(METH)acrylic resin particles, vehicle composition, slurry composition, and method for manufacturing electronic component

Abstract

The purpose of the present invention is to provide (meth)acrylic resin particles that exhibit an excellent low-temperature decomposability, provide a formed article having high strength, and further achieve an increase in the number of layers and film thinning to produce a ceramic laminate having an excellent characteristic. Moreover, the present invention has the purpose of providing a method for producing a vehicle composition, a slurry composition, and an electronic component containing said (meth)acrylic resin particles. The (meth)acrylic resin particles of the present invention have a weight average molecular weight of 1,100,000-5,000,000 and a weight concentration of the S atoms of 0.0020-1.0000 wt%.

Description

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

[0001] The present invention relates to (meth)acrylic resin particles, a vehicle composition, a slurry composition, and a method for producing electronic components.

[0002] A multilayer ceramic capacitor is known to have a structure comprising a laminate in which dielectric layers and internal electrodes are alternately stacked, and a pair of external electrodes sandwiching the laminate. The external electrodes are formed by applying a conductive paste for the external electrodes to the surface of the laminate and sintering the paste.

[0003] In recent years, there has been a demand for lower temperatures in the degreasing process, which removes binder resin, in order to reduce the energy required for firing ceramics. Furthermore, there is a growing demand for lighter, more powerful ceramic parts, and this has led to a demand for thinner, more multi-layered ceramic green sheets during the manufacturing process.

[0004] As such a binder resin for ceramic molding, Patent Document 1 describes a methacrylate ester copolymer obtained by copolymerizing isobutyl methacrylate, 2-ethylhexyl methacrylate, and a hydroxyl-containing methacrylate in a predetermined ratio. It is also stated that the use of such a binder resin can exhibit good moldability and degreasing properties. Patent Document 2 also describes the use of acrylic resin, polyvinyl butyral resin, polyvinyl acetal resin, ethyl cellulose resin, etc. as a binder resin, and in particular, the use of polyvinyl butyral resin or polyvinyl acetal resin to thin the sheet.

[0005] JP 10-167836 A JP 2011-84433 A

[0006] However, although the methacrylic acid ester copolymer described in Patent Document 1 can be degreased at low temperatures, the resin itself is brittle and cannot be made into a thin film. Furthermore, as described in Patent Document 2, although a thin film can be formed by using a polyvinyl butyral resin, the decomposition temperature is high and degreasing at low temperatures is not possible. Therefore, there is a demand for a binder resin that can achieve both a low degreasing temperature and thin film formation.

[0007] The present invention aims to provide (meth)acrylic resin particles that exhibit excellent low-temperature decomposition properties, can produce molded articles with high strength, and can be used to produce ceramic laminates with superior properties by achieving further multilayering and thinning. It is also an object of the present invention to provide a vehicle composition, a slurry composition, and a method for producing electronic components that contain the (meth)acrylic resin particles.

[0008] The present disclosure (1) is a (meth)acrylic resin particle having a weight-average molecular weight of 1.1 million to 5 million and a weight concentration of S atoms of 0.0020 wt % to 1.0000 wt %. The present disclosure (2) is a (meth)acrylic resin particle of the present disclosure (1) having a weight concentration of K atoms of 0.002 wt % to 1.000 wt %. The present disclosure (3) is a (meth)acrylic resin particle of the present disclosure (1) or (2) having a weight concentration of OH groups of 0.00 wt % to 1.50 wt %. The present disclosure (4) is a (meth)acrylic resin particle having an average particle diameter of 0.1 μm to 1.0 μm, which is an arbitrary combination with any of the present disclosures (1) to (3). The present disclosure (5) is a (meth)acrylic resin particle having an average carbon number Cp of ester substituents calculated by the following formula of 3 to 6, which is an arbitrary combination with any of the present disclosures (1) to (4). Average number of carbon atoms in the ester substituent of the (meth)acrylic resin Cp = cp1 × wp1 + cp2 × wp2 + ... + cpn × wpn (cpn: number of carbon atoms in the ester substituent in the segment derived from each (meth)acrylic acid ester constituting the (meth)acrylic resin, wpn: weight fraction of the segment derived from each (meth)acrylic acid ester in the (meth)acrylic resin). The present disclosure (6) is a vehicle composition containing the (meth)acrylic resin particles of any 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), in which the average number of carbon atoms Cs in the ester substituent of the organic solvent calculated by the following formula is 3 to 7. Average number of carbon atoms in the ester substituent of the organic solvent Cs = cs1 × ws1 + cs2 × ws2 + ... + csn × wsn (csn: number of carbon atoms in the ester substituent in each organic solvent, wsn: weight fraction of each organic solvent in the organic solvent) The present disclosure (8) is the vehicle composition of the present disclosure (6) or (7), in which the ratio (Cs / Cp) of the average number of carbon atoms Cs in the ester substituent of the organic solvent to the average number of carbon atoms Cp in the ester substituent of the (meth)acrylic resin is 0.3 to 3.0. The present disclosure (9) is a vehicle composition in any combination with any of the present disclosures (6) to (8), in which the solvent further contains water in an amount of 100 ppm by weight or more and 11,500 ppm by weight or less.The present disclosure (10) is a slurry composition containing the vehicle composition of any one of the present disclosures (6) to (9), inorganic particles, and a dispersant. The present disclosure (11) is a method for producing an electronic component using the slurry composition of the present disclosure (10). The present invention is described in detail below.

[0009] The present inventors have discovered that (meth)acrylic resin particles having a predetermined weight-average molecular weight and a weight concentration of S atoms exhibit excellent low-temperature decomposition properties, and that when used as a binder for dispersing inorganic particles, molded products with high strength can be obtained, enabling further multilayering and thinning. Furthermore, they have discovered that the use of such (meth)acrylic resin particles enables the production of ceramic laminates with excellent properties, leading to the completion of the present invention.

[0010] The (meth)acrylic resin particles have a weight-average molecular weight (Mw) of 1.1 million or more and 5 million or less. A weight-average molecular weight of 1.1 million or more results in high tensile properties of the resulting resin sheet. A weight-average molecular weight of 5 million or less reduces the likelihood of undissolved (meth)acrylic resin material being generated in the resulting resin sheet, resulting in high tensile properties. Therefore, by setting the weight-average molecular weight within the above range, the strength of the molded product can be increased, thereby enabling the production of thinner green sheets. The weight-average molecular weight (Mw) is preferably 1.3 million or more, more preferably 1.5 million or more, and even more preferably 2 million or more. The weight-average molecular weight (Mw) is preferably 4.5 million or less, more preferably 4 million or less, and even more preferably 3.5 million or less. The weight-average molecular weight (Mw) is preferably 1.3 million to 4.5 million, more preferably 1.5 million to 4 million, and even more preferably 2 million to 3.5 million.

[0011] The number-average molecular weight (Mn) of the (meth)acrylic resin particles is preferably 300,000 or more, more preferably 600,000 or more, and preferably 2,000,000 or less, and more preferably 1,500,000 or less. The number-average molecular weight (Mn) is preferably 300,000 to 2,000,000, and more preferably 600,000 to 1,500,000. 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 1 or more, preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.5 or less. The Mw / Mn is preferably 1 to 5.0, more preferably 1 to 4.0, and even more preferably 1 to 3.5. Within the above range, fine undissolved matter is less likely to be generated in the vehicle composition, the strength of the resin sheet can be sufficiently increased, and the generation of voids in the ceramic laminate after firing can be prevented. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are average molecular weights calculated in terms of polystyrene, and can be obtained by GPC measurement using, for example, Column LF-804 (manufactured by Showa Denko K.K.).

[0012] The weight concentration of S atoms contained in the (meth)acrylic resin particles is 0.0020 wt% or more and 1.0000 wt% or less. By setting it within this range, both low-temperature decomposability and the strength of the molded article can be achieved. The weight concentration of S atoms is preferably 0.0030 wt% or more, more preferably 0.0060 wt% or more, even more preferably 0.0100 wt% or more, preferably 0.9000 wt% or less, more preferably 0.1000 wt% or less, and even more preferably 0.0400 wt% or less. The weight concentration of S atoms is preferably 0.0030 to 0.9000 wt%, more preferably 0.0060 to 0.1000 wt%, and even more preferably 0.0100 to 0.0400 wt%. When it is below the upper limit, low-temperature decomposability can be improved, and when it is above the lower limit, tensile performance can be kept in a good range and the strength of the molded article can be further increased. The weight concentration of S atoms means the ratio of the weight of 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: 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 all monomers + weight of all chain transfer agents + weight of all polymerization initiators)] × 100 The weight concentration of S atoms can also be determined by ICP-AES (inductively coupled plasma-atomic emission spectroscopy).

[0013] From the viewpoint of the strength of the molded article, the weight concentration of K atoms contained in the (meth)acrylic resin particles is preferably 0.002 wt% or more and preferably 1.000 wt% or less. The weight concentration of K atoms is more preferably 0.010 wt% or more, even more preferably 0.015 wt% or more, more preferably 0.500 wt% or less, and even more preferably 0.030 wt% or less. The weight concentration of K atoms is preferably 0.002 to 1.000 wt%, more preferably 0.010 to 0.500 wt%, and even more preferably 0.015 to 0.030 wt%. When the concentration is below the upper limit, low-temperature decomposition can be improved, and when the concentration is above the lower limit, tensile performance can be maintained in a good range and the strength of the molded article can be further increased. 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 according to the following formula: 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 all monomers+weight of all chain transfer agents+weight of all polymerization initiators)]×100. The weight concentration of K atoms can also be measured using an atomic absorption photometer.

[0014] From the viewpoint of low-temperature decomposition property, the weight concentration of OH groups contained in the (meth)acrylic resin particles is preferably 0.00 wt% or more, preferably 1.50 wt% or less, more preferably 0.50 wt% or less, and even more preferably 0.25 wt% or less. The weight concentration of OH groups is preferably 0.00 to 1.50 wt%, more preferably 0.00 to 0.50 wt%, and even more preferably 0.00 to 0.25 wt%. The weight concentration of OH groups means the ratio of the weight of OH groups in the (meth)acrylic resin structure to the weight of the (meth)acrylic resin particles, and can be calculated based on the following formula: 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) / (weight of all monomers+weight of all chain transfer agents+weight of all polymerization initiators)]×100. The weight concentration of OH groups can also be determined by ESCA analysis using a gas-phase chemical modification method.

[0015] The weight concentration of COOH groups contained in the (meth)acrylic resin particles is not particularly limited, but from the viewpoint of low-temperature decomposition, it is preferred that the (meth)acrylic resin particles contain no COOH groups, and that the weight concentration of COOH groups is 0 wt %.

[0016] The average particle size of the (meth)acrylic resin particles is preferably 0.1 μm or more and preferably 1.0 μm or less. By setting the average particle size within this range, the solubility of the (meth)acrylic resin particles can be further improved. The average particle size is more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and more preferably 0.9 μm or less, and even more preferably 0.8 μm or less. The average particle size is preferably 0.1 to 1.0 μm, more preferably 0.2 to 0.9 μm, and even more preferably 0.3 to 0.8 μm. The average particle size can be determined, for example, by measuring the volume average particle size using a laser diffraction / scattering particle size distribution analyzer. The average particle size can be adjusted by the type and amount of polymerization initiator. For example, a high content of polymerization initiator tends to result in a smaller average particle size, while a low content of polymerization initiator tends to result in a larger average particle size. Furthermore, the average particle size tends to be smaller when persulfates such as ammonium persulfate or potassium persulfate are used.

[0017] The CV value of the particle size of the (meth)acrylic resin particles is preferably 15% or less, more preferably 12% or less, even more preferably 10% or less, and even more preferably 8% or less. By setting the CV value within this range, the solubility of the (meth)acrylic resin particles can be further improved. Improved solubility increases productivity, and the reduction in undissolved resin improves tensile performance. The lower limit is not particularly limited, and is, for example, 0%. The CV value of the particle size is preferably 0 to 15%, more preferably 0 to 12%, even more preferably 0 to 10%, and even more preferably 0 to 8%. The CV value can be calculated from the average particle size and standard deviation of 100 particles observed using a scanning electron microscope. The CV value tends to be smaller when a persulfate such as ammonium persulfate or potassium persulfate is used.

[0018] The (meth)acrylic resin particles preferably contain a segment derived from a (meth)acrylic acid ester having an ester substituent with 8 or less carbon atoms. The ester substituent with 8 or less carbon atoms means that the total number of carbon atoms in the (meth)acrylic acid ester other than the carbon atoms constituting the (meth)acryloyl group is 8 or less. Examples of the (meth)acrylic acid ester having an ester substituent with 8 or less carbon atoms include (meth)acrylic acid esters having a linear, branched, or cyclic alkyl group. Examples of the (meth)acrylic acid ester having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. Examples of the (meth)acrylic acid ester having a branched alkyl group include isopropyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples of the (meth)acrylic acid ester having a cyclic alkyl group include cyclohexyl (meth)acrylate and benzyl (meth)acrylate. Furthermore, examples of the (meth)acrylic acid ester having an ester substituent with 8 or less carbon atoms include (meth)acrylates having a hydroxyl group or a carboxyl group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (meth)acrylic acid, as well as (meth)acrylic acid esters 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. Of these, (meth)acrylic acid esters having a linear alkyl group and (meth)acrylic acid 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 acid ester having a linear alkyl group and a (meth)acrylic acid ester having a branched alkyl group is preferred.

[0019] The (meth)acrylic acid ester having an ester substituent with 8 or less carbon atoms may be a (meth)acrylic acid ester having an ester substituent with 1 to 4 carbon atoms, or a (meth)acrylic acid ester having an ester substituent with 5 to 8 carbon atoms. Of these, a (meth)acrylic acid ester having an ester substituent with 1 to 4 carbon atoms is preferred. Furthermore, the (meth)acrylic acid ester having an ester substituent with 8 or less carbon atoms preferably does not include a (meth)acrylic acid ester having a glycidyl group.

[0020] The content of the segment derived from a (meth)acrylic acid ester having 8 or less carbon atoms in the ester substituent in the (meth)acrylic resin particles is preferably 40% by weight or more, more preferably 60% by weight or more, and even more preferably 80% by weight or more. There is no particular upper limit, but it 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 derived from a (meth)acrylic acid ester having 8 or less carbon atoms in the ester substituent is preferably 40 to 100% by weight, more preferably 60 to 99% by weight, and even more preferably 80 to 98% by weight. The content of the segment in the (meth)acrylic resin particles can be calculated based on the ratio of each monomer to 100 parts by weight of raw material monomers, excluding the polymerization initiator and chain transfer agent, among the raw materials used to prepare the (meth)acrylic resin constituting the (meth)acrylic resin particles.

[0021] The content of the segment derived from a (meth)acrylic acid ester having a branched alkyl group in the ester substituent having 8 or less carbon atoms in the (meth)acrylic resin particles is preferably 30% by weight or more, more preferably 35% by weight or more, and is preferably 70% by weight or less, more preferably 60% by weight or less. The content of the segment derived from a (meth)acrylic acid ester having a branched alkyl group in the ester substituent having 8 or less carbon atoms is preferably 30 to 70% by weight, more preferably 35 to 60% by weight.

[0022] The content of the segment derived from a (meth)acrylic acid ester having 1 to 4 carbon atoms in the ester substituent in the (meth)acrylic resin particles is preferably 40% by weight or more, more preferably 60% by weight or more, and even more preferably 80% by weight or more. There is no particular upper limit, but it is, for example, 100% by weight or less. The content of the segment derived from a (meth)acrylic acid ester having 1 to 4 carbon atoms in the ester substituent is preferably 40 to 100% by weight, more preferably 60 to 100% by weight, and even more preferably 80 to 100% by weight.

[0023] The content of the segment derived from a (meth)acrylic acid ester having 5 to 8 carbon atoms in the ester substituent in the (meth)acrylic resin particles is preferably 60% by weight or less, more preferably 40% by weight or less, and even 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 the segment derived from a (meth)acrylic acid ester having 5 to 8 carbon atoms in the ester substituent is preferably 0 to 60% by weight, more preferably 0 to 40% by weight, and even more preferably 0 to 20% by weight.

[0024] The content of the methyl methacrylate-derived segment in the (meth)acrylic resin particles is preferably 5% by weight or more, more preferably 10% by weight or more, and is preferably 40% by weight or less, more preferably 30% by weight or less. The content of the methyl methacrylate-derived segment is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.

[0025] The content of the ethyl methacrylate-derived segment in the (meth)acrylic resin particles is preferably 10% by weight or more, more preferably 20% by weight or more, and is preferably 30% by weight or less, more preferably 25% by weight or less. The content of the ethyl methacrylate-derived segment is preferably 10 to 30% by weight, more preferably 20 to 25% by weight.

[0026] The content of the n-butyl methacrylate-derived segment in the (meth)acrylic resin particles is preferably 25% by weight or more, more preferably 30% by weight or more, and is preferably 50% by weight or less, more preferably 40% by weight or less. The content of the n-butyl methacrylate-derived segment is preferably 25 to 50% by weight, more preferably 30 to 40% by weight.

[0027] The content of the isobutyl methacrylate-derived segment in the (meth)acrylic resin particles is preferably 30% by weight or more, more preferably 35% by weight or more, and is preferably 60% by weight or less, more preferably 50% by weight or less. The content of the isobutyl methacrylate-derived segment is preferably 30 to 60% by weight, more preferably 35 to 50% by weight.

[0028] The (meth)acrylic resin particles may have a segment derived from a (meth)acrylic acid ester in which the carbon number of the ester substituent is 9 or more. The carbon number of the ester substituent is preferably 10 or more, and more preferably 30 or less, and more preferably 20 or less. The carbon number of the ester substituent is preferably 9 to 30, and more preferably 10 to 20.

[0029] Examples of the (meth)acrylic acid ester having an ester substituent with 9 or more carbon atoms include a (meth)acrylic acid ester having a linear or branched alkyl group with 9 or more carbon atoms, and polyalkylene glycol (meth)acrylate.

[0030] Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, and isostearyl (meth)acrylate. Examples of the polyalkylene glycol (meth)acrylate include those having ethylene glycol units, propylene glycol units, butylene glycol units, and the like. The polyalkylene glycol (meth)acrylate may have an alkoxy group at the terminal, or may have an ethylhexyl group at the terminal. The polyalkylene glycol (meth)acrylate may have a linear alkylene glycol unit, or may have a branched alkylene glycol unit.

[0031] The content of the segment derived from a (meth)acrylic acid ester having 9 or more carbon atoms in the ester substituent in the (meth)acrylic resin particles is preferably 60% by weight or less, more preferably 40% by weight or less, and even 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 the segment derived from a (meth)acrylic acid ester having 9 or more carbon atoms in the ester substituent is preferably 0 to 60% by weight, more preferably 0 to 40% by weight, and even more preferably 0 to 20% by weight.

[0032] The content of the acrylic monomer-derived segment in the (meth)acrylic resin particles is preferably 5% by weight or less, more preferably 1% by weight or less, since a smaller content has the advantage of improving low-temperature decomposition. The lower limit is not particularly limited, but is, for example, 0% by weight or more. The content of the acrylic monomer-derived segment is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, and even more preferably 0% by weight. The acrylic monomer refers to acrylic acid and acrylic acid esters.

[0033] The (meth)acrylic resin particles preferably have an average carbon number Cp of 3 or more, and preferably 6 or less, of the ester substituents calculated by the following formula. When the average carbon number Cp is 3 or more, the resulting resin sheet has good elongation at break and improved tensile performance. When the average carbon number Cp is 6 or less, the yield stress is high and improved tensile performance. The average carbon number Cp is more preferably 3.3 or more, and more preferably 4.5 or less. The average carbon number Cp is preferably 3 to 6, and more preferably 3.3 to 4.5. Average carbon number Cp of ester substituents = cp1 × wp1 + cp2 × wp2 + ... + cpn × wpn (cpn: number of carbon atoms of ester substituents in segments derived from each (meth)acrylic acid ester constituting the (meth)acrylic resin, wpn: weight fraction of segments derived from each (meth)acrylic acid ester constituting the (meth)acrylic resin)

[0034] 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 the temperature within this range, the amount of plasticizer added can be reduced and low-temperature decomposition properties can be further improved. The Tg is more preferably 32°C or higher, even more preferably 42°C or higher, more preferably 80°C or lower, and even more preferably 75°C or lower. The Tg is preferably 30 to 85°C, more preferably 32 to 80°C, and even more preferably 42 to 75°C. The glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC) or the like.

[0035] The (meth)acrylic resin particles preferably have a 90 wt % decomposition temperature of 280°C or lower, more preferably 270°C or lower, and even more preferably 260°C or lower, when heated from 30°C at a rate of 5°C / min. The lower limit is not particularly limited, and is 30°C or higher, and the lower the temperature, the better. The 90 wt % decomposition temperature is preferably 30 to 280°C, more preferably 30 to 270°C, and even more preferably 30 to 260°C.

[0036] Examples of methods for producing the (meth)acrylic resin particles include a method in which an organic solvent or the like is added to a raw material monomer mixture containing a (meth)acrylic acid ester or the like to prepare a monomer mixture, and then a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture to copolymerize the raw material monomers. The polymerization method is not particularly limited, and examples include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among these, emulsion polymerization is preferred.

[0037] Examples of the organic solvent 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, 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, dihydroterpineol, 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. Also, butyl acetate, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate are more preferred. These organic solvents may be used alone or in combination of two or more.

[0038] Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, t-butyl hydroxyperoxide, cyclohexanone peroxide, disuccinic acid peroxide, etc. Also usable are acid mixtures of imidazole-based azo compounds such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]sulfatohydrate, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]; 2,2'-azobis(2-methylpropionamidine)dihydrochloride; 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropane]; water-soluble azo compounds such as [2-methyl-N-(2-hydroxyethyl)propionamidine]tetrahydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and 4,4'-azobis-4-cyanovaleric acid; oxoacids such as potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate), and sodium persulfate (sodium peroxodisulfate); and peroxides such as hydrogen peroxide, peracetic acid, performic acid, and perpropionic acid. Among these, polymerization initiators containing an S atom and polymerization initiators containing a K atom are preferably used. Furthermore, potassium persulfate, ammonium persulfate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] are preferred, and potassium persulfate and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] are more preferred.

[0039] The amount of the polymerization initiator added is preferably 0.03 parts by weight or more and 4.0 parts by weight or less, more preferably 0.05 parts by weight or more and more preferably 3.6 parts by weight or less, relative to 100 parts by weight of the raw material monomers. The amount of the polymerization initiator added is preferably 0.03 to 4.0 parts by weight, more preferably 0.05 to 3.6 parts by weight, relative to 100 parts by weight of the raw material monomers.

[0040] As the chain transfer agent, a chain transfer agent having an S atom is preferably used, and examples thereof include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, 2-mercaptobenzimidazole, mercaptosuccinic acid, mercaptoacetic acid, etc. Of these, 3-mercapto-1,2-propanediol is preferably used.

[0041] The amount of the chain transfer agent added is preferably 0.01 part by weight or more, more preferably 0.02 part by weight or more, and is preferably 10.0 parts by weight or less, more preferably 5.0 parts by weight or less, relative to 100 parts by weight of the raw material monomers. The amount of the chain transfer agent added is preferably 0.01 to 10.0 parts by weight, more preferably 0.02 to 5.0 parts by weight, relative to 100 parts by weight of the raw material monomers.

[0042] The temperature during polymerization is preferably 50° C. or higher, more preferably 60° C. or higher, and is preferably 90° C. or lower, more preferably 80° C. or lower. The temperature during polymerization is preferably 50 to 90° C., more preferably 60 to 80° C.

[0043] A vehicle composition can be prepared using the (meth)acrylic resin particles and a solvent containing an organic solvent. The vehicle composition containing the (meth)acrylic resin particles and a solvent containing an organic solvent also constitutes one aspect of the present invention.

[0044] The content of the (meth)acrylic resin particles in the vehicle composition is preferably 5% by weight or more, more preferably 10% by weight or more, and is preferably 50% by weight or less, more preferably 40% by weight or less. The content of the (meth)acrylic resin particles is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

[0045] 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, and N-methylpyrrolidone. 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, 2-butyl-2-ethyl-1,3-propanediol, and neopentyl glycol. Examples of the 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, Texanol, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, and ethylene glycol ethyl ether. Examples of the terpene alcohols include terpineol, dihydroterpineol, terpineol acetate, and dihydroterpineol acetate. Examples of the aromatic alcohols include benzyl alcohol. Examples of the aromatic hydrocarbons include toluene. Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, dodecyl acetate, isoamyl acetate, butyl butyrate, butyl lactate, dioctyl phthalate, and dioctyl adipate. Examples of the ketones include methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone. Of these, esters are preferred, with methyl acetate, ethyl acetate, butyl acetate, hexyl acetate and dodecyl acetate being more preferred, and ethyl acetate, butyl acetate and hexyl acetate being even more preferred.

[0046] The organic solvent preferably has an average carbon number Cs of ester substituents calculated by the following formula of 3 or more and preferably 7 or less. Within this range, the affinity between the acrylic resin and the organic solvent is increased, and tensile performance can be improved. The average carbon number Cs is more preferably 3.5 or more, and even more preferably 4.5 or less. The Cs is preferably 3 to 7, and more preferably 3.5 to 4.5. Average carbon number Cs of ester substituents of organic solvent = cs1 x ws1 + cs2 x ws2 + ... + csn x wsn (csn: number of carbon atoms of ester substituents in each organic solvent, wsn: weight fraction of each organic solvent in the organic solvent)

[0047] In the vehicle composition, the ratio (Cs / Cp) of the average carbon number Cs of the ester substituents of the organic solvent to the average carbon number Cp of the ester substituents of the (meth)acrylic resin particles is preferably 0.3 or more and 3.0 or less, from the viewpoint of the strength of the molded article. Within this range, the affinity between the (meth)acrylic resin particles and the organic solvent is increased, thereby improving tensile performance. Furthermore, within this range, the affinity between the (meth)acrylic resin particles and the organic solvent is increased, thereby improving the solubility of the resin. Cs / Cp is more preferably 0.5 or more and more preferably 1.5 or less. Cs / Cp is preferably 0.3 to 3.0, more preferably 0.5 to 1.5.

[0048] The content of the organic solvent in the vehicle composition is not particularly limited, but is preferably 65% ​​by weight or more, more preferably 70% by weight or more, and is preferably 90% by weight or less, more preferably 85% by weight or less. The content of the organic solvent is preferably 65 to 90% by weight, more preferably 70 to 85% by weight.

[0049] In the vehicle composition, the solvent preferably further contains water. The water content in the solvent is preferably 100 ppm by weight or more, and preferably 11,500 ppm by weight or less. By containing water within the above range, compatibility with the dispersant improves and low-temperature decomposition properties are further improved. The water content in the solvent is more preferably 300 ppm by weight or more, even more preferably 400 ppm by weight or more, more preferably 1,000 ppm by weight or less, and even more preferably 700 ppm by weight or less. The water content is preferably 100 to 11,500 ppm by weight, more preferably 300 to 1,000 ppm by weight, and even more preferably 400 to 700 ppm by weight.

[0050] The content of water in the vehicle composition is preferably 100 ppm by weight or more and 10,000 ppm by weight or less, and more preferably 100 to 10,000 ppm by weight.

[0051] The content of the solvent in the vehicle composition is not particularly limited, but is preferably 65% ​​by weight or more, more preferably 70% by weight or more, and is preferably 90% by weight or less, more preferably 85% by weight or less. The content of the solvent is preferably 65 to 90% by weight, more preferably 70 to 85% by weight.

[0052] The vehicle composition may be produced, for example, by adding an organic solvent, water, etc. to the (meth)acrylic resin particles obtained by the above method and stirring and mixing them.

[0053] A slurry composition can be prepared using the vehicle composition, inorganic particles, and dispersant. A slurry composition containing the vehicle composition, inorganic particles, and dispersant also constitutes one aspect of the present invention.

[0054] The content of the (meth)acrylic resin particles in the slurry composition is preferably 3% by weight or more, preferably 5% by weight or more, and is preferably 10% by weight or less, and is preferably 8% by weight or less. The content of the (meth)acrylic resin particles is preferably 3 to 10% by weight, and more preferably 5 to 8% by weight.

[0055] The content of the organic solvent in the slurry composition is preferably 25% by weight or more, more preferably 30% by weight or more, and is preferably 70% by weight or less, and more preferably 60% by weight or less. The content of the organic solvent is preferably 25 to 70% by weight, more preferably 30 to 60% by weight.

[0056] The water content in the slurry composition is preferably 30 ppm by weight or more, more preferably 1000 ppm by weight or more, and even more preferably 5000 ppm by weight or more, and is preferably 15000 ppm by weight or less, more preferably 10000 ppm by weight or less, and even more preferably 7000 ppm by weight or less. The water content is preferably 30 to 15000 ppm by weight, more preferably 1000 to 10000 ppm by weight, and even more preferably 5000 to 7000 ppm by weight.

[0057] The content of the solvent in the slurry composition is preferably 25% by weight or more, more preferably 30% by weight or more, and is preferably 70% by weight or less, and more preferably 60% by weight or less. The content of the solvent is preferably 25 to 70% by weight, more preferably 30 to 60% by weight.

[0058] The slurry composition contains inorganic particles, and the inorganic particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor particles, silicon oxide particles, and metal particles.

[0059] The glass powder is not particularly limited, and examples thereof include glass powders such as bismuth oxide glass, silicate glass, lead glass, zinc glass, and boron glass, and CaO—Al ２ O ３ -SiO ２ system, MgO-Al ２ O ３ -SiO ２ system, LiO ２ -Al ２ O ３ -SiO ２ Examples of the glass powder include glass powders of various silicon oxides such as SnO—B ２ O ３ -P ２ O ５ -Al ２ O ３ mixture, PbO-B２ 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 -SiO２ -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, SrO-ZnO-P ２ O ５ Mixture, BaO-ZnO-B ２ O ３ -SiO ２ Glass powders such as mixtures can also be used. R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn. In particular, PbO—B ２ O ３ -SiO ２ Mixture glass powder and lead-free BaO-ZnO-B ２ O ３ -SiO ２ Mixture or ZnO-Bi ２ O ３ -B ２ O ３ -SiO ２ Lead-free glass powders such as mixtures are preferred.

[0060] The 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 zirconate titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, and forsterite. ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, and lanthanum chromite can also be used. The phosphor particles are not particularly limited, and examples of the phosphor material include blue, red, and green phosphor materials conventionally known as phosphor materials for displays. The blue phosphor material is, for example, MgAl １０ O １７ : Eu, 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-based, BaMg ２ Al １４ O ２７ :Eu-based and ZnS:(Ag,Cd)-based materials are used. ２ O ３ : Eu-based, Y ２ SiO ５ : Eu-based, Y ３ Al ５ O １２ : Eu-based, Zn ３ (P.O. ４ ) ２ : Mn-based, YBO ３ :Eu-based, (Y,Gd)BO ３ : Eu-based, GdBO３ : Eu-based, ScBO ３ : Eu-based, LuBO ３ : Eu-based materials are used. As 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 series, BaMgAl １４ O ２３ : Mn-based, LuBO ３ :Tb series, GdBO ３ :Tb series, ScBO ３ :Tb series, Sr6Si ３ O ３ Cl ４ Other examples include ZnO:Zn, ZnS:(Cu,Al), ZnS:Ag, Y ２ O ２ S: Eu-based, ZnS: Zn-based, (Y, Cd)BO ３ :Eu-based, BaMgAl １２ O ２３ : Eu-based materials can also be used.

[0061] The metal particles are not particularly limited, and examples thereof include powders of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof. Metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, and the like and are easily oxidized, can also be suitably used. These metal particles may be used alone or in combination of two or more types. In addition to metal complexes, various carbon blacks, carbon nanotubes, and the like may also be used as the metal particles.

[0062] The inorganic particles preferably contain lithium or titanium. Specifically, for example, LiO ２ ・Al ２ O ３ SiO ２ low-melting-point glass such as inorganic glass, Li ２ S-M ｘ Sｙ Lithium sulfur-based glass such as (M=B, Si, Ge, P), LiCeO ２ Lithium cobalt composite oxides such as LiMnO ４ Lithium manganese composite oxide, lithium nickel composite oxide, lithium vanadium composite oxide, lithium zirconium composite oxide, lithium hafnium composite oxide, lithium silicophosphate (Li ３．５ Si ０．５ P ０．５ O ４ ), lithium titanium phosphate (LiTi ２ (P.O. 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 (P.O. ４ ) ３ ), Li ２ -SiS-based glass, Li ４ GeS ４ -Li ３ P.S. ４ LiSiO based glass ３ , LiMn ２ O ４ , Li ２ S-P ２ S ５ 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 ２ O-P ２ O ５ -B ２ O ３ , Li ２ O-GeO ２ Lithium oxide compounds such as Ba, Li ｘ Al ｙ Tiｚ (P.O. ４ ) ３ Glasses containing La ｘ Li ｙ TiO ｚ Li-based glass ｘ Ge ｙ P ｚ O ４ Li-based glass ７ La ３ Zr ２ O １２ Li-based glass ｖ Si ｗ P ｘ S ｙ Cl ｚ LiNbO ３ Lithium niobium oxides such as Li-β-alumina, lithium alumina compounds such as Li １４ Zn(GeO ４ ) ４ Lithium zinc oxides such as those mentioned above are also included.

[0063] The average particle size of the inorganic particles is preferably 0.01 μm or more and 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 size of the inorganic particles is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, and even more preferably 0.1 to 1 μm. The average particle size can be determined, for example, by measuring the volume average particle size using a laser diffraction / scattering particle size distribution analyzer.

[0064] The content of the inorganic particles in the slurry composition is preferably 30% by weight or more and preferably 90% by weight or less. Within this range, the slurry composition has sufficient viscosity, excellent coating properties, and excellent inorganic particle dispersibility. The content of the inorganic particles is more preferably 40% by weight or more and more preferably 70% by weight or less. The content of the inorganic particles is preferably 30 to 90% by weight, more preferably 40 to 70% by weight.

[0065] The slurry composition contains a dispersant. Suitable examples of the dispersant include fatty acids, aliphatic amines, alkanolamides, and phosphate esters. A silane coupling agent may also be added. The fatty acids are not particularly limited, and examples include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and coconut fatty acid; and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, tallow fatty acid, and hardened castor fatty acid. Among these, lauric acid, stearic acid, and oleic acid are preferred. The aliphatic amines are not particularly limited, and examples include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl (coconut) amines, alkyl (hardened tallow) amines, alkyl (beef tallow) amines, and alkyl (soybean) amines. The alkanolamide is not particularly limited, and examples thereof include coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, etc. The phosphate ester is not particularly limited, and examples thereof include polyoxyethylene alkyl ether phosphate ester, polyoxyethylene alkyl allyl ether phosphate ester.

[0066] The content of the dispersant in the slurry composition is preferably 0.1 wt % or more, more preferably 0.15 wt % or more, and is preferably 1.5 wt % or less, and is preferably 1.0 wt % or less. The content of the dispersant is preferably 0.1 to 1.5 wt %, more preferably 0.15 to 1.0 wt %.

[0067] The slurry composition may further contain additives such as a plasticizer, a surfactant, etc. Examples of the plasticizer include di(butoxyethyl adipate), dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, triethyl acetylcitrate, tributyl acetylcitrate, diethyl acetylcitrate, dibutyl acetylcitrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, and diethyl ethoxymalonate.

[0068] The surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants. The nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant with an HLB value of 10 to 20. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. For example, for an ester-based surfactant, the saponification value is S, the acid value of the fatty acid constituting the surfactant is A, and the HLB value is defined as 20 (1-S / A). Specifically, nonionic surfactants having polyethylene oxide with an alkylene ether attached to the fatty chain are suitable, and specific examples of suitable surfactants include polyoxyethylene lauryl ether and polyoxyethylene cetyl ether. Although the nonionic surfactant has good thermal decomposition properties, adding a large amount may reduce the thermal decomposition properties of the inorganic particle dispersion slurry composition. Therefore, the preferred upper limit of the content is 5 wt%.

[0069] The viscosity of the slurry composition is not particularly limited, but when measured at 25°C using a Brookfield viscometer, the viscosity is preferably 200 mPa·s or more, more preferably 500 mPa·s or more, and preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less. The viscosity is preferably 200 to 100,000 mPa·s, more preferably 500 to 50,000 mPa·s. By setting the viscosity within the above range, it becomes possible for the resulting inorganic particle-dispersed sheet to maintain a predetermined shape after coating by a die coating printing method or the like. Furthermore, problems such as indelible die coating marks can be prevented, resulting in excellent printability.

[0070] The method for preparing the slurry composition is not particularly limited, and examples thereof include conventionally known stirring methods, specifically, for example, a method in which the vehicle composition, the inorganic particles, the dispersant, and other components added as needed, such as an additional solvent and a plasticizer, are stirred using a triple roll, etc. The order of addition of the components of the slurry composition can be appropriately determined.

[0071] Electronic components can be produced using the above-mentioned slurry composition. A method for producing an electronic component using the above-mentioned slurry composition also constitutes one aspect of the present invention. Examples of the electronic component include die attach paste (ACP), die attach film (ACF), TSV, TGV via electrodes, touch panels, various circuits for RFID and sensor substrates, various die bonding agents, sealants for MEMS devices, solar cells, multilayer ceramic capacitors, LTCC, silicon capacitors, and electrode materials for all-solid-state batteries. In addition to the above-mentioned electrode circuit applications, the composition can also be used for antibacterial materials, electromagnetic wave shielding, catalysts, fluorescent materials, and the like.

[0072] For example, the slurry composition may be applied to a support film having one side subjected to a release treatment, the organic solvent may be dried, and the resulting product may be molded to produce an inorganic particle-dispersed molded product. The shape of the inorganic particle-dispersed molded product is not particularly limited, and may be, for example, a sheet.

[0073] Examples of methods for producing the inorganic particle-dispersed molded product include a method in which the slurry composition is applied to a support film by a coating method such as a roll coater, die coater, squeeze coater, or curtain coater to form a uniform coating film.

[0074] For example, when the inorganic particle-dispersed molded product is in the form of a sheet, the support film used in producing the inorganic particle-dispersed molded product is preferably a resin film that is heat-resistant, solvent-resistant, and flexible. The flexibility of the support film allows the inorganic particle-dispersed slurry composition to be applied to the surface of the support film using a roll coater, blade coater, or the like, and the resulting inorganic particle-dispersed sheet-forming film can be stored and supplied in a rolled state.

[0075] Examples of resins that form the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorine-containing resins such as polyfluoroethylene, nylon, cellulose, etc. The thickness of the support film is preferably, for example, 10 to 100 μm. In addition, the surface of the support film is preferably subjected to a release treatment, which makes it easy to peel off the support film in the transfer step.

[0076] The slurry composition can be applied and dried to produce an inorganic particle dispersion molded product. Furthermore, the slurry composition and the inorganic particle dispersion molded product can be used in a conductive paste for external electrodes to produce a multilayer ceramic capacitor, which is an electronic component.

[0077] A method for producing the multilayer ceramic capacitor includes a step of printing a conductive paste on the inorganic particle dispersion molding and drying it to produce a dielectric sheet, and a step of laminating the dielectric sheets.

[0078] The conductive paste contains a conductive powder. The material of the conductive powder is not particularly limited as long as it is a conductive material, 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.

[0079] The method for printing the conductive paste is not particularly limited, and examples thereof include screen printing, die coating printing, offset printing, gravure printing, and inkjet printing.

[0080] In the method for manufacturing the multilayer ceramic capacitor, dielectric sheets on which the conductive paste is printed are stacked to produce a green ceramic laminate, which is then fired in a reducing atmosphere at a temperature of 300 to 1500°C, thereby obtaining a large number of component elements.

[0081] Next, a conductive paste for external electrodes containing the above-mentioned (meth)acrylic resin particles is applied to both end surfaces of each of these component elements by a dipping method, and then the applied paste is dried at 100 to 200°C and then fired at 300 to 800°C in a reducing atmosphere to form external electrodes on both end surfaces of the component elements.

[0082] Next, the external electrodes are subjected to electrolytic plating to successively form a Cu film, a Ni film, and a Sn film on the external electrodes, thereby obtaining a multilayer ceramic capacitor.

[0083] According to the present invention, there are provided (meth)acrylic resin particles that exhibit excellent low-temperature decomposition properties, can produce molded articles with high strength, and can realize further multilayering and thinning, thereby producing ceramic laminates with excellent properties. Furthermore, there are also provided a vehicle composition, a slurry composition, and a method for producing electronic components, each containing the (meth)acrylic resin particles.

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] (Examples 1 to 18, Comparative Examples 1 to 4) (Preparation of (meth)acrylic resin particles) A ​​2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen gas inlet was prepared, and a total of 100 parts by weight of monomers was charged into the 2 L separable flask so as to obtain the formulation shown in Table 1. 900 parts by weight of water was further mixed to obtain a monomer mixture. The following monomers were used: MMA: methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate HEMA: hydroxyethyl methacrylate LMA: n-lauryl methacrylate

[0086] The resulting monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the atmosphere in the separable flask was replaced with nitrogen gas. The temperature of the water bath was raised to 80°C while stirring. Subsequently, a chain transfer agent and a polymerization initiator were added in the amounts shown in Table 1 to initiate polymerization. Seven hours after the start of polymerization, the mixture was cooled to room temperature to terminate the polymerization. The resulting resin solution was then dried in an oven at 100°C to remove water. This yielded (meth)acrylic resin particles. The following chain transfer agents and polymerization initiators were used. <Chain transfer agent> CT-1: 3-mercapto-1,2-propanediol <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.)

[0087] (Preparation of vehicle composition for dispersing inorganic particles) 90 parts by weight of a solvent having the formulation shown in Table 3 was added to 10 parts by weight of the obtained (meth)acrylic resin particles, and stirred until homogeneous to obtain a vehicle composition for dispersing inorganic particles.

[0088] (Preparation of inorganic particle dispersion slurry composition) To the obtained vehicle composition for dispersing inorganic particles, a solvent, a dispersant, and inorganic particles were added according to the formulation shown in Table 4, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic particle dispersion slurry composition. The solvent used in preparing the vehicle composition for dispersing inorganic particles was used in the same ratio. The dispersant and inorganic particles used were as follows. <Dispersant> Nopcosperse 092 (manufactured by Sanyo Chemical Industries Co., Ltd.) <Inorganic particles> Barium titanate (BT-02, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.2 μm)

[0089] <Evaluation> The (meth)acrylic resin particle and inorganic particle dispersion slurry compositions obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 2, 3 and 5.

[0090] (1) Average Number of Carbons Cp and Cs of Ester Substituents The average number of carbons Cp of the ester substituents of the (meth)acrylic resin particles and the average number of carbons Cs of the ester substituents of the organic solvent were calculated by the following method: Average number of carbons Cp = cp1 × wp1 + cp2 × wp2 + ... + cpn × wpn (cpn: number of carbons of the ester substituents in the segments derived from each (meth)acrylic acid ester constituting the (meth)acrylic resin, wpn: weight fraction of the segments derived from each (meth)acrylic acid ester in the (meth)acrylic resin) Average number of carbons Cs = cs1 × ws1 + cs2 × ws2 + ... + csn × wsn (csn: number of carbons of the ester substituents in each organic solvent, wsn: weight fraction of each organic solvent in the organic solvent)

[0091] (2) Weight Concentration of S Atoms, Weight Concentration of K Atoms, Weight Concentration of OH Groups The weight concentrations of S atoms, OH groups, COOH groups, and K atoms contained in the (meth)acrylic resin particles were calculated by the following method. 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 all monomers+weight of all chain transfer agents+weight of all 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 all monomers+weight of all chain transfer agents+weight of all 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) / (weight of all monomers+weight of all chain transfer agents+weight of all polymerization initiators)]×100

[0092] (3) Particle size The obtained (meth)acrylic resin particles were fed to a laser diffraction / scattering particle size distribution measuring device (LA-950, manufactured by Horiba, Ltd.) to measure the volume average particle size of the (meth)acrylic resin particles.

[0093] (4) CV Value The obtained (meth)acrylic resin particles were observed using a scanning electron microscope (Regulus 8220 manufactured by Hitachi High-Technologies Corporation), and the particle sizes of 100 particles were measured. The CV value was calculated from the average particle size D [μm] and the standard deviation σ of the particle sizes using the following formula: CV value of particle size [%] = σ / D × 100

[0094] (5) Glass Transition Temperature (Tg) The glass transition temperature (Tg) of the obtained (meth)acrylic resin particles was measured using a differential scanning calorimeter (DSC).

[0095] (6) Average Molecular Weight The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained (meth)acrylic resin particles were measured in terms of polystyrene by gel permeation chromatography using an LF-804 (manufactured by SHOKO Corporation) as a column.

[0096] (7) Low-temperature decomposition (TG-DTA) The obtained inorganic particle dispersion slurry composition was packed into a platinum pan of a TG-DTA, and the temperature was raised from 30°C at a rate of 5°C / min in a nitrogen atmosphere to evaporate the solvent and thermally decompose the resin and dispersant. Thereafter, the time (minutes) until 90 wt% degreasing was completed (the weight was 40.4 wt%) was measured.

[0097] (8) Tensile Test The obtained (meth)acrylic resin particles were dissolved in butyl acetate, and the resulting resin solution was applied to a release-treated PET film using an applicator. The film was then dried for 10 minutes in a 100°C air-blowing oven to produce a 20 μm-thick resin sheet. Using graph paper as a cover film, strip-shaped test pieces 1 cm wide were prepared with scissors. The obtained test pieces were subjected to a tensile test using an Autograph AG-IS (manufactured by Shimadzu Corporation) at a chuck distance of 3 cm and a tensile speed of 10 mm / min under conditions of 23°C and 50 RH, and the stress-strain characteristics (yield stress, elongation at break, and tensile performance (yield stress x elongation at break)) were confirmed.

[0098] (9) Thin Film Test The obtained inorganic particle dispersion slurry composition was applied to a release-treated PET film using an applicator and dried for 10 minutes in a 100°C air oven to produce green sheets with dried thicknesses of 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, 7.0 μm, 8.0 μm, 9.0 μm, and 10.0 μm. The green sheets were checked for tears when peeled from the PET film, and the one with the smallest thickness among those without tears was used as the evaluation result.

[0099] (10) Solubility Test 90 parts by weight of a solvent having the formulation shown in Table 2 was added to 10 parts by weight of the obtained (meth)acrylic resin particles, and the mixture was heated to 50°C with stirring. Stirring was continued until the resin particles were dissolved and the solution became homogeneous. The time from the start to the end of stirring was measured.

[0100]

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[0102]

[0103]

[0104]

[0105] According to the present invention, there are provided (meth)acrylic resin particles that exhibit excellent low-temperature decomposition properties, can produce molded articles with high strength, and can realize further multilayering and thinning, thereby producing ceramic laminates with excellent properties. Furthermore, there are also provided a vehicle composition, a slurry composition, and a method for producing electronic components, each containing the (meth)acrylic resin particles.

Claims

1. The weight average molecular weight is 1.1 million or more and 5 million or less, (Meth)acrylic resin particles having a weight concentration of S atoms of 0.0020% by weight or more and 1.0000% by weight or less.

2. The (meth)acrylic resin particles according to claim 1, wherein the weight concentration of K atoms is 0.002% by weight or more and 1.000% by weight or less.

3. The (meth)acrylic resin particles according to claim 1 or 2, wherein the weight concentration of OH groups is 0.00% by weight or more and 1.50% by weight or less.

4. The (meth)acrylic resin particles according to claim 1 or 2, having an average particle size of 0.1 μm or more and 1.0 μm or less.

5. 3. The (meth)acrylic resin particles according to claim 1, wherein the average carbon number Cp of the ester substituents calculated by the following formula is 3 to 6. Average number of carbon atoms of ester substituents of (meth)acrylic resin Cp=cp1×wp1+cp2×wp2+...+cpn×wpn (cpn: number of carbon atoms of ester substituents in segments derived from each (meth)acrylic acid ester constituting the (meth)acrylic resin, wpn: weight fraction of segments derived from each (meth)acrylic acid ester in the (meth)acrylic resin)

6. A vehicle composition comprising the (meth)acrylic resin particles according to claim 1 or 2 and a solvent containing an organic solvent.

7. 7. The vehicle composition according to claim 6, wherein the average carbon number Cs of the ester substituent of the organic solvent calculated by the following formula is 3 to 7. Average number of carbon atoms of ester substituents of organic solvents Cs = cs1 × ws1 + cs2 × ws2 + ... + csn × wsn (csn: number of carbon atoms of ester substituents in each organic solvent, wsn: weight fraction of each organic solvent in the organic solvent)

8. 7. The vehicle composition according to claim 6, wherein the ratio (Cs / Cp) of the average number of carbon atoms Cs of the ester substituents of the organic solvent to the average number of carbon atoms Cp of the ester substituents of the (meth)acrylic resin particles is 0.3 to 3.

0.

9. 7. The vehicle composition according to claim 6, wherein the solvent further contains water in an amount of 100 ppm by weight or more and 11,500 ppm by weight or less.

10. A slurry composition comprising the vehicle composition according to claim 6, inorganic particles, and a dispersant.

11. A method for producing an electronic component, comprising using the slurry composition according to claim 10.