TW202120570A - Binder composition for forming green sheet, slurry for forming green sheet, green sheet and method for producing same, and device and method for producing same - Google Patents

Abstract

Provided is a binder composition for forming a green sheet, the composition being easily thermally decomposable in the production of a green sheet and being able to increase the strength of a green sheet. This binder composition for forming a green sheet contains a polymer (A) and a liquid medium (B). The polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group. The weight average molecular weight (Mw) of the polymer (A) is 100,000 or more.

Description

Adhesive composition for green sheet forming, green sheet forming slurry, green sheet and manufacturing method thereof, and device and manufacturing method thereof

The present invention relates to an easily thermally decomposable green sheet forming adhesive composition, a green sheet forming slurry containing the composition, and a green sheet formed by coating the slurry on a substrate and drying it. A sheet and its manufacturing method, and a device provided with the green sheet and its manufacturing method.

Ceramics have excellent properties such as strength, insulation, chemical resistance, dielectric properties, and piezoelectricity, and are used as parts of ceramic circuit boards, multilayer ceramic capacitors, and all-solid-state batteries. These ceramic circuit boards or multilayer ceramic capacitors are usually manufactured by a method generally referred to as the green chip method. The green sheet method refers to forming a ceramic green sheet (hereinafter referred to as "green sheet") mainly composed of various ceramic powders and adhesives, and printing and sintering the wiring with a metal paste to form a composite of ceramic and metal Manufacturing Technology.

In the green sheet method, resin systems such as acrylic resins, ethyl cellulose, and polyvinyl butyral are used as binders. This binder system requires improving the dispersibility of ceramic powder or improving the strength of green flakes.

In addition, in the manufacture of multilayer ceramic capacitors, the above-mentioned ceramic green sheet is coated with a metal paste as an internal electrode, then multiple sheets are laminated, and heated and press-bonded to obtain a multilayer body. After thermally decomposing and removing the binder contained in the laminated body, the so-called degreasing treatment is performed, and the external electrode is sintered on the end surface of the ceramic sintered body obtained by firing. At the time of sintering, in order to avoid adverse effects on product characteristics, it is also required to reduce thermal decomposition residues (refer to Patent Documents 1 and 2). If organic matter remains in the capacitor, the performance will be deteriorated. Therefore, the organic matter is removed by prolonging the firing time, and this will lead to deterioration of productivity. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-167836 [Patent Document 2] Japanese Patent Application Laid-Open No. 05-213663

[The problem to be solved by the invention]

When ethyl cellulose or polyvinyl butyral is used as a binder component, there are many organic residues after the degreasing treatment step, and there is a problem of deterioration in thermal decomposition properties. On the other hand, when acrylic resin such as polybutyl methacrylate is used as the binder component, the organic residue after the degreasing treatment step is small, but the strength of the green sheet is insufficient, and the green sheet is prone to cracking during the production step. And it is not easy to become a thin film.

Therefore, several aspects of the present invention provide an adhesive composition for forming green sheets that is easy to thermally decompose during the production of green sheets and can achieve high-strength green sheets. In addition, several aspects of the present invention provide a green sheet forming slurry containing the composition. In addition, several aspects of the present invention provide a green sheet with excellent degreasing properties and processability, and a manufacturing method of the green sheet. Furthermore, several aspects of the present invention provide a device made of the green sheet and a method of manufacturing the device. [Means to solve the problem]

The present invention was accomplished in order to solve at least a part of the above-mentioned problems, and can be realized in any of the following modes.

The same form of the adhesive composition for green sheet molding of the present invention contains a polymer (A) and a liquid medium (B), The aforementioned polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group, The weight average molecular weight (Mw) of the aforementioned polymer (A) is 100,000 or more.

(上述式(1)中，R¹ ～R⁵ 各自獨立地表示氫原子、羧基、羥基、經取代或者未取代之烴基或R² 及R³ 彼此結合而與此等所鍵結之碳原子共同所構成之環員數3～6之環結構的一部分；惟，R¹ ～R⁵ 中的至少1個為經取代或者未取代之具有乙烯性不飽和基之烴基)。In the same form of the aforementioned adhesive composition for green sheet molding, the aforementioned aromatic carboxylic acid having an ethylenically unsaturated group may include a compound represented by the following general formula (1):

(In the above formula (1), R ¹ to R ⁵ each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a substituted or unsubstituted hydrocarbon group, or R ² and R ³ are combined with each other to share the same carbon atom to which they are bonded It constitutes a part of a ring structure with 3 to 6 ring members; ^{however, at least one of R 1} to R ⁵ is a substituted or unsubstituted hydrocarbon group having an ethylenically unsaturated group).

In any of the aforementioned green sheet forming adhesive compositions, The aforementioned polymer (A) contains a structure selected from the group consisting of carboxyl groups, hydroxyl groups, nitrogen-containing functional groups, phosphorus atoms, sulfur atoms, chlorine atoms, bromine atoms, iodine atoms, alkali metals, alkaline earth metals, and transition metals. The content ratio of the repeating unit (a2) derived from at least one type of ethylenically unsaturated monomer (excluding the aforementioned aromatic carboxylic acid and polyalkylene glycol monomethacrylate having ethylenically unsaturated groups), When the total of the repeating units contained in the aforementioned polymer (A) is 100 parts by mass, it may be less than 5 parts by mass.

In any of the aforementioned green sheet forming adhesive compositions, The aforementioned polymer (A) further contains a repeating unit (a3) derived from methacrylate (except for the aforementioned repeating unit (a1) and the aforementioned repeating unit (a2)) and a repeating unit (a5) derived from an aromatic vinyl compound ) (Except for the aforementioned repeating unit (a1) and the aforementioned repeating unit (a2)), When the total of the repeating units contained in the polymer (A) is 100 parts by mass, the total of the repeating unit (a1), the repeating unit (a3), and the repeating unit (a5) may be 90 parts by mass the above.

In any of the aforementioned green sheet forming adhesive compositions, In the polymerization of the aforementioned polymer (A), when the total of all monomers used for the polymerization of the aforementioned polymer (A) is 100 parts by mass, a structure containing a sulfur atom, a nitrogen atom or a carboxyl group is introduced as the initiator The amount of the polymerization initiator at the end may be less than 1 part by mass.

In any of the aforementioned green sheet forming adhesive compositions, In the polymerization of the aforementioned polymer (A), when the total of all monomers used in the aforementioned polymerization of the aforementioned polymer (A) is 100 parts by mass, the amount of the chain transfer agent may not be less than 1 part by mass.

In any of the aforementioned green sheet forming adhesive compositions, When the aforementioned polymer (A) is subjected to differential scanning calorimetry (DSC) in accordance with JIS K7121, an endothermic peak is observed in the temperature range of -40°C to 80°C.

In any aspect of the aforementioned green sheet forming adhesive composition, it can be used for all solid-state battery forming.

The same state of the green sheet forming slurry of the present invention contains the green sheet forming binder composition, inorganic particles, and liquid medium in any of the foregoing forms.

In the same state of the aforementioned green sheet forming slurry, The aforementioned inorganic particles may contain at least one element selected from lithium and titanium.

The green sheet of the present invention is formed by coating the green sheet forming slurry in any of the foregoing states on the substrate and drying it.

The uniform state of the device of the present invention is made of the aforementioned uniform green sheet.

One aspect of the manufacturing method of the green sheet of the present invention includes the step of coating the green sheet forming slurry in any of the foregoing aspects on the substrate and drying it.

One aspect of the manufacturing method of the device of the present invention is to manufacture the device through the green sheet manufacturing method as described above. [Effects of Invention]

According to the adhesive composition for green sheet molding of the present invention, the green sheet is easily thermally decomposed during the production of the green sheet, and the green sheet can be increased in strength.

[The form of implementing the invention]

The preferred embodiments of the present invention will be described in detail below. In addition, the present invention is not limited to only the embodiments described below, and it should be understood that various modifications implemented within a range that does not change the gist of the present invention are also included. In addition, "(meth)acrylic-" in this specification means the concept including both "acrylic-" and "methacrylic-". Similarly, "~(meth)acrylate" refers to the concept including both "~acrylate" and "~methacrylate". Similarly, "(meth)acrylamide" refers to the concept including both "acrylamide" and "methacrylamide".

In this manual, the numerical range described in "X～Y" is interpreted as the following limit includes the value X, and the above limit includes the value Y.

1. Adhesive composition for green sheet forming The adhesive composition for green sheet molding according to an embodiment of the present invention contains a polymer (A) and a liquid medium (B). The adhesive composition for green sheet forming of this embodiment can improve the easy thermal decomposition and the strength of the green sheet. Hereinafter, each component contained in the adhesive composition for green sheet molding of the present embodiment will be described in detail.

1.1. Polymer (A) The binder composition for green sheet molding of this embodiment contains the polymer (A). The polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group, and has a weight average molecular weight (Mw) of 100,000 or more.

The polymer (A) contained in the adhesive composition for green sheet molding of this embodiment may be in the form of an emulsion dispersed in the liquid medium (B), or may be in a state of being dissolved in the liquid medium (B). In either case, the green sheet forming slurry (hereinafter simply referred to as "slurry") made by using the polymer (A) mixed with inorganic particles, etc., has good stability, and the stability of the slurry to the substrate The coating properties are all good and better.

Hereinafter, each repeating unit constituting the polymer (A), the physical properties of the polymer (A), and the production method will be described in order.

1.1.1. Each repeating unit constituting the polymer (A) 1.1.1.1. Repeating units derived from aromatic carboxylic acids with ethylenically unsaturated groups (a1) The polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group (hereinafter abbreviated as "repeating unit (a1)"). The aromatic carboxylic acid having an ethylenically unsaturated group is preferably a compound represented by the following general formula (1):

。

.

In the above formula (1), R ¹ to R ⁵ each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a substituted or unsubstituted hydrocarbon group, or R ² and R ³ are combined with each other to form a combination with the carbon atom to which these are bonded. It constitutes a part of a ring structure with 3 to 6 ring members; ^{however, at least one of R 1} to R ⁵ is a substituted or unsubstituted hydrocarbon group having an ethylenically unsaturated group.

Specific examples of aromatic carboxylic acids having ethylenically unsaturated groups include 2-methacryloxyethyl phthalic acid and trimellitic acid (2-methacryloxy) ethyl monoester , 4-vinyl benzoic acid, etc. Among these, 2-methacryloxyethyl phthalic acid having a carboxyl group at a position away from the hydrocarbon group having an ethylenically unsaturated group is preferred. By having such a structure, it is easier to maintain the methacrylic acid skeleton, and it is possible to suppress the generation of a structure that is not easily thermally decomposable. In addition, these monomers may be used individually by 1 type, and may be used in combination of 2 or more types.

The lower limit of the content ratio of the aforementioned repeating unit (a1), when the total amount of repeating units contained in the polymer (A) is 100 parts by mass, is preferably 0.5 parts by mass, more preferably 3 parts by mass, especially Preferably, it is 5 parts by mass. On the other hand, the upper limit of the content ratio of the repeating unit (a1) is preferably 80 parts by mass, more preferably 60 parts by mass when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass. Parts, particularly preferably 40 parts by mass. When the permeable polymer (A) contains the repeating unit (a1) in the aforementioned range, the polymer (A) has excellent thermal decomposition properties and can reduce organic residues in the degreasing step. In addition, the strength of the obtained green sheet can be improved. Furthermore, since the carboxyl group content in the polymer (A) is a suitable amount, the dispersibility of the inorganic particles in the slurry is also good.

1.1.1.2. Other repeating units In addition to the aforementioned repeating unit (a1), the polymer (A) may also contain repeating units derived from other monomers copolymerizable with these as shown below.

<Repeating units derived from ethylenically unsaturated monomers containing specific functional groups (a2)> The polymer (A) may also contain a structure selected from carboxyl group, hydroxyl group, nitrogen-containing functional group, phosphorus atom, sulfur atom, chlorine atom, bromine atom, iodine atom, alkali metal, alkaline earth metal and transition metal (in this specification) At least one type of ethylenically unsaturated monomer (except the aforementioned aromatic carboxylic acids and polyalkylene glycol monomethacrylates having ethylenically unsaturated groups) in the group consisting of "specific functional groups, etc.") Derived repeating unit (a2) (hereinafter referred to as "repeating unit (a2)").

Examples of ethylenically unsaturated monomers containing carboxyl groups in the structure include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and 2-(meth)acryloxyethyl succinate. Mono or dicarboxylic acids such as acids. These monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of ethylenically unsaturated monomers containing hydroxyl groups in the structure include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 4-hydroxybutyl meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, etc. . These monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of ethylenically unsaturated monomers containing nitrogen-containing functional groups in the structure include vinyl amine, allyl amine, amino styrene, 2-(tertiary butylamino) ethyl methacrylate, methyl methacrylate, etc. Dimethylaminoethyl acrylate and diethylaminoethyl methacrylate are equal to _{ethylenically unsaturated monomers containing -NH 2} , -NHR or -NR ₂ (R: alkyl) in the structure; acrylonitrile, methyl methacrylate Acrylonitrile, α-chloroacrylonitrile, α-ethacrylonitrile, dicyandiethylene are equal to ethylenically unsaturated monomers containing -CN group in the structure; acrylamide, methacrylamide, N-isopropyl Acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide Amide, N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, N-methylol methacrylamide, N-methylol propylene Amide, diacetone acrylamide, and amide maleate are equal to ethylenically unsaturated monomers containing amide in the structure. These monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of ethylenically unsaturated monomers containing phosphorus atoms in the structure include 2-(meth)acryloyloxyethyl phosphoric acid, bis(2-(meth)acryloyloxyethyl phosphoric acid), 2- (Meth) acryloxyethyl phosphatidylcholine and the like. These monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of ethylenically unsaturated monomers containing sulfur atoms in the structure include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, sulfoethyl (meth)acrylate, and sulfo (meth)acrylic acid. Propyl ester, sulfobutyl (meth)acrylate, 2-propenamide-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamide propanesulfonic acid, acrylamide tertiary butyl sulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, vinyl thiophene, etc. These monomers can be used individually by 1 type or in combination of 2 or more types.

Examples of ethylenically unsaturated monomers containing chlorine, bromine or iodine atoms in the structure include vinyl chloride, 4-(chloromethyl)styrene, 2-bromoethyl (meth)acrylate, (methyl) ) 2,3-dibromopropyl acrylate, pentabromobenzyl (meth)acrylate, included in the structure as amines such as trimethyl-2-methacryloxyethyl ammonium chloride, etc. The basic functional group monomer is an ethylenically unsaturated monomer with the chlorine atom, bromine atom or iodine atom of the anion. These monomers can be used individually by 1 type or in combination of 2 or more types.

The content ratio of the repeating unit (a2) is preferably less than 5 parts by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. The upper limit of the content ratio of the repeating unit (a2) is more preferably 3 parts by mass, and particularly preferably 1 part by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. If the content ratio of the repeating unit (a2) is within the aforementioned range, the thermal decomposition property of the polymer (A) is little affected, and good degreasing properties can be maintained. Moreover, since the content of the functional group in the polymer (A) is an appropriate amount, the dispersibility of the inorganic particles in the slurry is good. Moreover, it is also preferable that the polymer (A) does not contain the aforementioned repeating unit (a2).

<Repeating unit derived from methacrylate (a3)> The polymer (A) preferably contains a repeating unit (a3) derived from methacrylate (except for the foregoing repeating unit (a1) and the foregoing repeating unit (a2); hereinafter referred to as "repeating unit (a3)").

The methacrylate can include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl N-Amyl acrylate, isoamyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, nonyl methacrylate, methyl Decyl acrylate, lauryl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 1,10-decanediol dimethacrylate, dimethacrylic acid Ethylene glycol ester, propylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, allyl methacrylate, vinyl ether monomethacrylic acid Esters, propylene glycol monomethacrylate, etc. Among these, it is preferably selected from ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 1,10- One or more of decanediol dimethacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, and propylene glycol monomethacrylate, particularly preferably 2-methacrylic acid 2- Ethoxyethyl. These monomers can be used individually by 1 type or in combination of 2 or more types. In addition, although propylene glycol monomethacrylate is a hydroxyl group-containing monomer, it has little adverse effect on the thermal decomposability, so it is exceptionally regarded as the repeating unit (a2) instead of the repeating unit (a3).

The lower limit of the content ratio of the aforementioned repeating unit (a3) is preferably 5 parts by mass, more preferably 7 parts by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. Preferably it is 10 parts by mass. On the other hand, the upper limit of the content ratio of the repeating unit (a3), when the total amount of the repeating units contained in the polymer (A) is 100 parts by mass, is preferably 99.5 parts by mass, more preferably 70 parts by mass Parts, particularly preferably 50 parts by mass. When the polymer (A) contains the repeating unit (a3) in the aforementioned range, and the glass transition temperature (Tg) of the polymer (A) is suitable, the strength and handling properties of the obtained green sheet can be improved. In addition, the thermal decomposability of the polymer (A) can be improved, and a device with good characteristics can be obtained.

<Repeat unit derived from acrylate (a4)> The polymer (A) may also contain a repeating unit (a4) derived from acrylate (except for the repeating unit (a1) and the repeating unit (a2); hereinafter referred to as "repeating unit (a4)").

Acrylic esters include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, hexyl acrylate, acrylic ring Hexyl ester, 2-ethylhexyl acrylate, n-octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-propylene Acetoxyethyl phthalate, ethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, allyl acrylate, and the like. Among these, preferably one or more selected from ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and 2-propenoxyethyl phthalate, Particularly preferred is n-butyl acrylate.

The lower limit of the content ratio of the repeating unit (a4) is preferably 0.5 parts by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. On the other hand, the upper limit of the content ratio of the repeating unit (a4) is preferably 20 parts by mass, more preferably 10 parts by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. Parts, particularly preferably 5 parts by mass. When the polymer (A) contains the repeating unit (a4) in the aforementioned range, a soft green sheet can be produced, and the handling in the device manufacturing process can be improved. In addition, the influence on the thermal decomposability of the polymer (A) is very slight, and good degreasing properties can be maintained.

<Repeating unit derived from aromatic vinyl compound (a5)> The polymer (A) may also contain a repeating unit (a5) derived from an aromatic vinyl compound (except for the repeating unit (a1) and the repeating unit (a2); hereinafter referred to as "repeating unit (a5)").

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, and divinylbenzene. Among these, styrene and α-methylstyrene are preferred.

The lower limit of the content ratio of the aforementioned repeating unit (a5), when the total amount of repeating units contained in the polymer (A) is 100 parts by mass, is preferably 0 parts by mass, more preferably 5 parts by mass, especially Preferably it is 10 parts by mass. On the other hand, the upper limit of the content ratio of the repeating unit (a5) is preferably 50 parts by mass, more preferably 30 parts by mass when the total amount of repeating units contained in the polymer (A) is 100 parts by mass. Parts, particularly preferably 20 parts by mass. When the polymer (A) contains the repeating unit (a5) in the aforementioned range, the solubility of the polymer (A) in a low-polar solvent can be improved, and a slurry with good dispersibility can be produced.

When the total of the repeating units contained in the polymer (A) is 100 parts by mass, the total amount of the repeating unit (a1), the repeating unit (a3), and the repeating unit (a5) is preferably 90 parts by mass Parts or more, more preferably 92 parts by mass or more, particularly preferably 95 parts by mass or more. If the total amount of the repeating unit (a1), the repeating unit (a3), and the repeating unit (a5) is in the above range, the polymer (A) can exhibit good thermal decomposition properties, and a green sheet with good degreasing properties can be obtained , And it is easy to improve the characteristics of the device.

1.1.2. Physical properties of polymer (A) ＜Weight average molecular weight (Mw)＞ The weight average molecular weight (Mw) of the polymer (A) is 100,000 or more, preferably 300,000 or more, and more preferably 500,000 or more when measured by size exclusion chromatography (SEC) in accordance with JIS K7252. In addition, the upper limit of the weight average molecular weight (Mw) of the polymer (A) is preferably 5,000,000 or less, more preferably 4,000,000 or less, and particularly preferably 3,500,000 or less. If the weight average molecular weight (Mw) of the polymer (A) is in the aforementioned range, the strength of the green sheet can be improved, which is preferable.

＜Glass transition temperature＞ When the polymer (A) is subjected to differential scanning calorimetry (DSC) in accordance with JIS K7121, it is preferable that there is only one endothermic peak in the temperature range of -40°C to 80°C. The temperature of the endothermic peak (that is, the glass transition temperature (Tg)) is preferably in the range of -40°C to 80°C, more preferably in the range of -30°C to 70°C, and particularly preferably in the range of -20°C to 50°C. When there is only one endothermic peak of the polymer (A) in the DSC analysis, and the peak temperature is in the aforementioned range, the green sheet obtained has good flexibility and hot pressure viscosity and is better.

＜Viscosity＞ The viscosity of the polymer (A) with a solid content concentration of 10% varies with the type of solvent, and is preferably 50 to 10,000 mPa･s, more preferably 50 to 8,000 mPa･s, and particularly preferably 100 to 5,000 mPa･s. If the viscosity of the 10% solid content concentration of the polymer (A) is more than the aforementioned lower limit, the dispersibility of the inorganic particles is good, and a homogeneous slurry can be produced, which is preferable. If the viscosity of the polymer (A) with a solid content concentration of 10% is less than the aforementioned upper limit, the coating property of the slurry is good and preferable.

In addition, the viscosity of the polymer (A) with a solid content concentration of 10% is a value measured at a temperature of 25.0°C using a B-type viscometer and in accordance with JIS Z 8803. As the B-type viscometer, for example, "RB-80L" or "TVB-10" manufactured by Toki Sangyo Co., Ltd. can be used.

1.1.3. Synthesis method of polymer (A) The method for synthesizing the polymer (A) is not particularly limited, and it is preferably suspension polymerization in the presence of a well-known chain transfer agent, polymerization initiator, dispersant, etc., in a solvent containing water as the main component.

Specific examples of the chain transfer agent used in the synthesis of the polymer (A) include, for example, n-hexyl mercaptan, n-octyl mercaptan, third octyl mercaptan, n-dodecyl mercaptan, and third- Alkyl mercaptans such as lauryl mercaptan and n-stearyl mercaptan; xanthogen oxygen compounds such as dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide; terpinolene, Tetramethylthiolane disulfide, tetraethylthiolane disulfide, tetramethylthiolane monosulfide and other sulfur blue compounds; 2,6-di-tert-butyl-4-methylphenol, styrene Phenol compounds such as phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; α-benzyloxystyrene, α-benzyloxyacrylonitrile, α- Benzyloxyacrylamide and other vinyl ether compounds, as well as triphenylethane, pentaphenylethane, acrolein, tripolyacrylaldehyde, thioglycolic acid, thiomalic acid, thioglycolic acid 2-ethyl Alkylhexyl ester, α-methylstyrene dimer, etc. These chain transfer agents can be used individually by 1 type or in combination of 2 or more types. The use ratio of the chain transfer agent is preferably less than 1 part by mass, more preferably less than 0.5 part by mass when the total of all monomers used in the polymerization of the aforementioned polymer (A) is 100 parts by mass, It is particularly preferable that it does not contain substantially. If the use ratio of the chain transfer agent is in the aforementioned range, the organic residues during the degreasing step of the green flakes can be further reduced.

Specific examples of the polymerization initiator used in the synthesis of the polymer (A) include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; benzyl peroxide, laurel peroxide Azobis(2-methylpropionic acid) dimethyl ester, 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid) Other oil-soluble polymerization initiators; redox polymerization initiators composed of a combination of reducing agents such as sodium bisulfite, iron (II) salts, tertiary amines, and oxidizing agents such as persulfates or organic peroxides, etc. . These polymerization initiators can be used individually by 1 type or in combination of 2 or more types. The use ratio of the polymerization initiator is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total monomers used.

In addition, when a polymerization initiator introduced with a structure containing a sulfur atom, a nitrogen atom or a carboxyl group as the initiator terminal is used as the polymerization initiator, the use ratio of the polymerization initiator is determined in the polymerization of the aforementioned polymer (A). When the total of all the monomers used is 100 parts by mass, it is preferably less than 1 part by mass, more preferably less than 0.5 part by mass, and particularly preferably not contained substantially. If the use ratio of the polymerization initiator to which a structure containing a sulfur atom, a nitrogen atom, or a carboxyl group is introduced as the initiator terminal is within the aforementioned range, the organic residue during the degreasing step of green chips can be further reduced.

Specific examples of the dispersant used in the synthesis of the polymer (A) include polymer dispersants such as polyvinyl alcohol, polyacrylate, polymethacrylate, polyacrylamide, and cellulose derivatives, or Anionic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, etc. These dispersants can be used individually by 1 type or in combination of 2 or more types. The use ratio of the dispersant is preferably 0.01-10 parts by mass, and more preferably 0.02-5 parts by mass relative to 100 parts by mass of the total monomers used.

The polymerization temperature during the synthesis of the polymer (A) is not particularly limited. If the production time or the conversion rate (reaction rate) of the monomer to the copolymer is considered, it is preferably 30°C to 95°C, more preferably 50°C to 85°C. ℃. In addition, during polymerization, for the purpose of improving the production stability, a pH adjuster, EDTA or a salt thereof as a metal ion chelating agent, etc. may also be used.

1.2. Liquid medium (B) The adhesive composition for green sheet molding of this embodiment contains a liquid medium (B). The liquid medium (B) includes water, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoisobutyl ether. , Trimethylpentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol Acetate, ester alcohol, toluene, ethyl acetate, butyl acetate, ethanol, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, glycol ethyl ether, isophor Ketone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, etc. Among these, terpineol and isopropanol are preferred from the viewpoint of the surface smoothness of the green sheet; and, from the viewpoints of reducing environmental load and reducing the cost of manufacturing equipment, an aqueous medium containing water is preferred, and more preferred For water.

1.3. Other additives The adhesive composition for green sheet molding of this embodiment may contain additives other than the above-mentioned components as required. Examples of such additives include polymers other than the polymer (A), preservatives, tackifiers, and plasticizers.

<Polymers other than polymer (A)> The binder composition for green sheet molding of this embodiment may contain polymers other than the polymer (A). Such polymers are not particularly limited, and examples include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polymethyl methacrylate, polymethacrylate, polyvinylidene chloride, poly Ethylene imine, polymethacrylonitrile, polyimide, polyamide acid, polyimide imine, polyester, polyethylene, polypropylene, polyvinyl acetate, nitrocellulose, polytetrafluoroethylene , Ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer (Na ⁺ ) ion crosslinked body, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid copolymer (Na ⁺ ) ion crosslinked body, ethylene-acrylic acid Methyl ester copolymer, (Na ⁺ ) ion cross-linked body of ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, (Na ⁺ ) ion cross-linked body of ethylene-methyl methacrylate copolymer , Macromolecules composed of monoalkyltrialkoxysilane polymers, macromolecules composed of monoalkyltrialkoxysilane polymers and tetraalkoxysilane monomers, styrene butadiene Rubber (SBR), butadiene rubber (BR), styrene/isoprene copolymer, isobutylene, isoprene copolymer (butyl rubber), ethylene, propylene, and diene copolymer (ethylene-propylene- Diene polymer), acrylonitrile and butadiene copolymer (NBR), hydrogenated styrene butadiene rubber, hydrogenated acrylonitrile and butadiene copolymer, ethylene-propylene-diene (EPDM), sulfide Fluorine-based polymers such as ethylene-propylene-diene compounds, PVDF (polyvinylidene fluoride), etc. These polymers may be used individually by 1 type, and may use 2 or more types together. By containing a polymer other than the polymer (A), the flexibility or adhesion of the green sheet can be further improved.

The content ratio of the polymer (A) in the adhesive composition for green sheet molding of this embodiment is relative to 100 parts by mass of the total of the polymer (A), polymers other than the polymer (A), and tackifier. It is preferably from 10 to 100 parts by mass, more preferably from 30 to 100 parts by mass, and particularly preferably from 50 to 100 parts by mass.

＜Preservatives＞ The adhesive composition for green sheet molding of this embodiment may also contain a preservative. By containing a preservative, when storing the adhesive composition for green sheet molding, it is possible to suppress the growth of bacteria, molds, etc. and the generation of foreign matter. Specific examples of preservatives include compounds described in Japanese Patent No. 5477610 and the like.

＜Tackifier＞ The adhesive composition for green sheet molding of this embodiment may also contain a tackifier. By containing a tackifier, the coatability or the characteristics of the resulting device can be further improved.

Specific examples of the thickener include, for example, cellulose compounds such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose; poly(meth)acrylic acid; the aforementioned cellulose compound or the aforementioned poly (Meth) ammonium salt or alkali metal salt of acrylic acid; polyvinyl alcohol (co)polymer such as polyvinyl alcohol, modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer; (meth)acrylic acid, maleic acid, Water-soluble polymers such as saponified products of copolymers of unsaturated carboxylic acids such as fumaric acid and vinyl esters. Among these, it is preferable to select ethyl cellulose, alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly(meth)acrylic acid, etc., in accordance with the properties of the liquid medium (B).

When the green sheet forming adhesive composition of this embodiment contains a thickener, the content of the thickening agent is preferably 5 parts by mass relative to 100 parts by mass of the total solid content of the green sheet forming adhesive composition Hereinafter, it is more preferably 0.1 to 3 parts by mass.

2. Paste for green sheet forming A slurry system for green sheet molding according to an embodiment of the present invention contains the aforementioned binder composition for green sheet molding, inorganic particles, and a liquid medium. Hereinafter, each component contained in the green sheet forming slurry of this embodiment will be described in detail.

2.1. Adhesive composition for green sheet forming Regarding the adhesive composition for green sheet molding, since it has been described above, its detailed description is omitted. The content of the polymer (A) in the green sheet forming slurry of this embodiment is preferably 1-30% by mass, more preferably 2-25% by mass when the total mass of the slurry is 100% by mass %, particularly preferably 3-20% by mass. By making the content of the polymer (A) within the aforementioned range, sintering at a low temperature can also produce degreasing green flakes.

2.2. Inorganic particles Examples of the inorganic particles include glass powder, ceramic powder, phosphor particles, and metal particles.

The above-mentioned glass powders include, for example, glass powders such as bismuth oxide glass, silicate glass, lead glass, zinc glass, and boron glass, or CaO-Al ₂ O ₃ -SiO ₂ series, MgO-Al ₂ O ₃ -SiO ₂ series , LiO ₂ -Al ₂ O ₃ -SiO ₂ series and other silicon oxide glass powders. In addition, SnO-B ₂ O ₃ -P ₂ O ₅ -Al ₂ O ₃ mixture, PbO-B ₂ O ₃ -SiO ₂ mixture, BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture, ZnO-Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ mixture, Bi ₂ O ₃ -B ₂ O ₃ -BaO-CuO mixture, Bi ₂ O ₃ -ZnO-B ₂ O ₃ -Al ₂ O ₃ -SrO mixture, ZnO- Bi ₂ O ₃ -B ₂ O ₃ mixture, Bi ₂ O ₃ -SiO ₂ mixture, P ₂ O ₅ -Na ₂ O-CaO-BaO-Al ₂ O ₃ -B ₂ O ₃ mixture, P ₂ O ₅ -SnO Mixture, P ₂ O ₅ -SnO-B ₂ O ₃ mixture, P ₂ O ₅ -SnO-SiO ₂ mixture, CuO-P ₂ O ₅ -RO mixture, SiO ₂ -B ₂ O ₃ -ZnO-Na ₂ O- Li ₂ O-NaF-V ₂ O ₅ mixture, P ₂ O ₅ -ZnO-SnO-R ₂ O-RO mixture, B ₂ O ₃ -SiO ₂ -ZnO mixture, B ₂ O ₃ -SiO ₂ -Al ₂ O _{3- ZrO 2} mixture, SiO ₂ -B ₂ O ₃ -ZnO-R ₂ O-RO mixture, SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -RO-R ₂ O mixture, SrO-ZnO-P ₂ O ₅ mixture of glass _{powder, SrO-ZnO-P 2 O} 5 _{mixtures, BaO-ZnO-B 2 O} 3 -SiO 2 mixtures. In addition, R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn. Particularly preferred is a glass powder of a PbO-B ₂ O ₃ -SiO ₂ mixture, or a lead-free BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture or a ZnO-Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ Lead-free glass powders such as mixtures.

The ceramic powder may include, for example, alumina, ferrite, zirconia, zirconium, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, aluminum oxynitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, Cordierite, forsterite, etc. In addition, ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganate, lanthanum strontium cobalt ferrite, yttrium stabilized zirconia, gamma-doped cerium oxide, nickel oxide, lanthanum chromium, etc. can also be used.

As the phosphor particles, for example, a blue phosphor material, a red phosphor material, a green phosphor material, etc., which are conventionally known as phosphor materials for displays, can be used. For the blue phosphor material, for example, MgAl ₁₀ O ₁₇ : Eu-based, Y ₂ SiO ₅ : Ce-based, CaWO ₄ : Pb-based, BaMgAl ₁₄ O ₂₃ : Eu-based, BaMgAl ₁₆ O ₂₇ : Eu-based, BaMg ₂ Al ₁₄ O ₂₃ : Eu system, BaMg ₂ Al ₁₄ O ₂₇ : Eu system, ZnS: (Ag, Cd) system. As the red phosphor material, for example, Y ₂ O ₃ : Eu-based, Y ₂ SiO ₅ : Eu-based, Y ₃ Al ₅ O ₁₂ : Eu-based, Zn ₃ (PO ₄ ) ₂ : Mn-based, YBO ₃ : Eu system, (Y,Gd)BO ₃ : Eu system, GdBO ₃ : Eu system, ScBO ₃ : Eu system, LuBO ₃ : Eu system. For the green phosphor material, for example, Zn ₂ SiO ₄ : Mn based, BaAl ₁₂ O ₁₉ : Mn based, SrAl ₁₃ O ₁₉ : Mn based, CaAl ₁₂ O ₁₉ : Mn based, YBO ₃ : Tb based, BaMgAl ₁₄ O ₂₃ : Mn-based, LuBO ₃ : Tb-based, GdBO ₃ : Tb-based, ScBO ₃ : Tb-based, Sr ₆ Si ₃ O ₃ Cl ₄ : Eu-based. In addition, ZnO: Zn series, ZnS: (Cu, Al) series, ZnS: Ag series, Y ₂ O ₂ S: Eu series, ZnS: Zn series, (Y, Cd) BO ₃ : Eu series can also be used , BaMgAl ₁₂ O ₂₃ : Eu system.

Examples of the metal particles include powders composed of nickel, palladium, platinum, gold, silver, aluminum, tungsten, or alloys thereof. In addition, metals such as copper or iron, which have good adsorption properties for carboxyl groups, amino groups, amide groups, and the like, are easily oxidized. These metal powders may be used singly, or two or more of them may be used in combination. In addition to metal complexes, various carbon blacks, carbon nanotubes, etc. can also be used.

The above-mentioned inorganic particles may contain lithium. Specific examples include low melting point glasses such as _{LiO 2} ·Al ₂ O ₃ ·SiO _{2 based inorganic glasses, lithium chalcogenide glasses such as Li 2} SM _x S _y (M=B, Si, Ge, or P), and lithium such as _{LiCoO 2} Cobalt composite oxides, LiMnO ₄ and other lithium manganese composite oxides, lithium nickel composite oxides, lithium vanadium composite oxides, lithium zirconium composite oxides, lithium hafnium composite oxides, lithium silicophosphate (Li _3.5 Si _0.5 P _0.5 O ₄ ), lithium titanium phosphate (LiTi ₂ (PO ₄ ) ₃ ), lithium vanadium phosphate (Li ₃ V ₂ (PO ₄ ) ₃ ), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), Li _4/3 Ti _5/3 O ₄ , LiCoO ₂ , lithium germanium phosphate (LiGe ₂ (PO ₄ ) ₃ ), Li ₂ -SiS series glass, Li ₄ GeS ₄ -Li ₃ PS ₄ series glass, LiSiO ₃ , LiMn ₂ O ₄ , Li ₂ SP ₂ S ₅ series glass, ceramics, Li ₂ O-SiO ₂ , Li ₂ OV ₂ O ₅ -SiO ₂ , LiS-SiS ₂ -Li ₄ SiO ₄ series glass, LiPON plasma conductive oxide, Li ₂ OP ₂ O _5- Lithium oxide compounds such as B ₂ O ₃ , Li ₂ O-GeO _{2 Ba, Li x} Al _y Ti _z (PO ₄ ) ₃ series glass, La _x Li _y TiO _z series glass, Li _x Ge _y P _z O ₄ series glass , Li ₇ La ₃ Zr ₂ O ₁₂ series glass, Li _v Si _w P _x S _y Cl _z series glass, LiNbO ₃ and other lithium niobium oxides, Li-β-alumina and other lithium alumina compounds, Li ₁₄ Zn(GeO ₄ ) _4th grade lithium zinc oxide, etc.

When such inorganic particles are used as an electrode active material or a solid electrolyte, the average particle diameter is preferably 0.05 to 50 μm. The average particle diameter of the inorganic particles referred to herein refers to the volume average particle diameter calculated from the particle size distribution measured by a particle size distribution measuring device using a laser diffraction method as the measurement principle. Examples of such laser diffraction particle size distribution measuring devices include HORIBA LA-300 series and HORIBA LA-920 series (the above are manufactured by Horiba Manufacturing Co., Ltd.). In addition, when inorganic particles are used as the electrode active material, there is no clear distinction between the positive electrode active material and the negative electrode active material. For example, comparing the charge and discharge potentials of two compounds and using the higher potential for the positive electrode, the display will be lower. The potential is used for the negative electrode, which can form a battery of any voltage.

The content of the inorganic particles in the green sheet forming slurry of the present embodiment has a preferred lower limit of 10% by mass and a preferred upper limit of 90% by mass relative to the total solid content of the slurry. By setting it to 10% by mass or more, it is possible to form a material having sufficient viscosity and excellent coating properties; by setting it to be 90% by mass or less, it is possible to form a material having excellent dispersibility of inorganic particles.

2.3. Liquid medium The liquid medium is not particularly limited, but it is preferably one that is excellent in coating properties, drying properties, dispersibility of inorganic particles, and the like when producing green sheets.

Specific examples of the liquid medium include ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoethyl ether Methyl pentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetic acid Ester, ester alcohol, toluene, ethyl acetate, butyl acetate, ethanol, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethyl glycol ether, isophorone , Butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol. Moreover, these liquid media may be used individually by 1 type, and may use 2 or more types together. In addition, an aqueous medium containing water or the like can also be used.

The content of the liquid medium in the green sheet forming slurry of the present embodiment, when the total solid content of the slurry is 100 parts by mass, the preferred lower limit is 50 parts by mass, and the preferred upper limit is 250 parts by mass. By setting the content of the liquid medium within the aforementioned range, a slurry having good coating properties to the substrate and dispersibility of inorganic particles can be obtained.

2.4. Plasticizer The green sheet forming slurry of this embodiment may contain a plasticizer if necessary. In the green sheet forming slurry of this embodiment, it is preferable to use di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, and triethylene glycol bis(2-ethane). Hexanoate), triethylene glycol dihexanoate, tributyl acetyl citrate, dibutyl phthalate, dibutyl sebacate and other plasticizers. By using these plasticizers, the amount of plasticizer added can be reduced compared to when using general plasticizers.

The content of the plasticizer in the green sheet forming slurry of this embodiment has a preferred lower limit of 0.1% by mass and a preferred upper limit of 3% by mass relative to the total solid content of the slurry. By making the content of the plasticizer within the aforementioned range, the organic residue during the degreasing step of the green flakes can be further reduced.

2.5. Other additives In addition to the above-mentioned components, the slurry for green sheet molding of this embodiment may also contain additives such as flame retardant additives, tackifiers, defoamers, leveling agents, adhesion promoters, etc., if necessary.

2.6. Manufacturing method The manufacturing method of the green sheet forming slurry of this embodiment is not particularly limited, and conventionally well-known methods can be mentioned, including various mixers using ball mills, bead mills, blending mills, three-roll mills, etc. The method of mixing the ingredients.

3. Green film and device The green sheet of one embodiment of the present invention is formed by coating the above-mentioned green sheet forming slurry on a substrate and drying it. Specifically, a method of coating the above-mentioned green sheet molding slurry on a support film subjected to a single-sided mold release treatment, and drying the liquid medium to shape it into a sheet shape.

The support film is preferably a resin film having heat resistance and solvent resistance and flexibility. The permeable support film has flexibility, and the slurry can be applied to the surface of the support film by a roll coater, a knife coater, etc., and the obtained sheet can be stored and supplied in a state wound into a roll.

The material of the support film can include, for example, polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyvinyl fluoride and other fluorine-containing materials. Resin, nylon, cellulose, etc. The thickness of the support film is preferably, for example, 20 μm to 100 μm. In addition, it is preferable to perform a mold release treatment on the surface of the support film. Thereby, the peeling operation of the support film can be easily performed.

The device of an embodiment of the present invention is made of the above-mentioned green sheet. For example, the above-mentioned green sheet can be used as a dielectric green sheet, and a conductive paste can be further used to manufacture a multilayer ceramic capacitor.

A specific example of the manufacturing method of the above-mentioned multilayer ceramic capacitor includes: a step of printing and drying the conductive paste on the above-mentioned green sheet to produce a dielectric green sheet; and a method of laminating the above-mentioned dielectric sheet. The conductive paste is a paste composition containing conductive powder, binder resin, and liquid medium.

The material of the conductive powder is not particularly limited as long as it has conductivity, and examples include nickel, palladium, platinum, gold, silver, copper, and alloys of these. These conductive powders may be used singly, or two or more of them may be used in combination. In addition, the binder resin and the liquid medium are not particularly limited, and the same ones as the above-mentioned green sheet-forming binder composition or the above-mentioned green sheet-forming slurry can be used. It is particularly preferable to use the above-mentioned polymer (A) as a binder resin.

The method of printing the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die coating printing method, a planographic printing method, a gravure printing method, and an inkjet printing method.

Furthermore, by using the above-mentioned green sheet as the positive electrode, solid electrolyte and negative electrode material of the all solid state battery, an all solid state battery can be manufactured. The layered system of all solid-state batteries consists of a single cell composed of a positive electrode layer, a solid electrolyte layer and a negative electrode layer. The positive electrode layer is arranged on one side of the solid electrolyte layer, and the negative electrode layer is arranged on the other side of the solid electrolyte layer. In other words, the positive electrode layer and the negative electrode layer are arranged at positions facing each other with the solid electrolyte interposed therebetween. In addition, the positive electrode layer includes a solid electrolyte and a positive active material, the negative electrode layer includes a solid electrolyte and a negative active material, and the solid electrolyte layer includes a solid electrolyte. At least one of the positive electrode layer and the negative electrode layer contains carbon or the like as a conductive agent.

In order to manufacture the all-solid-state battery laminate, firstly: a first molded body formed of a slurry containing any one of the positive electrode active material and the negative electrode active material and the binder composition for green sheet molding, and A second molded body formed of a slurry containing a solid electrolyte and the aforementioned binder composition for green sheet molding (a molded body preparation step). Here, the adhesive composition used in the production of the first molded body and the adhesive composition used in the production of the second molded body may be the same composition or different compositions.

Next, the first molded body and the second molded volume layer are formed into a laminated molded body (a laminated molded body production step). Thereafter, the obtained laminated compact is fired to form a laminated fired body composed of an electrode layer and a solid electrolyte layer (layer fired body forming step). In this way, a formed body is produced from the slurry, and the formed volume layers of the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are formed into a laminated molded body, and the laminated molded body is fired to produce a laminated body of an all-solid battery.

The laminated fired body may be a laminated body of a single cell structure formed by laminating a positive electrode layer, a solid electrolyte layer, and a negative electrode, or a laminated body in which a plurality of laminated bodies of the above single cell structure are laminated via a current collector layer. . At this time, a stack of a plurality of single cell structures can also be stacked electrically in series or in parallel. The method of forming the above-mentioned molded body is not particularly limited, and die coating, chipped wheel coating, screen printing, etc. can be used. The method of forming the volume layer is not particularly limited, and the volume layer can be formed using a hot equalization method, a cold equalization method, and an equalization method.

4. Example The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. The "parts" and "%" in the examples and comparative examples are quality standards unless otherwise stated first.

4.1. Example 1 4.1.1. Synthesis and physical property evaluation of polymer (A) ＜Synthesis of polymer (A)＞ 20 parts by mass of 2-methacryloxyethyl phthalate, 80 parts by mass of 2-ethylhexyl methacrylate, and 2,2'-azobis(2-methylpropionic acid) were mixed A homogeneous solution of 2 parts by mass of dimethyl ester was added to 900 parts by mass of a 0.1% polyvinyl alcohol aqueous solution, and stirred with a homomixer at 500 rpm for 30 minutes. This dispersion liquid was put in a separable flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux cooler, and was heated at 70° C. for 4 hours under a nitrogen stream to perform polymerization. After the polymerization is completed, if it is left to cool, the reaction system separates into two layers of polymer and transparent water, and the emulsified polymer is hardly seen. This was filtered with a suction filter, and polymer particles were taken out, washing and filtering were repeated, and further dried to obtain 80 parts by mass of a polymer (A). With respect to the obtained polymer (A), the weight average molecular weight (Mw), glass transition temperature (Tg), and thermal decomposition residue were measured according to the following methods.

<Measurement of weight average molecular weight (Mw)> With respect to the polymer (A) obtained above, the weight average molecular weight (Mw) was calculated according to the size exclusion chromatography (SEC) according to JIS K7252. The measurement conditions are as follows. The results are shown in Table 1. (Measurement conditions) ・Measuring instrument: GPC manufactured by TOSOH Co., Ltd. (Model: HLC-8220) ・Column: TSKgel guardcolum HHR (manufactured by TOSOH Co., Ltd.), TSK-GEL GMHHR-H (manufactured by TOSOH Co., Ltd.) ・Eluent: THF ・Calibration line: standard polystyrene ・Measurement method: After dissolving the polymer (A) in the eluent so that the concentration of the polymer (A) becomes 0.3wt%, add 2mL methanol and 2mL trimethylsilyldiazomethane (10% Hexane solution). After that, the solution was stirred for 5 hours, filtered with a filter paper having a pore size of 1 μm, and measurement was started.

＜Measurement of glass transition temperature (Tg)＞ The polymer (A) obtained above was measured using a differential scanning calorimeter (DSC204F1 Phoenix manufactured by NETZSCH) in accordance with JIS K7121, and an endothermic peak of the polymer (A) was observed at 4°C.

<Measurement of thermal decomposition residue> For the polymer (A) obtained above, Hitachi High- The differential thermogravimetric simultaneous measuring device "STA7200RV" manufactured by Technologies, Inc., is heated from room temperature to 400°C at a temperature increase rate of 10°C/min in a nitrogen environment, and then maintained at 400°C for 1 hour. The sample tank before and after the test As a result of calculating the residual rate from the weight change, the polymer residue was 0.03%.

4.1.2. Modulation of conductive paste The adhesive composition (1) was prepared by dissolving the polymer (A) obtained above in an isopropanol solvent so that the solid content concentration became 10% by mass. With respect to 44 parts by mass of the adhesive composition (1) thus obtained, 55 parts by mass of nickel powder as a conductive powder and 1 part by mass of oleic acid as a dispersant were added and mixed with a three-roll mill to obtain conductive paste.

4.1.3. Production of ceramic green sheets The polymer (A) obtained above was dissolved in a butyl acetate solvent so that the solid content concentration became 7.5% by mass to prepare the adhesive composition (2). To 67 parts by mass of the adhesive composition (2) thus obtained, 32 parts by mass of barium titanate (average particle size 0.2μm) as inorganic particles and 1 part by mass of dibutyl phthalate as plasticizer are added , Use a ball mill to mix to obtain green sheet forming slurry. This green sheet forming slurry was coated on a polyester film with a mold release treatment to a thickness of 1μm after drying. After drying at room temperature for 1 hour, use a hot air dryer at 80°C for 3 hours, and then It was dried at 120°C for 2 hours to make ceramic green sheets.

4.1.4. Production of ceramic fired body On one side of the ceramic green sheet obtained above, the conductive paste obtained above is coated by a screen printing method to a thickness of 1.5 μm after drying, and then dried to form a conductive layer, and A ceramic green sheet with a conductive layer is obtained. The resulting ceramic green sheet with the conductive layer formed was cut into 5 cm squares, 100 sheets were stacked, and heated and pressure-bonded under the conditions of ^{a temperature of 70° C. and a pressure of 150 kg/cm 2 for 10 minutes to obtain a laminate.} The resultant layered body was heated to 400°C at a heating rate of 3°C/min under a nitrogen atmosphere, and after holding for 5 hours, it was heated to 1350°C at a heating rate of 5°C/min and held for 10 hours to produce a ceramic fired body.

4.1.5. Production of all-solid-state batteries <Production of slurry for positive and negative electrodes> The lithium-containing germanium phosphate compound (LAGP: Li _1.5 Al _0.5 Ge _1.5 (PO) with a sodium superion conductor (NASICON) type structure as a solid electrolyte ₄ ) _{3 ) 50 parts by mass of powder, 45 parts by mass of powder having a crystalline phase of Li 3} V ₂ (PO ₄ ) ₃ as an electrode active material, 5 parts by mass of carbon powder as a conductive agent, and a solid content equivalent to 4 The above-obtained binder composition (2) and a spherical medium made of zirconia with a diameter of 1 mm are sealed in a container together by mass parts and the container is rotated, and then the spherical medium is taken out to prepare a slurry for positive and negative electrodes.

＜Production of slurry for solid electrolyte＞ After 100 parts by mass of LAGP powder as a solid electrolyte and 4 parts by mass of the solid content of the binder composition (2) obtained above and a spherical medium made of zirconia with a diameter of 1 mm are sealed in a container and the container is rotated, The spherical medium is taken out to prepare a slurry for solid electrolyte.

＜Production of ceramic green sheet for all solid-state batteries＞ The positive and negative electrode slurry obtained above was coated on a polyethylene terephthalate (PET) film by a doctor blade method, and dried at 120° C. for 2 hours using a hot air dryer to form a ceramic green sheet. The electrode green sheet was formed by forming it into a thin sheet with a thickness of 50 μm and punching it into a disk shape with a diameter of 30 mm.

In addition, the solid electrolyte slurry obtained above was coated on a PET film by a doctor blade method, and formed into a sheet shape with a thickness of 30 μm, and punched into a disc shape with a diameter of 31 mm to form a solid electrolyte green sheet. .

＜Production of green sheet laminate for all solid-state batteries＞ Four solid electrolyte green sheets peeled from the PET film were laminated and laminated to form a solid electrolyte layer by applying pressure at a temperature of 60°C to form a solid electrolyte layer. The reason for laminating multiple solid electrolyte green sheets is that sufficient mechanical strength can be imparted to the solid electrolyte layer after firing, making the handling of the solid electrolyte layer in the following steps easier; even if multiple solid electrolytes are not laminated There is no major problem with the formation of a solid electrolyte layer from green sheets.

Next, a green sheet of the electrode peeled from the PET film was laminated on one side of the solid electrolyte layer obtained above, and press-bonded at a temperature of 60°C to form a positive electrode layer. In the same way, two electrode sheets were pressure-bonded on the opposite side of the solid electrolyte layer to form a negative electrode layer. In this way, a green sheet laminate for all-solid-state batteries is produced.

In addition, the reason for the difference in the number of electrode sheets used in the positive electrode layer and the negative electrode layer is that when Li ₃ V ₂ (PO ₄ ) _{3 is} used as a positive electrode active material and when used as a negative electrode active material, Li _{3 is considered.} The capacity per unit weight (gram) of V ₂ (PO ₄ ) _{3 is about 2 times different.} In addition, the thickness of the positive electrode layer and the negative electrode layer can be appropriately changed according to the material of the electrode active material used.

＜Sintering of green sheet laminates for all solid-state batteries＞ The polymer material is removed by heat-treating the green sheet laminate for all-solid-state batteries obtained above in an air environment at a temperature of 500°C (first firing step). Thereafter, the laminated body was sintered by heat treatment at a temperature of 900° C. in a nitrogen atmosphere to obtain a laminated sintered body (second sintering step).

＜Production of all solid-state batteries＞ On the negative electrode layer side of the produced laminated sintered body, a copper foil with a thickness of 25 μm and a wire with a width of 5 mm attached to a circle with a diameter of 25 mm was arranged to form a negative electrode. Similarly, an aluminum foil with a thickness of 25 μm and a wire with a width of 5 mm attached to a circle with a diameter of 25 mm was arranged on the side of the positive electrode layer to form a positive electrode. The aluminum laminate film is used for vacuum packaging to ensure the contact between the laminate sintered body and the copper foil and aluminum foil to form an all-solid-state battery.

4.1.6. Evaluation method ＜Evaluation of residual carbon＞ The ceramic green flakes and solid electrolyte green flakes obtained above were fired in an electric furnace at 500° C. for 1 hour. A carbon-sulfur analyzer (manufactured by Horiba, Ltd.) was used to measure residual carbon (ppm). When the residual carbon is less than 200 ppm, it is rated as "A", and when the residual carbon is more than 200 ppm, it is rated as "B".

＜Assessment of green sheet winding ability＞ Cut out a test piece of 2 cm wide x 12 cm long from the ceramic green sheet and solid electrolyte green sheet obtained above, abut the current collector side of the test piece against the SUS shaft with a diameter of 2 mmφ, and observe the top and bottom with an optical microscope The state of the coating layer when rubbed three times was evaluated for cracks in the coating layer according to the following four-level evaluation criteria. In this test, the less cracks in the coating layer, the higher the flexibility of the electrode plate. In addition, it is known that the flexibility of the electrode plate has a great correlation with the abrasion resistance or powder falling resistance; this evaluation test can also be used to evaluate the abrasion resistance or powder falling resistance of the electrode plate. (Assessment criteria) AA: No cracking of the coating layer is seen. A: Slight cracks are seen at the end of the coating layer. B: Cracks are seen only at the ends of the coating layer. C: Cracks are seen on the entire surface of the coating layer.

＜Battery characteristics evaluation of all solid-state batteries＞ The charge-discharge test of the all-solid-state battery obtained above was carried out, and the discharge capacity was measured. It is charged with a charging current of 50μA to a voltage of 4.5V (after the voltage reaches 4.5V, it is maintained at a voltage of 4.5V for 3 hours), and discharged with a discharge current of 50μA to a voltage of 3V. (Assessment criteria) AA: 100μAh or more and 150μAh or less. A: 50 μAh or more and less than 100 μAh. B: 10 μAh or more and less than 50 μAh. C: Cannot be operated with a secondary battery.

4.2. Examples 2-9, Comparative Examples 1-5 Except that the polymer of the polymer composition shown in Table 1 below was synthesized in the same manner as in the above-mentioned Example 1 <Synthesis of polymer (A)>, the adhesive composition was produced in the same manner as in the above-mentioned Example 1, Green sheets and all-solid-state batteries were evaluated in the same manner as in Example 1 above.

4.3. Evaluation results Table 1 below shows the polymer composition, each physical property value, and each evaluation result used in Examples 1-9 and Comparative Examples 1-5.

It can be seen from the results in Table 1 that according to the adhesive composition containing the polymer (A) shown in Examples 1-9, the polymer residue during thermal decomposition is extremely small, and the residual carbon during degreasing of the green sheet is also low. Show good battery characteristics. In addition, the intensity of the green film is also extremely high. As described above, with regard to Examples 1 to 9, the effect of the polymer (A) having an aromatic carboxylic acid structure resulted in improved thermal decomposition characteristics and green sheet strength.

On the other hand, although the green sheet strength of the adhesive compositions of Comparative Examples 1 to 3 is high, the thermal decomposition of the polymer is poor, and this will also adversely affect the battery characteristics. In addition, regarding the adhesive composition of Comparative Example 4, although the thermal decomposability of the polymer was good, the strength of the green sheet was extremely weak, and even the device could not be fabricated. Furthermore, the adhesive composition of Comparative Example 5 is a case in which the content of the chain transfer agent is changed to 1 part by mass in the composition of Comparative Example 4. It can be seen that the thermal decomposability of the polymer deteriorates, and the green sheet strength is also extremely high. The state of weakness.

It is well known that if a highly polar functional group is introduced into the polymer, the green sheet strength will increase due to the increased interaction with the filler, and the thermal decomposability will deteriorate, resulting in an increase in residual carbon. The reason is that since the highly polar chemical structure is thermally unstable, various side reactions occur before the polymer main chain is depolymerized to form a structure that is not easily thermally decomposable. Especially for carboxylic acids, it is believed that after decarbonation occurs, it is easy to form a structure that is not easily thermally decomposable; and for aromatic carboxylic acids, because the structure of the decarbonation part is an extremely stable structure of an aromatic ring, the reaction only stops at decarbonization. , And it is determined that it will not produce a structure that is not easily thermally decomposable. Therefore, the polymer (A) having an aromatic carboxylic acid structure has good thermal decomposition characteristics.

In addition, it can be seen that the main chain skeleton that does not have depolymerization, such as the acrylic esters of Comparative Examples 1 to 3, also has an adverse effect on the thermal decomposition property. Therefore, in order to have both the strength of the green sheet and the battery characteristics, as shown in Examples 1-9, all functional group structures or main chain skeletons can be taken into consideration. In this regard, it is the reason why the present invention is superior to the conventional adhesive composition for green sheets.

Furthermore, since the polymer (A) described in the examples of the present case can be obtained by simple radical polymerization, it is also advantageous that high-productivity polymerization methods such as suspension polymerization, solution polymerization, and emulsion polymerization can be used.

The present invention is not limited to the above-mentioned embodiment, and various modifications can be applied. The present invention includes substantially the same configuration as the configuration described in the embodiment (for example, the function, method, and result are the same configuration, or the purpose and effect are the same configuration). In addition, the present invention includes a configuration in which the non-essential part of the configuration described in the above embodiment is replaced with another configuration. In addition, the present invention also includes a configuration that can achieve the same function and effect as the configuration described in the above embodiment or a configuration that can achieve the same purpose. Furthermore, the present invention also includes a configuration in which the conventional technology is added to the configuration described in the above-mentioned embodiment.

Claims (14)

An adhesive composition for green sheet forming, wherein: It contains polymer (A) and liquid medium (B), The aforementioned polymer (A) contains a repeating unit (a1) derived from an aromatic carboxylic acid having an ethylenically unsaturated group, The weight average molecular weight (Mw) of the aforementioned polymer (A) is 100,000 or more. The adhesive composition for green sheet molding according to claim 1, wherein the aforementioned aromatic carboxylic acid having an ethylenically unsaturated group includes a compound represented by the following general formula (1):

(In the above formula (1), R ¹ to R ⁵ each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a substituted or unsubstituted hydrocarbon group, or R ² and R ³ are combined with each other to share the same carbon atom to which they are bonded It constitutes a part of a ring structure with 3 to 6 ring members; ^{however, at least one of R 1} to R ⁵ is a substituted or unsubstituted hydrocarbon group having an ethylenically unsaturated group). Such as the adhesive composition for green sheet forming of claim 1 or 2, in which, The aforementioned polymer (A) contains a structure selected from the group consisting of carboxyl groups, hydroxyl groups, nitrogen-containing functional groups, phosphorus atoms, sulfur atoms, chlorine atoms, bromine atoms, iodine atoms, alkali metals, alkaline earth metals, and transition metals. The content ratio of the repeating unit (a2) derived from at least one type of ethylenically unsaturated monomer (excluding the aforementioned aromatic carboxylic acid and polyalkylene glycol monomethacrylate having ethylenically unsaturated groups), When the total of the repeating units contained in the aforementioned polymer (A) is 100 parts by mass, it is less than 5 parts by mass. The adhesive composition for forming green sheets according to any one of claims 1 to 3, wherein: The aforementioned polymer (A) further contains a repeating unit (a3) derived from methacrylate (except for the aforementioned repeating unit (a1) and the aforementioned repeating unit (a2)) and a repeating unit (a5) derived from an aromatic vinyl compound ) (Except for the aforementioned repeating unit (a1) and the aforementioned repeating unit (a2)), When the total of the repeating units contained in the polymer (A) is 100 parts by mass, the total of the repeating unit (a1), the repeating unit (a3), and the repeating unit (a5) is 90 parts by mass or more . The adhesive composition for green sheet molding according to any one of claims 1 to 4, wherein when the polymer (A) is polymerized, the total of all monomers used in the polymer (A) is set When it is 100 parts by mass, the amount of the polymerization initiator that introduces a structure containing a sulfur atom, a nitrogen atom or a carboxyl group as the end of the initiator is less than 1 part by mass. The adhesive composition for green sheet molding according to any one of claims 1 to 5, wherein when the polymer (A) is polymerized, the total of all monomers used in the polymer (A) is set When it is 100 parts by mass, the amount of chain transfer agent is less than 1 part by mass. The adhesive composition for green sheet molding according to any one of claims 1 to 6, wherein the aforementioned polymer (A) is measured at -40°C to 80°C when differential scanning calorimetry (DSC) is performed in accordance with JIS K7121 The endothermic peak can be observed in the temperature range. The adhesive composition for forming green sheets according to any one of claims 1 to 7, which is used for forming all-solid-state batteries. A slurry for forming green sheets, which contains the binder composition for forming green sheets according to any one of claims 1 to 8, inorganic particles, and a liquid medium. The slurry for forming green sheets according to claim 9, wherein the aforementioned inorganic particles contain at least one element selected from lithium and titanium. A green sheet is formed by coating the green sheet forming slurry of claim 9 or 10 on a substrate and drying it. A device made of the green sheet of claim 11. A method for manufacturing green sheets, which comprises the steps of coating and drying the green sheet forming slurry of claim 9 or 10 on a substrate. A method of manufacturing a device, which uses the green sheet manufacturing method of claim 13 to manufacture the device.