glass-ceramic substrate that excels in the precision of drilling the grease sheet required for fine wiring. become. Here, the mechanical strength of the substrate according to the present invention is not less than about 1500 kg / cm ² , preferably 200 in terms of bending strength.
0 kg / cm ² or more, and less than 1500 kg / cm ² , the reliability becomes insufficient. In order to increase the speed, a dielectric constant of 7
Is preferably not more than 5.5.
Furthermore, as a characteristic of the multilayer glass ceramic substrate,
Thermal expansion coefficient 4.0 × 10 ~ ⁶ / ℃ or less, insulation resistance 10 ¹³ Ω
・ Cm or more is desirable.

The combination of the above-mentioned various characteristics is accompanied by the miniaturization due to the increase in the wiring density, the reduction in the wiring resistance,
It is possible to respond to the demands for lowering the dielectric constant of the substrate material and increasing the density of the wiring in response to high speed.

[0051]

The feature of the present invention is that the above-mentioned organic binder for ceramic molding is useful as an aqueous ceramic organic binder, and the organic binder for ceramic molding exhibits its function for bonding between ceramic fine powders. It satisfies the properties of the sheet, namely, flexibility, moldability, dispersibility, surface condition, and dimensional accuracy for drilling. Further, it satisfies various characteristics of the laminated body of the green sheet with the circuit pattern, that is, the lamination pressure bonding property, the mechanical strength, and the like.

[0052]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

When there is simply a percentage, it means weight%.

100 parts by weight of ceramic powder and 5 to 30 parts by weight of an organic binder for ceramic molding were added to obtain a ceramic precursor composition. This was kneaded in a ball mill. After preparing the ceramic precursor composition slurry in this manner, air was further removed from the slurry under reduced pressure. By adjusting the viscosity of the uniform slurry mixture prepared in this way, using a doctor blade type casting device,
A green sheet was prepared by coating on a polyester film and drying. Various physical properties of the sheet include moldability, flexibility,
The dispersibility was evaluated.

(Formability) After coating on a polyester film and drying, it was visually evaluated.

：: Good peeling of the green sheet with the polyester sheet, and no cracking.

Δ: Green sheet with some cracks.

X: No cracking to form a green sheet.

(Flexibility) The center portion of the green sheet was suppressed by each of five types of glass core rods having different diameters, and a 180 ° bending test was performed on the center. The flexibility was indicated by the diameter (mmφ) of the core rod immediately before the sheet cracked. The diameter of the core rod is 2, 3, 4, 6, 8 mm.

(Dispersibility) 〇: Small secondary aggregation in the dispersed state of ceramic fine particles in the green sheet.

△: The secondary aggregation is slightly increased in the dispersed state of the ceramic fine particles in the green sheet.

×: A large amount of secondary aggregation in the dispersed state of the ceramic fine particles in the green sheet.

Example 1 (Synthesis of Organic Binder for Ceramic Molding) Ion-exchanged water was placed in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas inlet tube under a nitrogen gas stream.
89 g of polyethylene oxide resin (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Paogen PP-15,
(Average molecular weight: about 100,000 to 140,000) was added to obtain an aqueous solution of a 10% by weight polyethylene oxide resin. Next, while adding 452.8 g of ion-exchanged water and replacing the polymerization system at a flow rate of nitrogen gas of 1.0 l / min until the start of polymerization,
Next, 300 g of n-butyl methacrylate, 21 g of plasticizer diisodecyl phthalate (DIDP), and 9 g of a 5% aqueous solution in which 0.45 g of ammonium persulfate were charged, and then a nitrogen gas was kept flowing for about 1 hour. 60 solution in flask
C. and the dispersion polymerization was continued for 5 hours. In order to complete the polymerization, the polymerization was carried out while gradually increasing the polymerization temperature to 70, 75, and 80 ° C., and continued for 2 hours. The polymerization solution was cooled to room temperature to obtain a ceramic molding organic binder having a solid content of 32%.

(Preparation of Green Sheet) Alumina powder is a main component, and the overall composition is mullite 94.9.
5% by weight, alumina 5.1% by weight, particle size 5
32 parts by weight of ion-exchanged water and 0.25 parts by weight of a dispersing aid are added to 100 parts by weight of a ceramic powder having a size of not more than micron,
After mixing, 18 parts by weight of an organic binder for forming a ceramic were added with stirring to obtain a ceramic precursor composition. This was kneaded for 24 hours in a ball mill using an alumina-lined container and alumina balls. After preparing the slurry of the ceramic precursor composition in this way, the slurry was further defoamed by heating under reduced pressure. The viscosity of the uniform slurry mixture thus prepared was adjusted to 2,000 to 5,000 cps, and applied to a polyester film using a doctor blade type casting device and dried at 120 ° C. to produce a green sheet. did. As shown in Table 1, the physical properties of the sheet were all good in moldability, flexibility and dispersibility.

(Preparation of Multilayer Wiring Ceramic Substrate) A green sheet was cut into a 200 mm × 200 mm square using a punch die, and a hole for a guide was formed. Thereafter, the green sheet was fixed using the guide holes, and a through-hole having a diameter of 0.1 mm was punched at a predetermined position by a punch method. Tungsten powder having a particle size of 5 μm or less: ethyl cellulose: α-terpineol: 2,2,4-trimethylpentaneddiol monoisobutyrate = 100: 2:
18 (weight ratio) of the conductive paste was filled in the through holes formed in the green sheet, and then a predetermined circuit pattern was printed on the surface of the green sheet by a screen printing method. The conductor was printed in this manner, and 40 sheets of the green sheet on which the circuit was formed were laminated with the positions of the holes for the guides aligned.
Hot press bonding was performed at 0 ° C. and a pressure of 100 kgf / cm ² . The obtained laminate is cut into a required shape, and 150 mm
A green sheet laminate having a size of 150 mm square was fired at 1600 ° C. for 2 hours in a firing furnace in a mixed atmosphere of nitrogen, hydrogen and steam. During the firing, the binder was sufficiently removed during the heating process. 120mm ×
A multilayer wiring ceramic substrate having a size of 120 mm square and a thickness of 7 mm was manufactured.

<Examples 2 to 15> (Synthesis of Organic Binder for Ceramic Molding) The types and amounts of water-soluble high-molecular-weight compounds, the compounding ratios of monomers, the types and amounts of polymerization initiators, and the types and amounts of dispersion media are shown in Tables. An experiment was conducted in the same manner as in Example 1 except that the composition was changed as shown in Example 1 to obtain an organic binder for ceramic molding.

(Preparation of Green Sheet) Example 1 was repeated except that the organic binder for ceramic molding and the amount added were changed.
Perform an experiment in the same manner as above to produce a green sheet,
The characteristics are shown in Table 1.

[0068]

[Table 1]

(Preparation of Multilayer Wiring Ceramic Substrate) An experiment was conducted in the same manner as in Example 1, and a multilayer wiring ceramic substrate was prepared from green sheets.

<Examples 12 to 31> (Synthesis of Organic Binder for Ceramic Molding) The types and amounts of water-soluble high molecular weight compounds, the compounding ratios of monomers, the types and amounts of polymerization initiators, and the types and amounts of dispersion media are shown in Tables. An experiment was conducted in the same manner as in Example 1 except that the composition was changed as shown in 2 and 3, and an organic binder for ceramic molding was obtained.

[0071]

[Table 2]

[0072]

[Table 3]

(Preparation of Green Sheet) For glass ceramic, borosilicate glass (84% by weight of SiO ₂ ,
9% by weight of B ₂ O _{3, 3} % by weight of Al ₂ O ₃ , 4% by weight of K ₂ O, particle size of 5 μm or less) 50 parts by weight of powder and 50 parts by weight of mullite were mixed with a dispersion aid A6114 (trade name, solid 0.125 parts by weight of 40%, manufactured by Toa Gosei Chemical Co., Ltd.), 32 g of ion-exchanged water, and 13.5 parts by weight of isopropyl alcohol, and 5 to 30 parts by weight of an organic binder for ceramic molding shown in Table 2 were added thereto. A combined ceramic precursor composition was obtained. This was kneaded for 24 hours in a ball mill using an alumina-lined container and alumina balls. Less than,
An experiment was conducted in the same manner as in Example 1 to produce a green sheet, and its properties are shown in Tables 2 and 3.

(Preparation of Multilayer Wiring Ceramic Substrate) Particle Size 5
Submicron copper powder: vehicle [ethyl cellulose:
2,2,4-trimethylpentanediole monoisobutyrate] = 89: 11 [10:90] (% by weight) using a conductive paste of nitrogen-hydrogen-steam,
The experiment was conducted in the same manner as in Example 1 except that the firing temperature was 350 to 850 ° C., the binder was removed for 20 hours, and then the main firing was performed at 950 to 1040 ° C. for 2 hours in a nitrogen atmosphere. did.

The characteristics of the obtained multilayer glass ceramic substrate are as follows: dielectric constant: 5.5 or less, flexural strength: 2000 kg
/ Cm ² or more, thermal expansion coefficient of 3.5 × 10 ⁶ / ° C. or less, and insulation resistance> 10 ¹³ Ω · cm.

Example 32 (Synthesis of Organic Binder for Ceramic Molding) Ion-exchanged water was placed in a 2 l flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube under a nitrogen gas stream. 0 g and 21 g of Paogen PP-15 (average molecular weight: about 100,000 to 140,000) were added with stirring and uniformly dissolved, and 336.2 g of ion-exchanged water was added.
The nitrogen gas was replaced in the same manner as in Example 1 for one minute. While stirring, 225.1 g of IPA, n-butyl methacrylate 30
0 g, 31.5 g of a plasticizer diisononyl phthalate and 0.45 g of a polymerization initiator ammonium persulfate were added, and nitrogen gas was replaced in 30 minutes to 1 hour. The polymerization temperature was continuously heated at 60 ° C. for 4 hours, and the polymerization temperature was raised stepwise or gradually to 80 ° C., and the polymerization was completed for 2 hours to complete the reaction. This was cooled to room temperature to obtain an organic binder for forming ceramics having a solid content of 32% [50% polymer average particle diameter: 3.0 μm or less, viscosity of suspension: 7 Pa · s,
Weight average molecular weight: 400,000. (Production of green sheet)
Borosilicate glass (84% by weight of SiO _2, 9% by weight of B ₂ O _{3, 3} % of Al ₂ O ₃ , 4% by weight of K ₂ O) Component composition, particle size 5
63.1 parts by weight of powder, mullite 36.9
40 parts by weight of ion-exchanged water (a part of the ion-exchanged water may be replaced with a water-soluble solvent such as IPA if necessary), a ceramic dispersant A6114 (trade name, solid content 4
(0.1% by weight, 0%, manufactured by Toa Gosei Chemical Co., Ltd.) and kneaded for 2 hours in an alumina lined container and a ball mill using alumina balls. Further, 20 parts by weight of an organic binder for forming a ceramic was added to obtain a ceramic precursor composition. This was kneaded for 24 hours in a ball mill using an alumina-lined container and alumina balls. After preparing the ceramic precursor composition slurry in this way, the slurry is further reduced in pressure to 133.3 Pa to 666.
Degassing was performed under 5 Pa (1 mmHg to 50 mmHg). The uniform slurry mixture prepared in this manner is further heated and reduced in pressure while spraying water and an organic solvent under reduced pressure to adjust the viscosity to 3 Pa · s to 10 Pa · s. It was cast on top and dried at 120 ° C. to produce a green sheet having a thickness of 0.2 mm. As shown in Table 3, the physical properties of the sheet were all good in moldability, flexibility and dispersibility.

(Preparation of Multilayer Wiring Ceramic Substrate) The obtained green sheet was cut into a 200 mm × 2 mm
It was cut into 00 mm squares and provided with holes for guides. Thereafter, the green sheet was fixed using the guide holes, and a through-hole having a diameter of 0.1 mm was punched at a predetermined position by a punch method. Cu powder with a particle size of 5 microns or less: vehicle [ethyl cellulose: 2,2,4-trimethylpentanediole monoisobutyrate] = 89: 11 [10: 9]
0] (% by weight) was filled in through holes formed in the green sheet using a conductor paste of (% by weight), and then a predetermined circuit pattern was printed on the surface of the green sheet by a screen printing method. The conductor is printed in this way, and 40 sheets of the green sheet on which the circuit is formed are laminated with the positions of the holes for the guides aligned, and 120 ° C., a pressure of 9.80 MPa (100 kgf / c)
m ² ), hot press bonding was performed. The obtained laminate was cut into a required shape to form a green sheet laminate of 150 mm × 150 mm square, and nitrogen-hydrogen-water vapor (pressure ratio;
(6 atm: 0.2 atm: 0.2 atm) in a mixed atmosphere baking furnace at 350 to 850 ° C for 20 hours after removing the binder, 95
It baked at 0-1040 degreeC for 2 hours. During the firing, the binder was sufficiently removed during the heating process. By this green sheet laminating method, a multilayer wiring ceramic substrate having a size of 120 mm × 120 mm square and a thickness of 7 mm was produced.

The properties of the obtained multilayer glass ceramic substrate were as follows: dielectric constant: 5.2, flexural strength: 2000 kg / cm ² ,
Thermal expansion coefficient of 3.5 × 10 ~ ⁶ / ℃, insulation resistance> 10 ¹³ Ω ·
cm.

Comparative Example 1 (Binder Resin) A polyvinyl acetate copolymer containing 4.0 mol% of octylacrylamide and 2.0 mol% of trimethyl-3- (1-methacrylamido-propyl) ammonium chloride. , 8 of its vinyl acetate component
8.7 mol% of a saponified modified PVA having a viscosity of 34 centipoise in a 4% aqueous solution at 20 ° C. was used as a binder.

(Preparation of Green Sheet) Alumina powder as a main component, the overall composition was 33% Al ₂ O ₃ ,
100 parts by weight of a ceramic powder having a particle size of 5 μm or less having components of 33% of iO _{2 and} 34% of borosilicate glass, 6 parts of the binder resin, 1 part of polyoxyethylene nonylphenol ether as a dispersant, and 5 parts of ion-exchanged water
0 parts were added to obtain a ceramic precursor composition. This was kneaded for 24 hours in a ball mill using an alumina-lined container and alumina balls. Thereafter, an experiment was performed in the same manner as in Example 1 to produce a green sheet, and various characteristics are shown in Table 4.

[0081]

[Table 4]

Comparative Example 2 (Binder resin) Monoethanolamine salt of a copolymer of acrylic acid, butyl acrylate, and ethyl acrylate having a polymerization ratio (50/25/25) and a weight average molecular weight of about 100,000
g of water / methanol polymerization ratio (5/5) 80
of ethyl acrylate in 0.4 g of a mixed solvent using 0.4 g of ammonium persulfate as a polymerization initiator to obtain a solid content of 50 g.
% Latex was obtained.

(Preparation of Green Sheet) Comparative Example 1 was repeated except that 24 parts of the latex and 18 parts of ion-exchanged water were used.
Perform an experiment in the same manner as above to produce a green sheet,
The properties are shown in Table 4.

Comparative Example 3 (Binder Resin) A latex having a composition of butyl acrylate, acrylic acid, and methacrylic acid (70/15/15) was obtained using a nonionic surfactant as a dispersant and an emulsifier. Was.

(Preparation of Green Sheet) An experiment was carried out in the same manner as in Comparative Example 1 except that 10 parts (solid content) of the latex and monoethanolamine and 25 parts of ion-exchanged water were used as a neutralizing agent. Were prepared, and the characteristics thereof are shown in Table 4.

Comparative Example 4 (Binder Resin) 4 parts by weight of glycine betaine chloride of polyoxyethylene octyl phenyl ether,
Using 4 parts by weight of dimethacrylic acid ester of polyoxypropylene polyoxyethylene glycol as an emulsifier, 2,2'-azobis (N, N 'dimethyleneisobutylamidine) hydrochloride as a polymerization initiator, and 75 parts by weight of ethyl acrylate A latex having a composition of 75 parts by weight of methyl methacrylate and 4.5 parts by weight of N-methylolacrylamide was obtained.

(Preparation of Green Sheet) 10 parts of the latex (solid content), 3 parts of polyethylene glycol (molecular weight: 200) as a plasticizer and ethyl carbitol 2
, And an experiment was conducted in the same manner as in Comparative Example 1 except that 25 parts by weight of ion-exchanged water was used, and a green sheet was produced.

Comparative Example 5 (Binder Resin) Aqueous Dispersion of Hydrophobic Polymer as Component (B): Methacrylate (MMA / n-BMA /
LMA / CHMA = 10/60/10/20, solid content 4
8%) and a 10% water-soluble polymer PVA (polymerization 500, saponification degree 88.5 mol%) as the component (A) were mixed at a 1/1 weight ratio, and an organic binder for green sheets (composite) was mixed. Binder).

(Preparation of Green Sheet) Alumina powder as the main component, the overall composition was 33% Al ₂ O ₃ ,
100 parts by weight of a ceramic powder having a particle size of 5 μm or less containing 33% of O _{2 and} 34% of borosilicate glass, 16 parts of the latex (solid content), 50 parts by weight of water, and a dispersing aid for ammonium polyacrylate 0 After mixing 3 parts with a ball mill for 2 hours, the composite binder was
Except that it was added and mixed uniformly with the powder. An experiment was performed in the same manner as in Comparative Example 1 to produce a green sheet, and various characteristics are shown in Table 4.

However, the abbreviations in Tables 1, 2, 3, 4, and 5 are as follows.

N-BMA: n-butyl methacrylate,
i-BMA: isobutyl methacrylate, t-BMA:
Tert-butyl methacrylate, HEMA: 2-hydroxyethyl methacrylate, St: styrene, EM
A: Ethyl methacrylate, LMA: Lauryl methacrylate, CHMA: Cyclohexyl methacrylate, M
MA: methyl methacrylate, PEO: polyethylene oxide, PVA: polyvinyl alcohol, EL: methyl lactate, IPA: isopropyl alcohol, BPO: benzoyl peroxide, AIBN: 2,2′-azobis (isobutyronitrile), APS: Ammonium persulfate, KPS: potassium persulfate, t-BHPO: tert-butyl hydroperoxide.

Next, Examples 1, 6, 11, 16, 20,
The organic binders obtained in 22, 24, 26, 30, 32 and Comparative Examples 1 to 5 were put into a platinum crucible, ashed in an electric furnace at 600 ° C. under a nitrogen atmosphere for 3 hours, and the weight was measured. . Five green sheets obtained in Examples 1, 6, and 11 were subjected to hot press compression at 120 ° C. and 100 kgf / cm ² . The number of peelings at this time was visually observed. Further, in an atmosphere of nitrogen-hydrogen-steam (pressure ratio: 0.6 atm: 0.2 atm: 0.2 atm), the temperature is set to 1600 ° C,
After firing for a time, a ceramic sheet was obtained. Example 16 and 2
0, 22, 24, 26, 30, 32 and 5 green sheets obtained in Comparative Examples 1 to 5 at 120 ° C. and 100 kgf /
Hot press bonding was performed at cm ² . The number of peelings at this time was visually observed. Further, this laminated body was subjected to nitrogen-hydrogen-water vapor (pressure ratio: 0.65 atm: 1 × 10 to ⁴ atm: 0.3
After removing the binder at 350 to 850 ° C. for 20 hours in an atmosphere (5 atm), main firing was performed at 950 to 1040 ° C. for 2 hours in a nitrogen atmosphere. The density of these sheets was measured, and the surface condition was visually observed. Table 5 shows the results.

[0093]

[Table 5]

[0094]

The organic binder for ceramic molding obtained according to the present invention is a ceramic green excellent in ceramic dispersibility, surface smoothness, density and mechanical strength without using or using a water-insoluble organic solvent at all. Sheets can be generated, from the viewpoint of low pollution and resource saving,
It is advantageous. Particularly in the doctor blade method, it is possible to shift from an organic solvent system to a safe and sanitary water system, and it also has excellent properties such as improved mechanical strength, and is useful as a binder for ceramics. is there.

Continuing on the front page (72) Inventor Kinoshita Enji, Hitachi, Ltd. Production Technology Laboratory, 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Takeshi Fujita 1-Horiyamashita, Hadano-shi, Kanagawa Prefecture Hitachi, Ltd. Within the Computer Division (72) Inventor Norio Chiishi 1st Horiyamashita, Hadano-shi, Kanagawa Prefecture Within the General-purpose Computer Division of Hitachi, Ltd. (72) Inventor Fumiko Kobayashi 1st Horiyamashita, Hadano-shi, Kanagawa Hitachi, Ltd. General-purpose computer business In-house Examiner Yuichi Fukakusa (58) Field surveyed (Int. Cl. ⁷ , DB name) C04B 35/632 C08L 71/02 C09J 171/02

Claims (16)

(57) [Claims] 1. A water-soluble high molecular weight compound (A) having an average molecular weight of 30,000 or more obtained by addition polymerization of (A) an alkylene oxide having an ethylene oxide content of 70% by weight or more.
Using 30 parts by weight of a component as a dispersion stabilizer for polymerization, (C)
An organic binder for ceramic molding, comprising: (B) a polymer obtained by dispersion-polymerizing 100 parts by weight of at least one kind of vinyl monomer in water or water and a water-soluble organic solvent. 2. An (A) organic compound having two active hydrogen groups is subjected to addition polymerization of an alkylene oxide having an ethylene oxide content of 70% by weight or more to have an average molecular weight of 30.
(C) in water or water and a water-soluble organic solvent, and (B) at least one or more vinyl-based monomers. An organic binder for ceramic molding, comprising a polymer obtained by dispersing and polymerizing parts by weight. 3. An average molecular weight obtained by subjecting (A) an organic compound having two active hydrogen groups to addition polymerization of an alkylene oxide having an ethylene oxide content of 70% by weight or more to be 10 or more.
A reaction product of at least 00 polyhydroxyl compound and a polyvalent carboxylic acid or a lower alkyl ester thereof,
An ethylene oxide content of 68% by weight or more;
And 1 to 30 parts by weight of a water-soluble high-molecular weight compound having a degree of polymerization of 4.5 to 21 and an average molecular weight of 30,000 or more is used as a dispersion stabilizer for polymerization. B) An organic binder for ceramic molding, comprising: a polymer obtained by dispersion-polymerizing 100 parts by weight of at least one kind of vinyl monomer. Wherein said (A) according to claim 1, wherein the ceramic molding an organic binder, characterized in that component a is an ethylene oxide content of from 70 to 98 wt%. Wherein said component (B) is a vinyl monomer (meth) according to claim 1, wherein the ceramic molding an organic binder, wherein the acrylic acid ester. Wherein said (B) is a component (meth) acrylic acid ester, a carbon number 1 to 18 alkyl groups or /
And an ester of a cyclic alkyl group and / or an aryl group having 3 to 12 carbon atoms.
The organic binder for ceramic molding according to the above. 7. The (meth) acrylic ester as the component (B) is an alkyl group having 1 to 18 carbon atoms or / and
And 50% of an ester of a cyclic alkyl group having 3 to 12 carbon atoms and / or an aryl group and a hydroxyalkyl group
2. The organic binder for ceramic molding according to claim 1, comprising the above and 50% or less of a vinyl monomer copolymerizable therewith. 8. At least one kind of vinyl monomer,
When the dispersion polymerization is carried out in the presence of a dispersion stabilizer, a polymerization initiator and water or water and a water-soluble organic solvent, which are water-soluble high molecular weight compounds, an alkylene having an ethylene oxide content of component (A) of 70% by weight or more. Using 1 to 30 parts by weight of a water-soluble high molecular weight compound having an average molecular weight of 30,000 or more obtained by addition polymerization of an oxide as a polymerization stabilizer, and (C) at least one of (B) in water or water and a water-soluble organic solvent. A method for producing an organic binder for ceramic molding, comprising a polymer obtained by dispersing and polymerizing 100 parts by weight of the vinyl monomer. 9. at least one or more vinyl monomers,
When dispersion polymerization is carried out in the presence of a water-soluble high molecular weight compound, a dispersion stabilizer, a polymerization initiator and water or water and a water-soluble organic solvent, (A) an organic compound having two active hydrogen groups contains ethylene oxide. (C) water or water and a water-soluble organic compound; 1-30 parts by weight of a water-soluble high-molecular-weight compound having an average molecular weight of 30,000 or more obtained by addition polymerization of an alkylene oxide having a rate of 70% by weight or more; And (B) a polymer obtained by dispersion-polymerizing 100 parts by weight of at least one vinyl monomer in a solvent. (10) When the dispersion polymerization is carried out in the presence of at least one kind of a vinyl monomer, a water-soluble high molecular weight compound, a dispersion stabilizer, a polymerization initiator and water or water and a water-soluble organic solvent, A) An organic compound having two active hydrogen groups, an addition compound of an alkylene oxide having an ethylene oxide content of 70% by weight or more is addition-polymerized, and a polyhydroxyl compound having an average molecular weight of 1000 or more, a polyvalent carboxylic acid or a lower alkyl thereof. A reaction product with an ester, which has an ethylene oxide content of 68% by weight or more, a degree of polymerization of 4.5 to 21, and an average molecular weight of 30.
(C) in water or water and a water-soluble organic solvent, and (B) at least one or more vinyl-based monomers. A method for producing an organic binder for ceramic molding, comprising: a polymer obtained by dispersing and polymerizing parts by weight. 11. A (D) 100 parts by weight of ceramic powder,
(E) A ceramic precursor composition comprising 5 to 30 parts by weight of the organic binder for ceramic molding according to any one of claims 1 to 3 as a binder. 12. (D) 100 parts by weight of ceramic powder;
(E) A ceramic obtained by sintering a ceramic precursor composition comprising 5 to 30 parts by weight of the organic binder for ceramic molding according to any one of claims 1 to 3 as a binder. 13. The component (D) having an average particle size of 20.0%.
(E) 100 parts by weight of ceramic powder of
A ceramic green sheet comprising a thin film of a ceramic precursor composition comprising 5 to 30 parts by weight of the organic binder for ceramic molding according to any one of claims 1 to 3 as a binder as a component. 14. The component (D) having an average particle size of 20.0%.
(E) 100 parts by weight of ceramic powder of
A ceramic sheet obtained by sintering a ceramic green sheet comprising 5 to 30 parts by weight of the organic binder for ceramic molding according to any one of claims 1 to 3 as a binder as a component. 15. The method according to claim 15, wherein the ceramic green sheet layer comprises (D)
4. A ceramic powder having an average particle diameter of 20.0 [mu] m or less as a component, 100 parts by weight, and an organic binder for ceramic molding according to any one of claims 1 to 3 as a binder as the component (E). A multilayer wiring ceramic substrate comprising a ceramic precursor composition comprising: a plurality of conductor layers formed into a laminate with the ceramic sheet layer interposed therebetween; and sintering the laminate. 16. A ceramic green sheet layer comprising a ceramic precursor composition comprising the component (D) and the component (E) according to claim 12, wherein the ceramic green sheet layer is a laminate. At least one of the ceramic, ceramic sheet or multilayer wiring ceramic substrate obtained by sintering has a dielectric constant of 7 or less and a flexural strength of 1500 kg.
A multilayer wiring ceramic substrate having characteristics of at least / cm2.