WO2024048303A1

WO2024048303A1 - (meth)acrylic resin particles, vehicle composition, slurry composition, and method for manufacturing electronic components

Info

Publication number: WO2024048303A1
Application number: PCT/JP2023/029724
Authority: WO
Inventors: 丈大塚; 健司山内
Original assignee: 積水化学工業株式会社
Priority date: 2022-08-30
Filing date: 2023-08-17
Publication date: 2024-03-07

Abstract

The present invention provides (meth)acrylic resin particles that have excellent low-temperature decomposition properties, and when used as a binder for dispersing inorganic particles, are capable of preventing deterioration caused by oxidation of inorganic particles such as copper, and can be used to manufacture an inorganic-particle-dispersed slurry composition that has particularly excellent dispersibility of fine inorganic particles. In addition, provided are (meth)acrylic resin particles that, by being used as a binder for external electrodes of a layered ceramic capacitor, enable manufacture of a layered ceramic capacitor having excellent reliability. Furthermore, provided are a vehicle composition, a slurry composition, and a method for manufacturing electronic components. The (meth)acrylic resin particles of the present invention have a weight average molecular weight of 100,000-1,000,000 and a weight concentration of S atoms of 0.03-2.50 wt%.

Description

(Meth)acrylic resin particles, vehicle composition, slurry composition, and method for producing electronic components

The present invention relates to (meth)acrylic resin particles, vehicle compositions, slurry compositions, and methods for producing electronic components.

2. Description of the Related Art Multilayer ceramic capacitors are known to have a structure including a laminate in which a plurality of dielectric layers and internal electrodes are alternately stacked, and a pair of external electrodes provided to sandwich the laminate. The external electrodes are formed by applying a conductive paste for external electrodes on the surface of the laminate and sintering the paste.

In recent years, with the miniaturization of multilayer ceramic capacitors, the inorganic particles used for external electrodes have also been miniaturized. Fine inorganic particles tend to aggregate in the paste, and when agglomeration occurs, voids tend to remain during the degreasing and firing processes, and when made into a multilayer ceramic capacitor, the dispersibility of the inorganic particles decreases, resulting in problems with the product. This causes deterioration of electrical characteristics.

As the binder resin used for the external electrode, for example, ethyl cellulose is generally used. For example, Patent Document 1 discloses a method for efficiently dispersing ceramic powder in a configuration using these binders. Specifically, a method is disclosed in which ceramic powder such as calcium titanate is primarily crushed in a solvent such as ethanol, and then a resin such as polyvinyl butyral resin or ethyl cellulose resin is added.
Further, Patent Document 2 discloses a method using an acrylic resin or the like as a binder.

JP2011-84433A JP 2021-111525 Publication

However, the polyvinyl acetal resin described in Patent Document 1 has a problem that it has a high decomposition temperature and cannot be applied to applications where low-temperature firing is desirable, for example, applications using easily oxidized metals such as copper or low-melting glass.
Further, Patent Document 2 describes the use of an acrylic resin, but when using fine inorganic particles with an average particle diameter of less than 1 μm, there is a problem that the dispersibility deteriorates. Furthermore, the acrylic resin described in Patent Document 2 has a problem in that it deteriorates due to oxidation during degreasing, which requires a high firing temperature.

The present invention is an inorganic particle that has excellent low-temperature decomposition properties, can prevent deterioration due to oxidation of inorganic particles such as copper when used as a binder for dispersing inorganic particles, and has particularly excellent dispersibility of fine inorganic particles. An object of the present invention is to provide (meth)acrylic resin particles that can be used to prepare a dispersed slurry composition. Another object of the present invention is to provide (meth)acrylic resin particles that can be used as a binder for the external electrodes of a multilayer ceramic capacitor to produce a multilayer ceramic capacitor with excellent reliability. Furthermore, it is an object to provide vehicle compositions, slurry compositions, and methods of manufacturing electronic components.

The present disclosure (1) is (meth)acrylic resin particles having a weight average molecular weight of 100,000 to 1,000,000 and a weight concentration of S atoms of 0.03 to 2.50 weight%.
The present disclosure (2) is the (meth)acrylic resin particles of the present disclosure (1) in which the weight concentration of COOH groups is 0.06% by weight or more and 3.00% by weight or less.
The present disclosure (3) is the (meth)acrylic resin particles of the present disclosure (1) or (2), in which the weight concentration of K atoms is 0.010% by weight or more and 1.000% by weight or less.
The present disclosure (4) is (meth)acrylic resin particles in any combination with any of the present disclosures (1) to (3), in which the content of a component derived from an acrylic monomer is 5% by weight or less.
The present disclosure (5) is (meth)acrylic resin particles in any combination with any of the present disclosures (1) to (4), which have an average particle diameter of 0.1 μm or more and 1.0 μm or less.
The present disclosure (6) is a vehicle composition containing the (meth)acrylic resin particles according to any one of the present disclosures (1) to (5) and a solvent containing an organic solvent.
The present disclosure (7) is the vehicle composition of the present disclosure (6), wherein the solvent further contains water in an amount of 100 ppm to 40,000 ppm by weight.
The present disclosure (8) provides the present disclosure (6), wherein the organic solvent contains a compound having two or more OH groups, and the content of the compound having two or more OH groups in the solvent is 10% by weight or more and 50% by weight or less. ) or (7).
The present disclosure (9) is a slurry composition containing the vehicle composition of any of the present disclosures (6) to (8), inorganic particles, and a dispersant.
The present disclosure (10) is a method for manufacturing an electronic component using the slurry composition of the present disclosure (9).
The present invention will be explained in detail below.

The present inventors have discovered that (meth)acrylic resin particles having a predetermined weight average molecular weight and weight concentration of S atoms have excellent low-temperature decomposition properties, and when used as a binder for dispersing inorganic particles, they can oxidize inorganic particles such as copper. We have found that deterioration caused by Furthermore, it has been found that by using such a (meth)acrylic resin, an inorganic particle-dispersed slurry composition having particularly excellent dispersibility of fine inorganic particles can be obtained. Furthermore, the inventors have discovered that by using such (meth)acrylic resin particles as a binder for the external electrodes of a multilayer ceramic capacitor, a multilayer ceramic capacitor with excellent reliability can be produced, and the present invention has been completed.

The (meth)acrylic resin particles have a weight average molecular weight (Mw) of 100,000 or more and 1,000,000 or less.
By setting it as the said range, when it forms an inorganic particle dispersion slurry composition, the dispersibility of inorganic particles can be improved. In addition, it has sufficient viscosity and printability can be improved.
The weight average molecular weight (Mw) is preferably 150,000 or more, particularly preferably 170,000 or more. Further, the weight average molecular weight (Mw) is preferably 900,000 or less, more preferably 800,000 or less, even more preferably 700,000 or less, and particularly preferably 500,000 or less.
Furthermore, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth)acrylic resin particles is preferably 8 or less, more preferably 6 or less, and even more preferably 5 or less.
The above weight average molecular weight (Mw) and the above number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and are obtained by performing GPC measurement using, for example, column LF-804 (manufactured by Showa Denko) as a column. be able to.

The weight concentration of S atoms contained in the (meth)acrylic resin particles is 0.03% by weight or more and 2.50% by weight or less.
By setting it within the above range, when an inorganic particle-dispersed slurry composition is prepared, it can be made to have particularly excellent dispersibility in inorganic particles.
The weight concentration of the S atoms is preferably 0.30% by weight or more, preferably 2.00% by weight or less, more preferably 0.50% by weight or more, more preferably 1.80% by weight or less, and 0.70% by weight. % or more is more preferable, and 1.50 weight % or less is still more preferable.
The weight concentration of the S atoms means the weight ratio of the S atoms in the (meth)acrylic resin structure to the weight of the (meth)acrylic resin particles, and can be calculated based on the following formula. Furthermore, the above values are rounded to the third decimal place.
Weight concentration of S atoms contained in (meth)acrylic resin particles = [(Weight of S atoms contained in all monomers + Weight of S atoms contained in all chain transfer agents + S contained in all polymerization initiators) weight of atoms)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Further, the weight concentration of the S atoms can also be determined by ICP-AES (Inductively Coupled Plasma Emission Spectroscopy).

The weight concentration of COOH groups contained in the (meth)acrylic resin particles is preferably 0.06% by weight or more, and preferably 3.00% by weight or less.
Within the above range, there is an advantage that the inorganic particles have particularly excellent dispersibility.
The weight concentration of the COOH group is more preferably 0.50% by weight or more, more preferably 2.70% by weight or less, still more preferably 1.00% by weight or more, and even more preferably 2.50% by weight or more.
The weight concentration of the COOH group means the ratio of the weight of the COOH group in the (meth)acrylic resin structure to the weight of the (meth)acrylic resin particles, and can be calculated based on the following formula. Furthermore, the above values are rounded to the third decimal place.
Weight concentration of COOH groups contained in (meth)acrylic resin particles = [(Weight of COOH groups contained in all monomers + Weight of COOH groups contained in all chain transfer agents + COOH contained in all polymerization initiators) weight of group)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Furthermore, the weight concentration of the COOH group can also be determined by ESCA analysis using a gas phase chemical modification method.

The weight concentration of K atoms contained in the (meth)acrylic resin particles is preferably 0.001% by weight or more, and preferably 1.500% by weight or less.
Within the above range, storage stability is improved.
The weight concentration of the K atoms is more preferably 0.005% by weight or more, and more preferably 1.200% by weight or less.
The weight concentration of K atoms means the ratio of the weight of K atoms in the (meth)acrylic resin structure to the weight of the (meth)acrylic resin particles, and can be calculated based on the following formula. Furthermore, the above values are rounded to the fourth decimal place.
Weight concentration of K atoms contained in (meth)acrylic resin particles = [(Weight of K atoms contained in all monomers + Weight of K atoms contained in all chain transfer agents + K contained in all polymerization initiators) weight of atoms)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Moreover, the weight concentration of K atoms can also be measured using an atomic absorption spectrophotometer.

The weight concentration of OH groups contained in the (meth)acrylic resin particles is preferably 0.05% by weight or more, preferably 3.00% by weight or less, more preferably 0.08% by weight or more, and 2.50% by weight. The following is more preferable, 0.10% by weight or more is even more preferable, and even more preferably 2.00% by weight or less. By being within the above range, storage stability, viscosity stability, and degradability are improved.
The weight concentration of the OH group means the ratio of the weight of the OH group in the (meth)acrylic resin structure to the weight of the (meth)acrylic resin particles, and can be calculated based on the following formula. Furthermore, the above values are rounded to the third decimal place.
Weight concentration of OH groups contained in (meth)acrylic resin particles = [(Weight of OH groups contained in all monomers + Weight of OH groups contained in all chain transfer agents + OH contained in all polymerization initiators) weight of group)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Further, the weight concentration of the OH group can also be determined by ESCA analysis using a gas phase chemical modification method.

The ratio of the weight concentration of COOH groups to the weight concentration of S atoms contained in the (meth)acrylic resin particles (weight concentration of COOH groups/weight concentration of S atoms) is preferably 0.03 or more, and 3. 00 or less, more preferably 0.05 or more, and even more preferably 1.00 or less.

The ratio of the weight concentration of OH groups to the weight concentration of S atoms contained in the (meth)acrylic resin particles (weight concentration of OH groups/weight concentration of S atoms) is preferably 0.10 or more and 3.00 or less. is preferable, 0.15 or more is more preferable, and 1.20 or less is more preferable.

The ratio of the weight concentration of K atoms to the weight concentration of S atoms contained in the (meth)acrylic resin particles (weight concentration of K atoms/weight concentration of S atoms) is preferably 0.01 or more and 1.50 or less. is preferable, 0.05 or more is more preferable, and 1.20 or less is more preferable.

The average particle diameter of the (meth)acrylic resin particles is preferably 0.1 μm or more, and preferably 1.0 μm or less.
By setting it as the said range, the solubility of (meth)acrylic resin particles can be improved more.
The average particle diameter is more preferably 0.2 μm or more, more preferably 0.9 μm or less, even more preferably 0.3 μm or more, and even more preferably 0.8 μm or less.
The average particle diameter can be determined, for example, by measuring the volume average particle diameter using a laser diffraction/scattering particle size distribution measuring device.
Note that the above average particle diameter can be adjusted by adjusting the amount of the polymerization initiator. For example, when the content of the polymerization initiator is high, the average particle size tends to be small, and when the content of the polymerization initiator is low, the average particle size tends to be large.

The (meth)acrylic resin particles preferably contain a segment derived from a (meth)acrylic acid ester in which the number of carbon atoms in the ester substituent is 8 or less.
In addition, the fact that the number of carbon atoms in the ester substituent is 8 or less means that the total number of carbon atoms other than the carbon constituting the (meth)acryloyl group in the (meth)acrylic ester is 8 or less. Furthermore, in this specification, the (meth)acrylic ester in which the ester substituent has 8 or less carbon atoms refers to a (meth)acrylic ester other than the glycidyl group-containing (meth)acrylic ester described below.
Examples of the (meth)acrylic ester in which the ester substituent has 8 or less carbon atoms include (meth)acrylic esters having a linear, branched, or cyclic alkyl group.
Examples of the (meth)acrylic ester having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. It will be done.
Examples of the (meth)acrylic ester having a branched alkyl group include isopropyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. It will be done.
Examples of the (meth)acrylic acid ester having a cyclic alkyl group include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and the like.
In addition, examples of (meth)acrylic acid esters in which the number of carbon atoms in the ester substituent is 8 or less include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (meth)acrylic acid ester. (Meth)acrylates having hydroxyl groups or carboxyl groups such as acids can also be used.
Among these, (meth)acrylic esters having a linear alkyl group and (meth)acrylic esters having a branched alkyl group are preferred. Furthermore, methyl methacrylate, ethyl methacrylate, and isobutyl methacrylate are more preferred. Furthermore, a combination of a (meth)acrylic ester having a linear alkyl group and a (meth)acrylic ester having a branched alkyl group is preferred.

As the (meth)acrylic ester in which the ester substituent has 8 or less carbon atoms, a (meth)acrylic ester in which the ester substituent has 1 to 4 carbon atoms may be used; (Meth)acrylic acid esters having a number of 5 to 8 may also be used. Among these, (meth)acrylic esters in which the ester substituent has 1 to 4 carbon atoms are preferred.

The content of the segment derived from the (meth)acrylic acid ester in which the ester substituent has 8 or less carbon atoms in the (meth)acrylic resin particles is preferably 40% by weight or more, more preferably 60% by weight or more, More preferably 80% by weight or more. The upper limit is not particularly limited, but is preferably 100% by weight or less, more preferably 99% by weight or less, and even more preferably 98% by weight or less.
The content of the segment in the (meth)acrylic resin particles is based on the raw materials used to produce the (meth)acrylic resin constituting the (meth)acrylic resin particles, excluding the polymerization initiator and chain transfer agent. It can be calculated based on the ratio of each monomer to 100 parts by weight of the monomer.

The content of the segment derived from the (meth)acrylic ester in which the ester substituent has 1 to 4 carbon atoms in the (meth)acrylic resin particles is preferably 40% by weight or more, more preferably 60% by weight or more. , more preferably 80% by weight or more. The upper limit is not particularly limited, but is, for example, 100% by weight or less.

The content of the segment derived from the (meth)acrylic ester in which the ester substituent has 1 to 2 carbon atoms in the (meth)acrylic resin particles is preferably 35% by weight or more, more preferably 40% by weight or more, The content is preferably 65% by weight or less, more preferably 60% by weight or less.

The content of the segment derived from the (meth)acrylic ester in which the ester substituent has 5 to 8 carbon atoms in the (meth)acrylic resin particles is preferably 60% by weight or less, more preferably 40% by weight or less. , more preferably 20% by weight or less. The lower limit is not particularly limited, but is, for example, 0% by weight or more.

The content of segments derived from methyl methacrylate in the (meth)acrylic resin particles is preferably 30% by weight or more, preferably 60% by weight or less, more preferably 35% by weight or more, and more preferably 50% by weight or less.

The content of segments derived from ethyl methacrylate in the (meth)acrylic resin particles is preferably 10% by weight or more, preferably 30% by weight or less, more preferably 15% by weight or more, and more preferably 25% by weight or less.

The content of segments derived from isobutyl methacrylate in the (meth)acrylic resin particles is preferably 30% by weight or more, preferably 60% by weight or less, more preferably 35% by weight or less, and even more preferably 50% by weight or less.

The (meth)acrylic resin particles may have a segment derived from a (meth)acrylic acid ester in which the ester substituent has 9 or more carbon atoms.
The number of carbon atoms in the ester substituent is more preferably 10 or more, preferably 30 or less, and more preferably 20 or less.

As the (meth)acrylic ester in which the ester substituent has 9 or more carbon atoms, (meth)acrylic ester having a linear or branched alkyl group having 9 or more carbon atoms, polyalkylene glycol Examples include (meth)acrylate.

Examples of the linear or branched (meth)acrylic acid ester having an alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n-decyl (meth)acrylate. Acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, and the like.
Examples of the polyalkylene glycol (meth)acrylate include those having ethylene glycol units, propylene glycol units, butylene glycol units, and the like.
Further, the polyalkylene glycol (meth)acrylate may have an alkoxy group at the end, or may have an ethylhexyl group at the end.
Moreover, the polyalkylene glycol (meth)acrylate may have a linear alkylene glycol unit or may have a branched alkylene glycol unit.

The content of the segment derived from the (meth)acrylic ester in which the ester substituent has 9 or more carbon atoms in the (meth)acrylic resin particles is preferably 60% by weight or less, more preferably 40% by weight or less, More preferably, it is 20% by weight or less. The lower limit is not particularly limited, but is, for example, 0% by weight or more.

The (meth)acrylic resin particles may have a segment derived from a (meth)acrylic acid ester having a glycidyl group.
Examples of the (meth)acrylic acid ester having a glycidyl group include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexyl (meth)acrylate.

The content of the segment derived from the acrylic monomer in the (meth)acrylic resin particles is preferably 5% by weight or less, and more preferably 1% by weight or less, since the smaller the content, the better the low-temperature decomposition property is. preferable. The lower limit is not particularly limited, but is, for example, 0% by weight or more.
In addition, the said acrylic monomer means acrylic acid and acrylic acid ester.

The glass transition temperature (Tg) of the (meth)acrylic resin particles is preferably 30°C or higher, and preferably 85°C or lower.
By setting it as the said range, the addition amount of a plasticizer can be reduced and low-temperature decomposability can be improved.
The above Tg is more preferably 32°C or higher, more preferably 80°C or lower, even more preferably 42°C or higher, and even more preferably 75°C or lower.
Note that the glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).

The (meth)acrylic resin particles preferably have a 90% decomposition temperature of 280°C or lower, more preferably 270°C or lower, and 260°C or lower when heated from 30°C to 5°C/min. It is even more preferable that there be. The lower limit is not particularly limited, and is 30° C. or higher, and the lower the temperature, the more preferable.

As a method for manufacturing the above-mentioned (meth)acrylic resin particles, for example, an organic solvent or the like is added to a raw material monomer mixture containing (meth)acrylic acid ester, etc. to prepare a monomer mixture, and further, the obtained monomer mixture is A method of copolymerizing the above raw material monomers by adding a polymerization initiator and a chain transfer agent to the monomer can be mentioned.
The polymerization method is not particularly limited, and examples include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among these, solution polymerization is preferred.

Examples of the organic solvents include toluene, ethyl acetate, butyl acetate, pentyl acetate, hexyl acetate, ethyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and ethylene glycol ethyl ether. , ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydro Examples include terpineol, dihydroterpineol acetate, texanol, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, phenylpropylene glycol, and cresol. Among these, butyl acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferred. Moreover, butyl acetate, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate are more preferred. Note that these organic solvents may be used alone or in combination of two or more.

Examples of the polymerization initiator include t-butylperoxypivalate, P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, Examples include t-butyl hydroxy peroxide, cyclohexanone peroxide, and disuccinic acid peroxide. Also, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]sulfatohydrate, Acid mixtures of imidazole azo compounds such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2' -Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'- Water-soluble azo compounds such as azobis-4-cyanovaleric acid, oxoacids such as potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate), sodium persulfate (sodium peroxodisulfate), hydrogen peroxide , peroxides such as peracetic acid, performic acid, perpropionic acid, and the like.
Among these, polymerization initiators containing S atoms and polymerization initiators containing K atoms are preferably used. Also, potassium persulfate, ammonium persulfate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) ) propionamide] is preferred, and potassium persulfate and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] are more preferred.

The amount of the polymerization initiator added is preferably 0.03 parts by weight or more, preferably 4.0 parts by weight or less, more preferably 0.05 parts by weight or more, and 3.6 parts by weight based on 100 parts by weight of the raw material monomer. Part or less is more preferable.

As the chain transfer agent, a chain transfer agent having an S atom is preferably used, such as 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8- Examples include mercapto-1-octanol, 2-mercaptobenzimidazole, mercaptosuccinic acid, and mercaptoacetic acid.
Among them, 3-mercapto-1,2-propanediol and mercaptosuccinic acid are preferably used.

The amount of the chain transfer agent added is preferably 0.1 parts by weight or more, preferably 10.0 parts by weight or less, more preferably 0.4 parts by weight or more, and 5.0 parts by weight based on 100 parts by weight of the raw material monomer. Part or less is more preferable.

The temperature during polymerization is preferably 50°C or higher, preferably 90°C or lower, more preferably 60°C or higher, and more preferably 80°C or lower.

A vehicle composition can be prepared using the above (meth)acrylic resin particles and a solvent containing an organic solvent.
A vehicle composition containing the above-mentioned (meth)acrylic resin particles and a solvent including an organic solvent is also one aspect of the present invention.

The content of the (meth)acrylic resin particles in the vehicle composition is preferably 5% by weight or more, preferably 30% by weight or less, more preferably 10% by weight or more, and more preferably 20% by weight or less.

The vehicle composition contains an organic solvent.
Examples of the organic solvent include alcohols such as aliphatic alcohols, glycols, terpene alcohols, and aromatic alcohols, aromatic hydrocarbons, esters, ketones, N-methylpyrrolidone, and the like.
Examples of the aliphatic alcohols include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, texanol, Examples include 2-butyl-2-ethyl-1,3-propanediol and neopentyl glycol.
The above glycols include ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, ethylene glycol monoethyl ether acetate, trimethylpentanediol monoisobutyrate, butyl carbitol acetate, and texanol. , ethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol ethyl ether, and the like.
Examples of the terpene alcohols include terpineol, dihydroterpineol, terpineol acetate, dihydroterpineol acetate, and the like.
Examples of the aromatic alcohols include benzyl alcohol and the like.
Examples of the aromatic hydrocarbons include toluene and the like.
Examples of the esters include ethyl acetate, butyl acetate, hexyl acetate, isoamyl acetate, butyl butyrate, bityl lactate, dioctyl phthalate, dioctyl adipate, and the like.
Examples of the ketones include methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone.
Among these, aliphatic alcohols and terpene alcohols are preferred, and 2-butyl-2-ethyl-1,3-propanediol and dihydroterpineol acetate are more preferred.

It is preferable that the organic solvent has a compound having two or more OH groups.
The content of the compound having two or more OH groups in the above solvent is preferably 10% by weight or more, and preferably 50% by weight or less.
By setting it within the above range, there is an advantage that the inorganic particles can have particularly excellent dispersibility.

The content of the solvent in the vehicle composition is not particularly limited, but is preferably 65% by weight or more, preferably 90% by weight or less, more preferably 70% by weight or more, and more preferably 85% by weight or less.

In the above vehicle composition, the solvent preferably further contains water.
The content of water in the solvent is preferably at least 100 ppm by weight, and preferably at most 40,000 ppm by weight.
Containing water within the above range has the advantage of improving compatibility with the dispersant and improving thermal decomposition properties.
The content of water in the solvent is more preferably at least 300 ppm by weight, and more preferably at most 20,000 ppm by weight.

The weight concentration of S atoms contained in the vehicle composition is preferably 0.004% by weight or more, preferably 0.400% by weight or less, more preferably 0.100% by weight or more, and 0.200% by weight or less. More preferred.
The weight concentration of S atoms means the ratio of the weight of S atoms contained in the vehicle composition to the weight of the entire vehicle composition, and can be calculated based on the following formula.
Weight concentration of S atoms contained in the vehicle composition = [Content (% by weight) of (meth)acrylic resin particles in vehicle composition × Weight concentration (weight %) of S atoms contained in (meth)acrylic resin particles %)]÷100

The weight concentration of COOH groups contained in the vehicle composition is preferably 0.005% by weight or more, preferably 0.500% by weight or less, more preferably 0.009% by weight or more, and 0.300% by weight or less. More preferred.
The weight concentration of the COOH group means the weight ratio of the COOH group contained in the vehicle composition to the weight of the entire vehicle composition, and can be calculated based on the following formula.
Weight concentration of COOH groups contained in the vehicle composition = {[Content (% by weight) of (meth)acrylic resin particles in the vehicle composition × Weight concentration of COOH groups contained in the (meth)acrylic resin particles ( weight%)]+[Content of organic solvent in vehicle composition (weight%) x weight concentration of COOH group contained in organic solvent (weight%)]}÷100

The weight concentration of OH groups contained in the vehicle composition is preferably 0.01% by weight or more, preferably 13.00% by weight or less, more preferably 0.02% by weight or more, and 11.00% by weight or less. More preferred.
The weight concentration of the OH groups means the weight ratio of the OH groups contained in the vehicle composition to the weight of the entire vehicle composition, and can be calculated based on the following formula.
Weight concentration of OH groups contained in the vehicle composition = {[Content (% by weight) of (meth)acrylic resin particles in the vehicle composition × Weight concentration of OH groups contained in the (meth)acrylic resin particles ( (% by weight)] + [Content of organic solvent in vehicle composition (% by weight) x Weight concentration of OH groups contained in organic solvent (% by weight)] + [Content of water in vehicle composition (% by weight) %) x weight concentration of OH groups in water (weight %)] ÷ 100

The weight concentration of K atoms contained in the vehicle composition is preferably 0.001% by weight or more, preferably 0.200% by weight or less, more preferably 0.010% by weight or more, and 0.160% by weight or less. More preferred.
The weight concentration of K atoms means the weight ratio of K atoms contained in the vehicle composition to the weight of the entire vehicle composition, and can be calculated based on the following formula.
Weight concentration of K atoms contained in the vehicle composition = [Content of (meth)acrylic resin particles in the vehicle composition (wt%) x Weight concentration of K atoms contained in the (meth)acrylic resin particles (weight %)]÷100

Further, the ratio of the weight concentration of OH groups to the weight concentration of S atoms contained in the vehicle composition (weight concentration of OH groups/weight concentration of S atoms) is preferably 0.1 or more, and preferably 100 or less, It is more preferably 0.2 or more, and more preferably 75 or less.

Examples of the method for producing the vehicle composition include a method in which an organic solvent, water, etc. are added to the (meth)acrylic resin particles obtained by the above method, and the mixture is stirred.

A slurry composition can be prepared using the vehicle composition, inorganic particles, and dispersant described above.
A slurry composition containing the above vehicle composition, inorganic particles, and a dispersant is also part of the present invention.

The content of the (meth)acrylic resin particles in the slurry composition is preferably 3% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or more, and more preferably 8% by weight or less.

The content of the organic solvent in the slurry composition is preferably 25% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or more, and more preferably 35% by weight or less.

The content of water in the slurry composition is preferably at least 30 ppm by weight, preferably at most 15,000 ppm by weight, more preferably at least 1,000 ppm by weight, more preferably at most 10,000 ppm by weight, even more preferably at least 5,000 ppm by weight, and even more preferably at least 7,000 ppm by weight. It is more preferably less than ppm by weight.

The slurry composition contains inorganic particles.
The inorganic particles are not particularly limited, and include, for example, glass powder, ceramic powder, phosphor fine particles, silicon oxide, metal fine particles, and the like.

The above-mentioned glass powder is not particularly limited, and includes, for example, glass powder such as bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, CaO-Al ₂ O ₃ -SiO ₂ system, MgO-Al ₂ O Examples include glass powders of various silicon oxides such as _3- SiO ₂ series, LiO ₂ -Al ₂ O ₃ -SiO ₂ series, and the like.
In addition, as the above-mentioned glass powder, 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 Glass powders such as ₂ O ₅ mixture, SrO-ZnO-P ₂ O ₅ mixture, BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture can also be used. Note that R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn.
In particular, glass powder of PbO-B ₂ O ₃ -SiO ₂ mixture, lead-free BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture or ZnO-Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ mixture, etc. Lead-free glass powder is preferred.

The above ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, etc. It will be done.
ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
The phosphor fine particles are not particularly limited, and for example, blue phosphor substances, red phosphor substances, green phosphor substances, etc., which are conventionally known as phosphor substances for displays, can be used as the phosphor substance. Examples of blue phosphor substances include MgAl ₁₀ O ₁₇ :Eu system, Y ₂ SiO ₅ :Ce system, CaWO ₄ :Pb system, BaMgAl ₁₄ O ₂₃ :Eu system, BaMgAl ₁₆ O ₂₇ :Eu system, BaMg ₂ Al. ₁₄ O ₂₃ : Eu-based, BaMg ₂ Al ₁₄ O ₂₇ : Eu-based, and ZnS: (Ag, Cd)-based are used. Examples of red phosphor substances include 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. (Y,Gd)BO ₃ :Eu system, GdBO ₃ :Eu system, ScBO ₃ :Eu system, and LuBO ₃ :Eu system. Examples of green phosphor substances include Zn ₂ SiO ₄ :Mn system, BaAl ₁₂ O ₁₉ :Mn system, SrAl ₁₃ O ₁₉ :Mn system, CaAl ₁₂ O ₁₉ :Mn system, YBO ₃ :Tb system, BaMgAl ₁₄ O ₂₃ : Mn type, LuBO ₃ : Tb type, GdBO ₃ : Tb type, ScBO ₃ : Tb type, and Sr6Si ₃ O ₃ Cl ₄ : Eu type are used. Others include ZnO:Zn series _, _ZnS :(Cu,Al) series, ZnS:Ag series, Y2O2S:Eu series, ZnS:Zn series, (Y,Cd) _BO3 :Eu _series , _BaMgAl12O23 :Eu-based materials can also be used.

The metal fine particles are not particularly limited, and include, for example, powders made of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
Further, metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be suitably used. These metal powders may be used alone or in combination of two or more.
In addition to metal complexes, various carbon blacks, carbon nanotubes, etc. may be used as the metal fine particles.

The inorganic particles preferably contain lithium or titanium. Specifically, for example, low melting point glass such as LiO ₂ / Al ₂ O ₃ / SiO ₂ type inorganic glass, lithium sulfur type glass such as Li ₂ S-M _x S _y (M=B, Si, Ge, P), etc. , lithium cobalt composite oxide such as _LiCeO2 , lithium manganese composite oxide such as _LiMnO4 , lithium nickel composite oxide, lithium vanadium composite oxide, lithium zirconium composite oxide, lithium hafnium composite oxide, lithium silicate (Li _3.5 Si _0.5 P _0.5 O ₄ ), lithium titanium phosphate (LiTi 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 glass, Li ₄ GeS ₄ -Li ₃ PS ₄ glass, LiSiO ₃ , LiMn ₂ O ₄ , Li ₂ S- P ₂ S ₅ -based glass/ceramics, Li ₂ O-SiO ₂ , Li ₂ O-V ₂ O ₅ -SiO ₂ , LiS-SiS ₂ -Li ₄ SiO ₄ -based glass, ion conductive oxides such as LiPON, Li Lithium oxide compounds such as ₂ O-P ₂ O ₅ -B ₂ O ₃ and Li ₂ O-GeO ₂ Ba, Li _x Al _y T _z (PO ₄ ) ₃ -based glass, La _x Li _y TiO _z -based glass, Li _x Ge _y P _z O ₄ -based glass, Li ₇ La ₃ Zr ₂ O ₁₂ -based glass, Li _v Si _w P _x S _y Cl _z -based glass, lithium niobium oxide such as LiNbO ₃ , Li-β-alumina, etc. Examples include lithium alumina compounds, lithium zinc oxides such as Li ₁₄ Zn(GeO ₄ ) ₄ , and the like.

The average particle diameter of the inorganic particles is preferably 0.01 μm or more, preferably 5 μm or less, more preferably 0.05 μm or more, more preferably 3 μm or less, even more preferably 0.1 μm or more, and even more preferably 1 μm or less.
The average particle diameter can be determined, for example, by measuring the volume average particle diameter using a laser diffraction/scattering particle size distribution measuring device.

The content of the inorganic particles in the slurry composition is preferably 30% by weight or more, and preferably 90% by weight or less. When it is within the above range, it can have sufficient viscosity and excellent coating properties, and furthermore, can have excellent dispersibility of inorganic particles.
The content of the inorganic particles is more preferably 40% by weight or more, and more preferably 70% by weight or less.

The slurry composition contains a dispersant.
Suitable examples of the dispersant include fatty acids, aliphatic amines, alkanolamides, and phosphoric acid esters. Additionally, a silane coupling agent or the like may be added.
The above fatty acids are not particularly limited, and include, for example, saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and coconut fatty acids; oleic acid, linoleic acid, linolenic acid, and sorbic acid. , beef tallow fatty acid, unsaturated fatty acids such as castor hydrogenated fatty acid, and the like. Among these, lauric acid, stearic acid, oleic acid, etc. are preferred.
The above aliphatic amines are not particularly limited, and include, for example, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl (coconut) amine, alkyl (hardened beef tallow) amine, alkyl (beef tallow) amine, and alkyl (soybean) amine. etc.
The alkanolamide is not particularly limited, and includes, for example, coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, and the like.
The above-mentioned phosphoric acid ester is not particularly limited, and examples thereof include polyoxyethylene alkyl ether phosphoric ester and polyoxyethylene alkyl allyl ether phosphoric ester.

The content of the dispersant in the slurry composition is preferably 0.1% by weight or more, preferably 1% by weight or less, more preferably 0.15% by weight or more, and even more preferably 0.5% by weight or less.

The slurry composition may further contain additives such as a plasticizer and a surfactant.
Examples of the plasticizers include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, acetyl Triethyl citrate, acetyl tributyl citrate, acetyl diethyl citrate, acetyl dibutyl citrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate, and the like.

The above-mentioned surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
The nonionic surfactant is not particularly limited, but preferably has an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of surfactants, and several calculation methods have been proposed.For example, for ester surfactants, saponification value There are definitions such as S, the acid value of the fatty acid constituting the surfactant, A, and the HLB value of 20 (1-S/A). Specifically, a nonionic surfactant having polyethylene oxide with an alkylene ether added to a fatty chain is suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. It will be done. The above-mentioned nonionic surfactant has good thermal decomposition properties, but if added in large quantities, the thermal decomposition properties of the inorganic particle dispersed slurry composition may decrease, so the preferable upper limit of the content is 5% by weight. .

The viscosity of the slurry composition of the present invention is not particularly limited, but it is preferably 80,000 or more, preferably 2,000,000 or less, and 100,000 or more when measured at 25°C using a B-type viscometer. is more preferable, and more preferably 600,000 or less.
By setting it as the said range, it becomes possible for the inorganic particle dispersion sheet obtained to maintain a predetermined shape after coating by a die coat printing method etc. In addition, problems such as inability to erase die coating marks can be prevented, resulting in excellent printability.

The method for producing the slurry composition is not particularly limited, and examples thereof include conventionally known stirring methods. Specifically, for example, the above vehicle composition, the above inorganic particles, the above dispersant, and the above-mentioned dispersant are added as necessary. Examples include a method in which other components such as an additional solvent and a plasticizer are stirred using three rolls or the like. The order of addition of the constituent components of the slurry composition can be set as appropriate.

Electronic components can be manufactured using the above slurry composition.
A method of manufacturing an electronic component using the above slurry composition is also one aspect of the present invention.
The above electronic components include die attach paste (ACP), die attach film (ACF), via electrodes for TSV and TGV, touch panels, various circuits for RFID and sensor boards, various die bonding agents, sealants for MEMS devices, solar Examples include electrode materials for batteries, laminated ceramic capacitors, LTCCs, silicon capacitors, all-solid-state batteries, and the like. In addition to the above-mentioned electrode circuit applications, it can also be used for antibacterial materials, electromagnetic shields, catalysts, fluorescent materials, and the like.

For example, an inorganic particle-dispersed molded product can be produced by coating the slurry composition on a support film that has been subjected to a mold release treatment on one side, drying the organic solvent, and molding the slurry composition.
Although the shape of the inorganic particle-dispersed molded product is not particularly limited, it can be, for example, in the shape of a sheet or the like.

Examples of the method for manufacturing the inorganic particle dispersion molded product include a method in which the slurry composition is coated uniformly on a support film using a coating method such as a roll coater, die coater, squeeze coater, curtain coater, etc. Can be mentioned.

For example, when the inorganic particle dispersion molded product is in the form of a sheet, the support film used when manufacturing the inorganic particle dispersion molded product is a resin film that has heat resistance, solvent resistance, and flexibility. is preferred. Due to the flexibility of the support film, the inorganic particle-dispersed slurry composition can be applied to the surface of the support film using a roll coater, blade coater, etc., and the resulting inorganic particle-dispersed sheet-forming film is wound into a roll. It can be stored and supplied in this state.

Examples of the resin forming the support film include fluororesins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film is preferably, for example, 20 to 100 μm.
Further, it is preferable that the surface of the support film is subjected to a release treatment, so that the peeling operation of the support film can be easily performed in the transfer process.

An inorganic particle-dispersed molded product can be produced by applying and drying the slurry composition.
Further, by using the slurry composition and the inorganic particle dispersion molded product in a conductive paste for external electrodes, a multilayer ceramic capacitor, which is an electronic component, can be manufactured.

The method for manufacturing the multilayer ceramic capacitor includes a step of printing and drying a conductive paste on the inorganic particle dispersed molded product to prepare a dielectric sheet, and a step of laminating the dielectric sheets. can be mentioned.

The conductive paste contains conductive powder.
The material of the conductive powder is not particularly limited as long as it is conductive, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.

The method for printing the conductive paste is not particularly limited, and examples thereof include screen printing, die coat printing, offset printing, gravure printing, inkjet printing, and the like.

In the method for manufacturing a multilayer ceramic capacitor, a raw ceramic laminate is produced by laminating dielectric sheets printed with the conductive paste, and then a firing treatment is performed in a reducing atmosphere at a temperature of 1000 to 1500°C. , This allows a large number of component bodies to be obtained.

Next, a conductive paste for external electrodes containing the above-mentioned (meth)acrylic resin particles is applied to both end faces of each of these component bodies by dipping, and then, after drying at 100 to 200°C, under a reducing atmosphere. , 450 to 800° C. to form external electrodes at both ends of the component body.

Next, the external electrodes are subjected to electrolytic plating to sequentially form a Cu film, a Ni film, and a Sn film on the external electrodes, thereby obtaining a multilayer ceramic capacitor.

According to the present invention, the present invention has excellent low-temperature decomposition properties, can prevent deterioration of inorganic particles such as copper due to oxidation when used as a binder for dispersing inorganic particles, and has particularly excellent dispersibility of fine inorganic particles. It is possible to provide (meth)acrylic resin particles from which an inorganic particle-dispersed slurry composition can be made. In addition, by using the present invention as a binder for the external electrodes of a multilayer ceramic capacitor, it is possible to provide (meth)acrylic resin particles that can produce a multilayer ceramic capacitor with excellent reliability. Furthermore, vehicle compositions, slurry compositions, and methods of manufacturing electronic components can be provided.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Examples 1 to 21, Comparative Examples 1 to 4)
(Preparation of (meth)acrylic resin particles)
Prepare a 2L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet, and add a total of 100 parts by weight of monomers to the 2L separable flask as shown in Tables 1 and 2. was introduced. Furthermore, 50 parts by weight of butyl acetate as an organic solvent was mixed to obtain a monomer mixture.
In addition, the following monomers were used.
MMA: Methyl methacrylate EMA: Ethyl methacrylate iBMA: Isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate

After removing dissolved oxygen by bubbling the obtained monomer mixture with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised while stirring until the water bath reached 80°C. did. Thereafter, a chain transfer agent and a polymerization initiator were added in amounts shown in Tables 1 and 2 to initiate polymerization.
Seven hours after the start of polymerization, the mixture was cooled to room temperature to complete the polymerization. Thereafter, the resulting resin solution was dried in an oven at 130°C to remove the organic solvent. Thereby, (meth)acrylic resin particles were obtained.
The following were used as the chain transfer agent and polymerization initiator.
<Chain transfer agent>
CT-1: 3-mercapto-1,2-propanediol CT-2: Mercaptosuccinic acid <polymerization initiator>
KPS: Potassium persulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
VA-086: 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Preparation of vehicle composition for dispersing inorganic particles)
85 parts by weight of the solvent shown in Tables 3 and 4 were added to 15 parts by weight of the obtained (meth)acrylic resin particles, and the mixture was stirred until homogeneous to obtain a vehicle composition for dispersing inorganic particles.
The following solvents were used.
DHTA: dihydroterpineol acetate BEPG: 2-butyl-2-ethyl-1,3-propanediol

(Preparation of inorganic particle dispersed slurry composition)
To the obtained vehicle composition for dispersing inorganic particles, a dispersant and inorganic particles were added so as to have the formulations shown in Tables 3 and 4, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic particle dispersion slurry composition. Ta.
Note that the following were used as the dispersant and inorganic particles.
<Dispersant>
Nopcosperse 092 (manufactured by Sanyo Chemical Industries, Ltd.)
<Inorganic particles>
Copper powder (manufactured by Fujino Metal Co., Ltd., average particle size 0.1 μm)
Glass frit (manufactured by AGC, product name ASF-1094, main component Bi ₂ O _{3 ・}B ₂ O _{3 ・}SiO ₂ , average particle size 0.8 μm)

(Production of multilayer ceramic capacitor)
First, as the main component of the inner and outer ceramic layers, a perovskite oxide containing Ba and Ti was used as a dielectric material. A ceramic slurry was prepared by mixing 80 parts by weight of the ceramic dielectric powder, 8 parts by weight of an acrylic binder, 10 parts by weight of an organic solvent, 1 part by weight of a plasticizer, and 1 part by weight of a dispersant. Then, this ceramic slurry was formed on a resin film so that the thickness after drying would be 3.0 μm to produce a ceramic green sheet for inner layer or outer layer. The acrylic binder is Marproof MH-03041 (manufactured by NOF Corporation), the organic solvent is butyl acetate, the plasticizer is G-260 (Sekisui Chemical Co., Ltd.), and the dispersant is Nopcosperse 092 (Sanyo Chemical Co., Ltd.). (manufactured by Seiko Co., Ltd.) was used.

Next, conductive paste was applied to this ceramic green sheet for inner layer in a pattern corresponding to the size of the ceramic element after firing (3.2 mm x 1.6 mm) so that the thickness after drying was 1 ± 0.1 μm. I screen printed it to look like this.
The conductive paste contains 50 parts by weight of Ni powder, 5 parts by weight of a perovskite oxide containing Ba and Ti as co-materials, 44 parts by weight of the above vehicle composition for dispersing inorganic particles, and polycarbonate. A conductive paste containing 1 part by weight of an acidic dispersant was prepared. The blending ratio of the binder resin was 6.6 parts by weight/50 parts by weight of Ni, and a conductive paste was obtained using a ball mill.
The average particle diameter of the Ni powder used was 0.2 μm. Further, the average particle diameter of the perovskite oxide containing Ba and Ti was 30 nm.

Then, after peeling off the inner layer ceramic green sheets and the outer layer ceramic green sheets screen-printed with conductive paste from the resin film, a total of 350 sheets were stacked and pressed together to form a laminate. It was cut to size and divided into individual green ceramic bodies.
After degreasing each ceramic body in a nitrogen atmosphere at 400°C for 10 hours, it was degreased in a nitrogen-hydrogen-steam mixed atmosphere at a top temperature of 1200°C and an oxygen partial pressure of 10 ^-9 to 10 ^-10 MPa. Fired under the following conditions.
Next, the inorganic particle dispersed slurry composition obtained in each example and comparative example was applied to the obtained fired ceramic body by a dipping method so that the side surface thickness after drying was 50 μm, and then dried. Ta. Thereafter, an electrode layer was formed in a nitrogen-air-steam mixed atmosphere or a nitrogen-hydrogen-steam mixed atmosphere at a top temperature of 790 to 880° C. and an oxygen electromotive force of 220 to 280 mV at the top temperature.
After that, a first plating layer containing Ni is formed on the surface of the electrode layer, and a second plating layer containing Sn is formed on the surface of the first plating layer, thereby forming an external electrode having a three-layer structure. A multilayer ceramic capacitor was fabricated.

(Comparative Examples 5 and 6)
The procedure was the same as in Example 1 except that polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., BH-3) and ethyl cellulose resin (manufactured by Nisshin Kasei Co., Ltd., STD-100) were used instead of the (meth)acrylic resin particles. A vehicle composition for dispersing inorganic particles, a slurry composition for dispersing inorganic particles, and a laminated ceramic capacitor were obtained.

<Evaluation>
The following evaluations were performed on the (meth)acrylic resin particles and inorganic particle dispersed slurry compositions obtained in Examples and Comparative Examples. The results are shown in Tables 1 to 4.

(1) The weight concentration of S atoms, the weight concentration of OH groups, the weight concentration of COOH groups, and the weight concentration of K atoms contained in (meth)acrylic resin particles are determined by the following methods. The weight concentration, the weight concentration of COOH groups, and the weight concentration of K atoms were calculated.
Weight concentration of S atoms contained in (meth)acrylic resin particles = [(Weight of S atoms contained in all monomers + Weight of S atoms contained in all chain transfer agents + Weight of S atoms contained in all polymerization initiators) weight of S atoms)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Weight concentration of OH groups contained in (meth)acrylic resin particles = [(Weight of OH groups contained in all monomers + Weight of OH groups contained in all chain transfer agents + Weight of OH groups contained in all polymerization initiators) OH group weight)/(total monomer weight + total chain transfer agent weight + total polymerization initiator weight)] x 100
Weight concentration of COOH groups contained in (meth)acrylic resin particles = [(Weight of COOH groups contained in all monomers + Weight of COOH groups contained in all chain transfer agents + Weight of COOH groups contained in all polymerization initiators) weight of COOH group)/(weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)]×100
Weight concentration of K atoms contained in (meth)acrylic resin particles = [(Weight of K atoms contained in all monomers + Weight of K atoms contained in all chain transfer agents + Weight of K atoms contained in all polymerization initiators) Weight of K atoms) / (weight of total monomers + weight of total chain transfer agents + weight of total polymerization initiators)] x 100

(2) Particle size The obtained vehicle composition for dispersing inorganic particles is supplied to a laser diffraction/scattering particle size distribution analyzer (manufactured by Horiba, Ltd., LA-950) to obtain a volume average of (meth)acrylic resin particles. The particle size was measured.

(3) Average molecular weight The obtained (meth)acrylic resin particles were analyzed by gel permeation chromatography using LF-804 (manufactured by SHOKO) as a column to determine the weight average molecular weight (Mw) and number average molecular weight (Mw) in terms of polystyrene. Mn) was measured, and the molecular weight distribution (Mw/Mn) was calculated.

(4) Viscosity The viscosity of the obtained inorganic particle-dispersed slurry composition at 25° C. was measured using a B-type viscometer (DVII+Pro, manufactured by BROOK FIELD).

(5) Storage Stability The obtained inorganic particle dispersed slurry composition was stored in an environment at a temperature of 23° C. and a humidity of 50%. One month later, the state of the slurry composition was checked and evaluated according to the following criteria. If the storage stability is high, it can be said that the dispersibility of the inorganic particles is excellent.
○: No separation of the slurry composition or sedimentation of inorganic particles was observed, and the slurry remained in a smooth state.
Δ: Sedimentation of inorganic particles was not observed, but separation of the slurry composition was observed.
x: The inorganic particles were sedimented or the slurry composition was gelled.

(6) Viscosity Stability The viscosity at 20°C of the obtained inorganic particle dispersed slurry composition was taken as the initial viscosity measured in the same manner as in "(4) Viscosity". Further, the slurry composition after measurement was stored in a constant temperature room at 20° C. for one month, and the viscosity after storage was measured in the same manner. The rate of change in viscosity after storage relative to the initial viscosity ([(viscosity after storage - initial viscosity)/initial viscosity] x 100) was determined and evaluated according to the following criteria. If the stability is high, it can be said that the dispersibility of the inorganic particles is excellent.
◎: The viscosity change rate was less than 5%.
Good: The viscosity change rate was 5% or more and less than 10%.
Δ: The viscosity change rate was 10% or more and less than 20%.
×: The viscosity change rate was 20% or more.

(7) Printability Screen printing machine (manufactured by Microtech, MT-320TV), screen plate (manufactured by Tokyo Process Service, ST500, emulsion 2μm, 2012 pattern, screen frame 320mm x 320mm), printing glass substrate (soda glass, 150 mm x 150 mm, thickness 1.5 mm), the inorganic particle dispersed slurry composition was printed in an environment of temperature 23 °C and humidity 50%, and the solvent was dried in a blower oven at 100 °C for 30 minutes. I did it. The printed pattern was observed visually or with a magnifying microscope to confirm the shape of the edge of the printed surface, and evaluated based on the following criteria.
◎: Printing was performed according to the printing pattern, and no thread-like disordered portions were observed at the printed edges.
○: Printing was performed according to the printing pattern, and one part where the printing edge was disordered like threads was observed.
△: Printing was performed according to the printing pattern, and 2 to 4 areas where the printed edges were disordered like strings were observed.
×: Printing was not performed according to the printing pattern, or 5 or more portions were observed where the printed edges were disordered like strings.

(8) Degradability The obtained inorganic particle dispersed slurry composition was packed into a platinum pan of TG-DTA, and the temperature was raised from 30°C to 5°C/min in a nitrogen atmosphere to evaporate the solvent and remove the resin and dispersant. Pyrolyzed. Thereafter, the time (minutes) at which 61.9% by weight was reached (90% by weight degreasing was completed) was measured.

(9) Oxidation state The obtained inorganic particle dispersion slurry composition was packed into a platinum pan of TG-DTA, and the temperature was raised from 30°C to 5°C/min in a nitrogen atmosphere to evaporate the solvent and remove the resin and dispersant. Pyrolyzed. Thereafter, the time (minutes) at which 61.9% by weight was reached (90% by weight degreasing was completed) was measured.
In addition, the color of the contents of the platinum pan remaining after the measurement was visually evaluated according to the following criteria.
○: The color of the contents did not change from the color of the copper used to prepare the inorganic particle dispersed slurry composition.
×: The color of the contents had changed from the color of the copper used to prepare the inorganic particle dispersed slurry composition.

(10) Withstand voltage defect rate The withstand voltage defect rate was calculated by the following formula by measuring the presence or absence of short circuit defects when a DC voltage of 150 V was applied to 10,000 of the obtained multilayer ceramic capacitors.
Withstand voltage failure rate = number of shorted samples / 10000

(11) Incidence of products with reduced capacitance The incidence of products with reduced capacitance is determined by measuring the capacitance of 10,000 obtained multilayer ceramic capacitors, and measuring the capacitance of samples with less than 90% of the design capacity. were determined to be products with reduced capacity, and the occurrence rate was calculated.

According to the present invention, the present invention has excellent low-temperature decomposition properties, can prevent deterioration of inorganic particles such as copper due to oxidation when used as a binder for dispersing inorganic particles, and has particularly excellent dispersibility of fine inorganic particles. It is possible to provide (meth)acrylic resin particles from which an inorganic particle-dispersed slurry composition can be made. Furthermore, by using the present invention as a binder for the external electrode of a multilayer ceramic capacitor, it is possible to provide (meth)acrylic resin particles that can produce a multilayer ceramic capacitor with excellent reliability. Furthermore, vehicle compositions, slurry compositions, and methods of manufacturing electronic components can be provided.

Claims

The weight average molecular weight is 100,000 or more and 1,000,000 or less,
(Meth)acrylic resin particles having a weight concentration of S atoms of 0.03% by weight or more and 2.50% by weight or less.
The (meth)acrylic resin particles according to claim 1, wherein the weight concentration of COOH groups is 0.06% by weight or more and 3.00% by weight or less.
The (meth)acrylic resin particles according to claim 1 or 2, wherein the weight concentration of K atoms is 0.010% by weight or more and 1.000% by weight or less.
The (meth)acrylic resin particles according to any one of claims 1 to 3, wherein the content of components derived from acrylic monomers is 5% by weight or less.
The (meth)acrylic resin particles according to any one of claims 1 to 4, having an average particle diameter of 0.1 μm or more and 1.0 μm or less.
A vehicle composition comprising the (meth)acrylic resin particles according to any one of claims 1 to 5 and a solvent containing an organic solvent.
7. The vehicle composition according to claim 6, wherein the solvent further contains 100 to 40,000 ppm by weight of water.
The organic solvent contains a compound having two or more OH groups,
The vehicle composition according to claim 6 or 7, wherein the content of the compound having two or more OH groups in the solvent is 10% by weight or more and 50% by weight or less.
A slurry composition comprising the vehicle composition according to any one of claims 6 to 8, inorganic particles, and a dispersant.
A method for manufacturing an electronic component using the slurry composition according to claim 9.