TW202432641A - (Meth)acrylic resin particles, carrier composition, slurry composition and method for producing electronic parts - Google Patents

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, carrier composition, slurry composition and method for producing electronic parts

The present invention relates to a method for manufacturing (meth) acrylic resin particles, a carrier composition, a slurry composition and an electronic component.

As for the multilayer ceramic capacitor, it is known that the multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and internal electrodes are alternately stacked, and a pair of external electrodes are provided so as to sandwich the multilayer ceramic capacitor. The external electrodes are formed by coating a conductive paste for external electrodes on the surface of the multilayer ceramic capacitor and sintering the conductive paste.

In recent years, in order to reduce the energy required for ceramic firing, it is necessary to lower the temperature of the degreasing step to remove the binder resin. In addition, the demand for lightweight and high-performance ceramic parts has increased, and it is necessary to make the ceramic green sheet thinner and more multi-layered during the manufacturing process.

As such a binder resin for ceramic molding, Patent Document 1 discloses a methacrylate copolymer obtained by copolymerizing isobutyl methacrylate, 2-ethylhexyl methacrylate, and methacrylate having a hydroxyl group at a specific ratio. It is believed that by using such a binder resin, good molding properties or degreasing properties can be exhibited. In addition, Patent Document 2 discloses the use of acrylic resin, polyvinyl butyral resin, polyvinyl acetal resin, ethyl cellulose resin, etc. as a binder resin, and in particular, polyvinyl butyral resin or polyvinyl acetal resin is used for thinning of sheets. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 10-167836 [Patent Document 2] Japanese Patent Publication No. 2011-84433

[The problem that the invention wants to solve]

However, although the methacrylate 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. Also, although the polyvinyl butyral resin described in Patent Document 2 can be made into a thin film, it has a high decomposition temperature and cannot be degreased at low temperatures. Therefore, an adhesive resin that can take into account both lowering the degreasing temperature and making a thin film is needed.

The purpose of the present invention is to provide a (meth) acrylic resin particle that exhibits excellent low-temperature decomposition and can obtain a high-strength molded product, which can achieve further multi-layering and thin-filming to produce a ceramic laminate with excellent properties. In addition, the purpose of the present invention is to provide a carrier composition, a slurry composition, and a method for manufacturing electronic components containing the (meth) acrylic resin particles. [Technical means to solve the problem]

The present invention (1) is a (meth)acrylic resin particle having a weight average molecular weight of 1.1 million to 5 million, wherein the weight concentration of S atoms is 0.0020 wt% to 1.0000 wt%. The present invention (2) is a (meth)acrylic resin particle as described in the present invention (1), wherein the weight concentration of K atoms is 0.002 wt% to 1.000 wt%. The present invention (3) is a (meth)acrylic resin particle as described in the present invention (1) or (2), wherein the weight concentration of OH groups is 0.00 wt% to 1.50 wt%. The present invention (4) is a (meth)acrylic resin particle in any combination with any one of the present inventions (1) to (3), wherein the average particle size is 0.1 μm to 1.0 μm. The present invention (5) is a (meth)acrylic resin particle in any combination with any one of the present inventions (1) to (4), wherein the average carbon number Cp of the ester substituent calculated by the following formula is 3 to 6, The average carbon number Cp of the ester substituent of the (meth)acrylic resin = cp1×wp1+cp2×wp2+…+cpn×wpn (cpn: the carbon number of the ester substituent in the chain segment derived from each (meth)acrylic ester constituting the (meth)acrylic resin; wpn: the weight fraction of the chain segment derived from each (meth)acrylic ester in the (meth)acrylic resin). The present invention (6) is a carrier composition comprising the (meth)acrylic resin particle of any one of the present inventions (1) to (5) and a solvent comprising an organic solvent. The present invention (7) is a carrier composition as in the present invention (6), wherein the average carbon number Cs of the ester substituent of the organic solvent calculated by the following formula is 3 to 7, The average carbon number Cs of the ester substituent of the organic solvent = cs1×ws1+cs2×ws2+…+csn×wsn (csn: the carbon number of the ester substituent in each organic solvent; wsn: the weight fraction of each organic solvent in the organic solvent). The present invention (8) is a carrier composition as in the present invention (6) or (7), wherein the ratio (Cs/Cp) of the average carbon number Cs of the ester substituent of the organic solvent to the average carbon number Cp of the ester substituent of the (meth) acrylic resin is 0.3 to 3.0. The present invention (9) is a carrier composition in any combination with any one of the present inventions (6) to (8), wherein the solvent further contains water in an amount of not less than 100 ppm by weight and not more than 11,500 ppm by weight. The present invention (10) is a slurry composition, which contains the carrier composition of any one of the present inventions (6) to (9), inorganic particles and a dispersant. The present invention (11) is a method for manufacturing electronic components, which uses the slurry composition of the present invention (10). The present invention is described in detail below.

The inventors of the present invention have found that (meth)acrylic resin particles having a specific weight average molecular weight and a weight concentration of sulfur atoms exhibit excellent low-temperature decomposition properties and, when used as a binder for dispersing inorganic particles, can obtain a high-strength molded product, which can be further multi-layered and thin-filmed. The inventors have also found that by using such (meth)acrylic resin particles, a ceramic laminate having excellent properties can be manufactured, thereby completing the present invention.

The weight average molecular weight (Mw) of the (meth) acrylic resin particles is 1.1 million to 5 million. If the weight average molecular weight is 1.1 million or more, the tensile properties of the obtained resin sheet are improved. If the weight average molecular weight is 5 million or less, it becomes difficult to produce undissolved (meth) acrylic resin in the obtained resin sheet, and the tensile properties are improved. According to the above situation, by setting the above range, the strength of the molded product can be improved, so that a further thin film green sheet can be manufactured. The weight average molecular weight (Mw) is preferably 1.3 million or more, more preferably 1.5 million or more, and more preferably 2 million or more. In addition, the weight average molecular weight (Mw) is preferably 4.5 million or less, more preferably 4 million or less, and 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.

Furthermore, the number average molecular weight (Mn) of the (meth) acrylic resin particles is preferably 300,000 or more, more preferably 600,000 or more, preferably 2 million or less, and more preferably 1.5 million or less. The number average molecular weight (Mn) is preferably 300,000 to 2 million, and more preferably 600,000 to 1.5 million. 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 1 or more, preferably 5.0 or less, more preferably 4.0 or less, and more preferably 3.5 or less. The Mw/Mn is preferably 1 to 5.0, more preferably 1 to 4.0, and more preferably 1 to 3.5. If it is within the above range, it becomes difficult to generate fine undissolved matter in the carrier composition, which can fully improve the strength of the resin sheet and prevent the generation of voids in the ceramic laminate after firing. Furthermore, the above weight average molecular weight (Mw) and the above number average molecular weight (Mn) are average molecular weights converted based on polystyrene and can be obtained by using, for example, column LF-804 (manufactured by Showa Denko K.K.) as a column for GPC (Gel Permeation Chromatography) measurement.

The weight concentration of S atoms contained in the above-mentioned (meth) acrylic resin particles is 0.0020 wt% or more and 1.0000 wt% or less. By setting it in the above range, it is possible to take into account both low-temperature decomposition and the strength of the molded product. The weight concentration of the above-mentioned S atoms is preferably 0.0030 wt% or more, more preferably 0.0060 wt% or more, and further preferably 0.0100 wt% or more, and preferably 0.9000 wt% or less, more preferably 0.1000 wt% or less, and further preferably 0.0400 wt% or less. The weight concentration of the above-mentioned S atoms is preferably 0.0030 to 0.9000 wt%, more preferably 0.0060 to 0.1000 wt%, and further preferably 0.0100 to 0.0400 wt%. If it is below the upper limit, the low-temperature decomposition property can be made better, and if it is above the lower limit, the tensile performance can be in a good range, and the strength of the molded product can be further improved. 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, which can be calculated based on the following formula. The weight concentration of S atoms contained in (meth) acrylic resin particles = [(the weight of S atoms contained in all monomers + the weight of S atoms contained in all chain transfer agents + the weight of S atoms contained in all polymerization initiators) / (the weight of all monomers + the weight of all chain transfer agents + the weight of all polymerization initiators)] × 100. In addition, the weight concentration of the above-mentioned S atoms can also be obtained by ICP-AES (inductively coupled plasma-atomic emission spectrometry).

From the viewpoint of the strength of the molded product, 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, and more preferably 0.015 wt% or more, and more preferably 0.500 wt% or less, and 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 more preferably 0.015 to 0.030 wt%. If it is below the upper limit, the low-temperature decomposition property can be made better, and if it is above the lower limit, the tensile performance can be in a good range, and the strength of the molded product can be further improved. 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. The weight concentration of K atoms contained in (meth) acrylic resin particles = [(the weight of K atoms contained in all monomers + the weight of K atoms contained in all chain transfer agents + the weight of K atoms contained in all polymerization initiators) / (the weight of all monomers + the weight of all chain transfer agents + the weight of all polymerization initiators)] × 100. In addition, the weight concentration of K atoms can also be measured using an atomic absorption spectrophotometer.

From the viewpoint of low-temperature decomposition, the weight concentration of OH groups contained in the above-mentioned (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 further preferably 0.25 wt% or less. The weight concentration of the above-mentioned OH groups is preferably 0.00 to 1.50 wt%, more preferably 0.00 to 0.50 wt%, and further preferably 0.00 to 0.25 wt%. The weight concentration of the above-mentioned OH groups means the ratio of the weight of the OH groups in the above-mentioned (meth) acrylic resin structure to the weight of the above-mentioned (meth) acrylic resin particles, which can be calculated based on the following formula. The weight concentration of OH groups contained in (meth) acrylic resin particles = [(the weight of OH groups contained in all monomers + the weight of OH groups contained in all chain transfer agents + the weight of OH groups contained in all polymerization initiators) / (the weight of all monomers + the weight of all chain transfer agents + the weight of all polymerization initiators)] × 100. In addition, the above-mentioned weight concentration of OH groups can also be obtained by ESCA (electron spectroscopy for chemical analysis) analysis based on gas phase chemical modification method.

The weight concentration of COOH groups contained in the (meth)acrylic resin particles is not particularly limited, but preferably contains no COOH groups and has a weight concentration of 0% by weight from the viewpoint of low-temperature decomposition.

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 above 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, more preferably 0.3 μm or more, more preferably 0.9 μm or less, and 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 more preferably 0.3 to 0.8 μm. The average particle size can be obtained, for example, by measuring the volume average particle size using a laser diffraction/scattering particle size distribution measuring device. Furthermore, the above average particle size can be adjusted by the type and amount of the polymerization initiator. For example, if the content of the polymerization initiator is high, the average particle size tends to be smaller, and if the content of the polymerization initiator is low, the average particle size tends to be larger. Also, for example, if persulfates such as ammonium persulfate or potassium persulfate are used, the average particle size tends to be smaller.

The CV value of the particle size of the above-mentioned (meth) acrylic resin particles is preferably 15% or less, more preferably 12% or less, further preferably 10% or less, further preferably 8% or less. By setting the above range, the solubility of the (meth) acrylic resin particles can be further improved. If the solubility is improved, the productivity is improved, and the tensile performance is improved due to the reduction of undissolved resin. The lower limit is not particularly limited, for example, it is 0%. The CV value of the above-mentioned particle size is preferably 0-15%, more preferably 0-12%, further preferably 0-10%, further preferably 0-8%. The above-mentioned CV value can be observed by using a scanning electron microscope to observe the (meth) acrylic resin particles and calculate based on the average value and standard deviation of the particle size of 100 particles. If persulfates such as ammonium persulfate or potassium persulfate are used, the above CV value tends to decrease.

The (meth)acrylic resin particles preferably contain a chain segment of a (meth)acrylic acid ester having a carbon number of 8 or less derived from an ester substituent. Furthermore, the carbon number of the ester substituent being 8 or less means that the total number of carbon atoms in the (meth)acrylic acid ester excluding the carbon atoms constituting the (meth)acrylic acid group is 8 or less. As the (meth)acrylic acid ester having a carbon number of 8 or less in the ester substituent, there can be exemplified a (meth)acrylic acid ester having a linear, branched or cyclic alkyl group. As the (meth)acrylic acid ester having a linear alkyl group, there can be exemplified: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, etc. Examples of the (meth)acrylate having a branched alkyl group include isopropyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples of the (meth)acrylate having a cyclic alkyl group include cyclohexyl (meth)acrylate and benzyl (meth)acrylate. In addition, as the (meth)acrylate having an ester substituent with a carbon number of 8 or less, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, (meth)acrylic acid, and other (meth)acrylates having a hydroxyl or carboxyl group, and (meth)acrylates having a glycidyl group, etc., can also be used. As the above-mentioned (meth)acrylate having a glycidyl group, for example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxyhexyl (meth)acrylate, etc. can be cited. Among them, (meth)acrylate having a linear alkyl group and (meth)acrylate having a branched alkyl group are preferred. Moreover, methyl methacrylate, ethyl methacrylate, and isobutyl methacrylate are more preferred. Furthermore, a combination of a (meth)acrylate having a linear alkyl group and a (meth)acrylate having a branched alkyl group is preferred.

As the (meth)acrylate having 8 or less carbon atoms in the ester substituent, a (meth)acrylate having 1 to 4 carbon atoms in the ester substituent can be used, or a (meth)acrylate having 5 to 8 carbon atoms in the ester substituent can be used. Among them, a (meth)acrylate having 1 to 4 carbon atoms in the ester substituent is preferred. In addition, the (meth)acrylate having 8 or less carbon atoms in the ester substituent is preferably a (meth)acrylate not containing an epoxypropyl group.

The content of the chain segment of the (meth)acrylate ester in which the carbon number of the ester substituent is 8 or less in the (meth)acrylate resin particles is preferably 40% by weight or more, more preferably 60% by weight or more, and further 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 further preferably 98% by weight or less. The content of the chain segment of the (meth)acrylate ester in which the carbon number of the ester substituent is 8 or less is preferably 40-100% by weight, more preferably 60-99% by weight, and further preferably 80-98% by weight. Furthermore, the content of the above-mentioned chain segments in the above-mentioned (meth)acrylic resin particles can be calculated based on the following ratio: the ratio of each monomer to 100 parts by weight of the raw material monomers other than the polymerization initiator and the chain transfer agent in the raw materials for preparing the (meth)acrylic resin constituting the (meth)acrylic resin particles.

The content of the chain segment derived from the (meth)acrylate having a branched alkyl group with a carbon number of 8 or less in the ester substituent in the (meth)acrylic resin particles is preferably 30% by weight or more, more preferably 35% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less. The content of the chain segment derived from the (meth)acrylate having a branched alkyl group with a carbon number of 8 or less in the ester substituent is preferably 30-70% by weight, more preferably 35-60% by weight.

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

The content of the chain segment derived from the (meth)acrylate having 5 to 8 carbon atoms in the ester substituent in the (meth)acrylate resin particles is preferably 60 wt % or less, more preferably 40 wt % or less, and further preferably 20 wt % or less. The lower limit is not particularly limited, and for example, it is 0 wt % or more. The content of the chain segment derived from the (meth)acrylate having 5 to 8 carbon atoms in the ester substituent is preferably 0 to 60 wt %, more preferably 0 to 40 wt %, and further preferably 0 to 20 wt %.

The content of the chain segments derived from methyl methacrylate in the (meth)acrylic resin particles is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 40% by weight or less, more preferably 30% by weight or less. The content of the chain segments derived from methyl methacrylate is preferably 5-40% by weight, more preferably 10-30% by weight.

The content of the chain segments derived from ethyl methacrylate in the (meth)acrylic resin particles is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. The content of the chain segments derived from ethyl methacrylate is preferably 10-30% by weight, more preferably 20-25% by weight.

The content of the chain segments derived from n-butyl methacrylate in the (meth)acrylic resin particles is preferably 25% by weight or more, more preferably 30% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. The content of the chain segments derived from n-butyl methacrylate is preferably 25-50% by weight, more preferably 30-40% by weight.

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

The (meth) acrylic resin particles may also have a chain segment derived from a (meth) acrylic ester having an ester substituent having a carbon number of 9 or more. The carbon number of the ester substituent is preferably 10 or 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.

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

Examples of the (meth)acrylate having a linear or branched alkyl group with a carbon number of 9 or more 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, isostearyl (meth)acrylate, etc. Examples of the polyalkylene glycol (meth)acrylate include those having ethylene glycol units, propylene glycol units, butanediol units, etc. Furthermore, the polyalkylene glycol (meth)acrylate may have an alkoxy group at the end, or may have an ethylhexyl group at the end. Furthermore, the polyalkylene glycol (meth)acrylate may have a linear alkylene glycol unit, or may have a branched alkylene glycol unit.

The content of the chain segment derived from the (meth)acrylate having 9 or more carbon atoms in the ester substituent in the (meth)acrylate resin particles is preferably 60 wt % or less, more preferably 40 wt % or less, and further preferably 20 wt % or less. The lower limit is not particularly limited, and is, for example, 0 wt % or more. The content of the chain segment derived from the (meth)acrylate having 9 or more carbon atoms in the ester substituent is preferably 0 to 60 wt %, more preferably 0 to 40 wt %, and further preferably 0 to 20 wt %.

The content of the chain segment derived from the acrylic acid monomer in the above-mentioned (meth) acrylic resin particles has the advantage that the lower the content, the better the low-temperature decomposition property. Therefore, it is preferably 5% by weight or less, and more preferably 1% by weight or less. The lower limit is not particularly limited, for example, it is 0% by weight or more. The content of the chain segment derived from the acrylic acid monomer is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, and further preferably 0% by weight. Furthermore, the above-mentioned acrylic acid monomer means acrylic acid and acrylic ester.

The average carbon number Cp of the ester substituent of the (meth) acrylic resin particles calculated by the following formula is preferably 3 or more, preferably 6 or less. If the average carbon number Cp is 3 or more, the elongation at break of the obtained resin sheet becomes good, and the tensile performance is improved. If the average carbon number Cp is 6 or less, the yield stress becomes high, and the tensile performance is improved. 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. The average carbon number of the ester substituent Cp = cp1×wp1＋cp2×wp2＋…＋cpn×wpn (cpn: the carbon number of the ester substituent in the chain segment derived from each (meth)acrylate constituting the (meth)acrylate resin; wpn: the weight fraction of the chain segment derived from each (meth)acrylate constituting the (meth)acrylate resin)

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

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

As a method for producing the above-mentioned (meth) acrylic resin particles, for example, the following method can be cited: adding an organic solvent to a raw material monomer mixture containing (meth) acrylic acid esters to prepare a monomer mixture, and then adding a polymerization initiator and a chain transfer agent to the obtained monomer mixture to copolymerize the above-mentioned raw material monomers. The polymerization method is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, solution polymerization, etc. Among them, emulsion polymerization is preferred.

Examples of the organic solvent include toluene, ethyl acetate, butyl acetate, amyl acetate, hexyl acetate, ethyl butyrate, butyl butyrate, amyl butyrate, hexyl butyrate, isopropyl alcohol, 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, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate ... The organic solvents include 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 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. More preferred are butyl acetate, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate. Furthermore, the organic solvents may be used alone or in combination of two or more.

Examples of the polymerization initiator include t-butyl peroxypivalate, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, isopropylbenzene hydroperoxide, t-butyl hydroperoxide, cyclohexanone peroxide, and disuccinic acid peroxide. In addition, examples include: 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 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-( Water-soluble azo compounds such as [(2-methyl-N-(2-hydroxyethyl)-propionamide] tetrahydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis-4-cyanovaleric acid; oxygen-containing acids such as potassium persulfate (potassium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate), sodium persulfate (sodium peroxodisulfate); peroxides such as hydrogen peroxide, peracetic acid, performic acid, and perpropionic acid. Among them, polymerization initiators containing S atoms and polymerization initiators containing K atoms can be preferably used. Furthermore, potassium persulfate, ammonium persulfate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 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.

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, more preferably 3.6 parts by weight or less, relative to 100 parts by weight of the raw material monomer. The amount of the polymerization initiator added is preferably 0.03-4.0 parts by weight, more preferably 0.05-3.6 parts by weight, relative to 100 parts by weight of the raw material monomer.

As the above-mentioned chain transfer agent, a chain transfer agent having a S atom can be preferably used, for example: 3-butyl-1,2-propanediol, 3-butyl-1-propanol, 3-butyl-2-butanol, 8-butyl-1-octanol, 2-butylbenzimidazole, butylsuccinic acid, butylacetic acid, etc. Among them, 3-butyl-1,2-propanediol can be preferably used.

The amount of the chain transfer agent added is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, 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 monomer. 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 monomer.

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

The above-mentioned (meth) acrylic resin particles and a solvent containing an organic solvent can be used to prepare a carrier composition. The carrier composition containing the above-mentioned (meth) acrylic resin particles and a solvent containing an organic solvent is also one of the present inventions.

The content of the (meth)acrylic resin particles in the carrier composition is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less. The content of the (meth)acrylic resin particles is preferably 5-50% by weight, more preferably 10-40% by weight.

The carrier composition contains an organic solvent. Examples of the organic solvent include alcohols such as aliphatic alcohols, glycols, terpene alcohols, aromatic alcohols, aromatic hydrocarbons, esters, ketones, and N-methylpyrrolidone. Examples of the aliphatic alcohols include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecanol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecanol, oleyl alcohol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2-butyl-2-ethyl-1,3-propanediol, and neopentyl glycol. Examples of the above-mentioned diols 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, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol ethyl ether, etc. Examples of the above-mentioned terpene alcohols include terpineol, dihydroterpineol, terpineol acetate, dihydroterpineol acetate, etc. Examples of the above-mentioned aromatic alcohols include benzyl alcohol, etc. Examples of the above-mentioned aromatic hydrocarbons include toluene, etc. Examples of the above-mentioned esters include methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, dodecyl acetate, isoamyl acetate, butyl butyrate, butyl lactate, dioctyl phthalate, dioctyl adipate, etc. Examples of the above-mentioned ketones include methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, etc. Among them, esters are preferred, and methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, and dodecyl acetate are more preferred, and ethyl acetate, butyl acetate, and hexyl acetate are further preferred.

The average carbon number Cs of the ester substituent of the above organic solvent calculated by the following formula is preferably 3 or more, and preferably 7 or less. If it is within the above range, the affinity between the acrylic resin and the organic solvent becomes higher, and the tensile properties can be improved. The above average carbon number Cs is more preferably 3.5 or more, and further preferably 4.5 or less. The above Cs is preferably 3 to 7, and more preferably 3.5 to 4.5. The average carbon number Cs of the ester substituent of the organic solvent = cs1×ws1+cs2×ws2+…+csn×wsn (csn: the carbon number of the ester substituent in each organic solvent; wsn: the weight fraction of each organic solvent in the organic solvent)

From the perspective of the strength of the molded product, the ratio (Cs/Cp) of the average carbon number Cs of the ester substituent of the above-mentioned organic solvent in the above-mentioned carrier composition to the average carbon number Cp of the ester substituent of the above-mentioned (meth) acrylic resin particles is preferably 0.3 or more, preferably 3.0 or less. If it is within the above range, the affinity between the (meth) acrylic resin particles and the organic solvent becomes higher, which can improve the tensile performance. In addition, if it is within the above range, the affinity between the (meth) acrylic resin particles and the organic solvent becomes higher, which can improve the solubility of the resin. The above Cs/Cp is more preferably 0.5 or more, and more preferably 1.5 or less. The above Cs/Cp is preferably 0.3 to 3.0, and more preferably 0.5 to 1.5.

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

In the above-mentioned carrier composition, the solvent preferably further contains water. The content of the above-mentioned water in the above-mentioned solvent is preferably 100 weight ppm or more, preferably 11500 weight ppm or less. By containing water in the above-mentioned range, the affinity with the dispersant is improved, and the low-temperature decomposition property is further improved. The content of the above-mentioned water in the above-mentioned solvent is preferably 300 weight ppm or more, and more preferably 400 weight ppm or more, and more preferably 1000 weight ppm or less, and more preferably 700 weight ppm or less. The content of the above-mentioned water is preferably 100-11500 weight ppm, more preferably 300-1000 weight ppm, and more preferably 400-700 weight ppm.

The water content in the carrier composition is preferably 100 ppm by weight or more and preferably 10,000 ppm by weight or less. The water content is preferably 100 to 10,000 ppm by weight.

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

As a method for producing the above-mentioned carrier composition, for example, there can be mentioned a method in which an organic solvent, water, etc. are added to the (meth)acrylic resin particles obtained by the above-mentioned method, and the mixture is stirred and mixed.

The above-mentioned carrier composition, inorganic particles and dispersant can be used to prepare a slurry composition. The slurry composition containing the above-mentioned carrier composition, inorganic particles and dispersant is also one of the present inventions.

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

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

The water content in the slurry composition is preferably 30 wtppm or more, more preferably 1000 wtppm or more, further preferably 5000 wtppm or more, and preferably 15000 wtppm or less, more preferably 10000 wtppm or less, further preferably 7000 wtppm or less. The water content is preferably 30-15000 wtppm, more preferably 1000-10000 wtppm, further preferably 5000-7000 wtppm.

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

The slurry composition contains inorganic particles. The inorganic particles are not particularly limited, and examples thereof include glass powder, ceramic powder, fluorescent particles, silicon oxide, metal particles, etc.

The glass powder is not particularly limited and examples thereof include glass powders of bismuth oxide glass, silicate glass, lead glass, _zinc glass, boron glass, etc., or glass powders of various silicon oxides such as CaO- _Al2O3 - _SiO2 , MgO- _{Al2O3 - SiO2} , and LiO2 _{- Al2O3 - SiO2} . As the glass powder, a SnO-B ₂ O ₃ -P ₂ O ₅ -Al ₂ O ₃ mixture, a PbO-B ₂ O ₃ -SiO ₂ mixture, a BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture, a ZnO-Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ mixture, a Bi ₂ O ₃ -B ₂ O ₃ -BaO-CuO mixture, a Bi ₂ O ₃ -ZnO-B ₂ O ₃ -Al ₂ O ₃ -SrO mixture, a ZnO-Bi ₂ O ₃ -B ₂ O ₃ mixture, a Bi ₂ O ₃ -SiO ₂ mixture, a P ₂ O ₅ -Na ₂ O-CaO-BaO-Al ₂ O ₃ -B ₂ O ₃ mixture, a P ₂ O ₅ -SnO mixture, a P ₂ O ₅ -SnO-B ₂ O ₃ mixture, a P Glass powders of _{a 2} O ₅ -SnO-SiO ₂ mixture, a CuO-P ₂ O ₅ -RO mixture, a SiO ₂ -B ₂ O ₃ -ZnO-Na ₂ O-Li ₂ O-NaF-V ₂ O ₅ mixture, a P ₂ O ₅ -ZnO-SnO-R ₂ O-RO mixture, a B ₂ O ₃ -SiO ₂ -ZnO mixture, a B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -ZrO ₂ mixture, a SiO ₂ -B ₂ O ₃ -ZnO-R ₂ O-RO mixture, a SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -RO-R ₂ O mixture, a SrO-ZnO-P ₂ O ₅ mixture, a SrO-ZnO-P ₂ O ₅ mixture, a BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture, and the like. Furthermore, R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe and Mn. In particular, it is preferably a glass powder of a PbO- _{B2O3 - SiO2} mixture, or a lead-free glass powder of a lead-free BaO-ZnO- _{B2O3 - SiO2} mixture or a ZnO- _{Bi2O3 - B2O3 - SiO2} mixture.

The ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconium oxide, zirconite, barium zirconate, calcium zirconate, titanium oxide, barium titanium oxide, strontium titanium oxide, calcium titanium oxide, magnesium titanium oxide, zinc titanium oxide, neodymium titanium oxide, lead zirconium titanium oxide, aluminum nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, talc, cordierite, and magnesium silicate. In addition, ITO (indium tin oxide), FTO (fluorine-doped tin oxide), niobium oxide, vanadium oxide, tungsten oxide, strontium manganite, strontium cobalt ferrite, yttria-stabilized zirconia, gadolinium doped niobium oxide (gadolinium doped-ceria), nickel oxide, chromium chromide, etc. can also be used. The above-mentioned fluorescent particles are not particularly limited. For example, as the fluorescent material, blue fluorescent materials, red fluorescent materials, green fluorescent materials, etc., which are conventionally known as fluorescent materials for displays, can be used. As the blue fluorescent substance, for example, _MgAl10O17 :Eu, _{Y2SiO5 : Ce} system, _{CaWO4 :} Pb system, _BaMgAl14O23 : _Eu system, _BaMgAl16O27 :Eu system, BaMg2Al14O23 _: Eu _system , _{BaMg2Al14O27 :} Eu system, and _ZnS :(Ag, _Cd ) system can be used. As the red fluorescent substance, for example, _Y2O3 :Eu system, _{Y2SiO5 :} Eu system, _Y3Al5O12 :Eu system, _Zn3 ( _PO4 ) ₂ :Mn system, _YBO3 :Eu system, (Y, _Gd ) _BO3 :Eu system, _GdBO3 :Eu system _{, ScBO3} :Eu system, _{and LuBO3} :Eu system can be used. As the green fluorescent substance, for example _{, Zn2SiO4} :Mn system, _BaAl12O19 :Mn system, _SrAl13O19 :Mn system, _CaAl12O19 :Mn system, _YBO3 :Tb system, BaMgAl14O23:Mn system, _{LuBO3 :} Tb _system , _GdBO3 :Tb system, _{ScBO3 :} Tb system, _Sr6Si3O3Cl4 :Eu system can be used. In addition, _ZnO :Zn system, ZnS:(Cu _, Al) system, ZnS:Ag system, _Y2O2S :Eu system, ZnS: _Zn system _, (Y,Cd) _BO3 :Eu system, _BaMgAl12O23 :Eu _system can _also be used.

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

The inorganic particles preferably contain lithium or titanium. Specifically, for example, low melting point glasses _such as _LiO2・_Al2O3・_SiO2 inorganic glasses, lithium _{chalcogenide glasses} such as _Li2SMxSy (M＝B, Si, Ge, P), lithium cobalt composite oxides such as _LiCeO2 , lithium manganese composite oxides such as _LiMnO4 , lithium nickel composite oxides, lithium vanadium composite oxides, lithium zirconium composite oxides, lithium benzimidazole composite oxides, lithium silicophosphate ( _{Li3.5Si0.5P0.5O4} ), lithium titanium phosphate ( _LiTi2 ( _PO4 ) ₃ ), _lithium titanate _{( Li4Ti5O12 )} , _{Li4 / 3Ti5 / 3O4} , _LiCoO2 , lithium germanium phosphate ( _LiGe2 (PO ₄ ) ₃ ), Li ₂ -SiS glass, Li ₄ GeS ₄ -Li ₃ PS ₄ glass, LiSiO ₃ , LiMn ₂ O ₄ , Li ₂ SP ₂ S ₅ glass and ceramics, Li ₂ O-SiO ₂ , Li ₂ OV ₂ O ₅ -SiO ₂ , LiS-SiS ₂ -Li ₄ SiO ₄ glass, LiPON plasma conductive oxide, Li ₂ OP ₂ O ₅ -B ₂ O ₃ , Li ₂ O-GeO ₂ Ba and other lithium oxide compounds, Li _{x Aly} Ti _z (PO ₄ ) ₃ glass, La _x Li _y TiO _z glass, Li _x Ge _y P _z O ₄ glass, Li ₇ La ₃ Zr ₂ O ₁₂ glass, Li _v Si _w P _{x Sy} Cl _z glass, LiNbO ₃ and other lithium-niobium oxides, aluminum-lithium oxide compounds such as Li-β-alumina, lithium-zinc oxides such as Li ₁₄ Zn(GeO ₄ ) _4, etc.

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

The content of the above-mentioned inorganic particles in the above-mentioned slurry composition is preferably 30% by weight or more, preferably 90% by weight or less. If it is within the above range, it can have sufficient viscosity and excellent coating properties, and further, it can be made into one with excellent dispersibility of inorganic particles. The content of the above-mentioned inorganic particles is more preferably 40% by weight or more, and more preferably 70% by weight or less. The content of the above-mentioned inorganic particles is preferably 30-90% by weight, and more preferably 40-70% by weight.

The slurry composition contains a dispersant. As the dispersant, for example, fatty acids, fatty amines, alkanolamides, and phosphates are preferred. In addition, silane coupling agents may also be mixed. As the fatty acid, there is no particular limitation, and examples thereof include: saturated fatty acids such as oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and coconut fatty acid; unsaturated fatty acids such as oleic acid, linolenic acid, linolenic acid, sorbic acid, tallow fatty acid, and castor hydrogenated stearate. Among them, lauric acid, stearic acid, and oleic acid are preferred. The above-mentioned aliphatic amine is not particularly limited, and examples thereof include: laurylamine, myristic amine, cetylamine, stearylamine, oleylamine, alkyl (coconut) amine, alkyl (hydrogenated tallow) amine, alkyl (tallow) amine, alkyl (soy) amine, etc. The above-mentioned alkanolamide is not particularly limited, and examples thereof include: coconut fatty acid diethanolamide, tallow fatty acid diethanolamide, lauric acid diethanolamide, oleic acid diethanolamide, etc. The above-mentioned phosphate is not particularly limited, and examples thereof include: polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate.

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

The slurry composition may further include additives such as plasticizers and surfactants. Examples of the plasticizer include: di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl ester, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dicaproate, triethyl acetyl citrate, tributyl acetyl citrate, diethyl acetyl citrate, dibutyl acetyl citrate, dibutyl sebacate, triacetin, diethyl acetoxymalonate, diethyl ethoxymalonate, etc.

The above-mentioned surfactant is not particularly limited, and examples thereof include: cationic surfactant, anionic surfactant, and nonionic surfactant. As the above-mentioned nonionic surfactant, there is no particular limitation, and a nonionic surfactant with an HLB value of 10 or more and 20 or less is preferred. Here, the HLB value refers to an index used to represent the hydrophilicity and lipophilicity of the surfactant, and several calculation methods are proposed. For example, for ester-based surfactants, the saponification value is set to S, the acid value of the fatty acid constituting the surfactant is set to A, and the HLB value is set to 20 (1-S/A). Specifically, it is preferred to use a non-ionic surfactant having polyethylene oxide obtained by adding an alkyl ether to a fatty chain. Specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl wax ether, etc. can be preferably used. Furthermore, although the above non-ionic surfactant has good thermal decomposition properties, there is a situation where if a large amount is added, the thermal decomposition properties of the inorganic particle dispersion slurry composition will decrease. Therefore, the preferred upper limit of the content is 5% by weight.

The viscosity of the slurry composition is not particularly limited. When measured at 25°C using a B-type viscometer, the viscosity is preferably 200 mPa·s or more, more preferably 500 mPa·s or more, and preferably 100000 mPa·s or less, more preferably 50000 mPa·s or less. The above viscosity is preferably 200 to 100000 mPa·s, more preferably 500 to 50000 mPa·s. By setting the above range, after coating using a mold coating printing method, the obtained inorganic particle dispersion sheet can maintain a specific shape. In addition, it can prevent the undesirable situation that the coating marks of the mold cannot be eliminated, and produce a sheet with excellent printability.

The method for preparing the slurry composition is not particularly limited, and a conventionally known stirring method may be cited. Specifically, for example, a method of stirring the carrier composition, the inorganic particles, the dispersant, and other components such as additional solvents and plasticizers as needed by a three-roll mill may be cited. The order of adding the components of the slurry composition may be appropriately set.

By using the above-mentioned slurry composition, electronic parts can be manufactured. A method for manufacturing electronic parts using the above-mentioned slurry composition is also one of the present inventions. As the above-mentioned electronic parts, examples include: die attach paste (ACP), die attach film (ACF), via electrodes for TSV and TGV, touch panels, various circuits of RFID or sensor substrates, various die attach agents, sealants for MEMS devices, solar cells, multilayer ceramic capacitors, LTCC, silicon capacitors, all-solid-state batteries and other electrode materials. In addition to the above-mentioned electrode circuit uses, it can also be used for antibacterial components or electromagnetic wave shielding, catalysts, fluorescent materials, etc.

For example, by applying the slurry composition on a support film subjected to a one-side demolding treatment and drying the organic solvent to form a mold, an inorganic particle dispersed molded product can be produced. The shape of the inorganic particle dispersed molded product is not particularly limited, and it can be made into a sheet or the like, for example.

As a method for producing the above-mentioned inorganic particle dispersed molded product, for example, there can be cited a method in which the above-mentioned slurry composition is uniformly formed into a coating film on a support film by a coating method such as a roll coater, a die coater, an extrusion coater, a curtain coater, etc.

For example, when the inorganic particle dispersion molded product is in the form of a sheet, the support film used in manufacturing the inorganic particle dispersion molded product is preferably a resin film having heat resistance and solvent resistance and flexibility. By making the support film flexible, the inorganic particle dispersion slurry composition can be coated on the surface of the support film using a roll coater, a doctor blade coater, etc., and the obtained inorganic particle dispersion sheet-forming film can be stored and supplied in a rolled state.

As the resin forming the above-mentioned support film, for example, there can be cited: polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyvinyl fluoride and other fluorine-containing resins, nylon, cellulose, etc. The thickness of the above-mentioned support film is preferably 10 to 100 μm, for example. In addition, it is preferred to perform a demolding treatment on the surface of the support film, thereby making it easy to perform a peeling operation of the support film in the transfer step.

By applying and drying the above slurry composition, an inorganic particle dispersed molded product can be manufactured. In addition, by using the above slurry composition and inorganic particle dispersed molded product for conductive paste for external electrodes, a "multilayer ceramic capacitor for electronic parts" can be manufactured.

As a method for manufacturing the above-mentioned multilayer ceramic capacitor, there can be cited a manufacturing method having the following steps: a step of printing a conductive paste on the above-mentioned inorganic particle dispersion molded product and drying it to prepare a dielectric sheet; and a step of laminating the above-mentioned dielectric sheet.

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

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

In the manufacturing method of the above-mentioned multilayer ceramic capacitor, a dielectric sheet printed with the above-mentioned conductive glue is laminated to produce an unprocessed ceramic laminate body, and then a sintering treatment is performed in a reducing environment at a temperature of 300 to 1500° C., thereby obtaining a plurality of component blanks.

Next, a conductive glue for external electrodes containing the above-mentioned (meth) acrylic resin particles is applied to both end surfaces of each of the component blanks by an immersion method, and then dried at 100-200°C and sintered at 300-800°C in a reducing environment to form external electrodes at both ends of the component blanks.

Next, electrolytic plating is performed on the external electrode to sequentially form a Cu film, a Ni film, and a Sn film on the external electrode, thereby obtaining a multilayer ceramic capacitor. [Effect of the invention]

According to the present invention, a (meth)acrylic resin particle can be provided, which exhibits excellent low-temperature decomposition and can obtain a high-strength molded product, and can achieve further multi-layering and thin-filming to manufacture a ceramic laminate with excellent characteristics. In addition, a carrier composition, a slurry composition and a manufacturing method of an electronic component containing the (meth)acrylic resin particle can be provided.

The following disclosed embodiments further illustrate the present invention in detail, but the present invention is not limited to these embodiments.

(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 condenser, a thermometer, a hot water bath, and a nitrogen inlet was prepared, and a total of 100 parts by weight of monomers were added to the 2 L separable flask in a manner to form the composition shown in Table 1. Furthermore, 900 parts by weight of water were mixed to obtain a monomer mixed liquid. Furthermore, the following were used as monomers. MMA: methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate iBMA: isobutyl methacrylate 2EHMA: 2-ethylhexyl methacrylate HEMA: hydroxyethyl methacrylate LMA: n-lauryl methacrylate

After removing dissolved oxygen by bubbling the obtained monomer mixture with nitrogen for 20 minutes, the separable flask system was replaced with nitrogen and heated to 80°C in a hot water bath while stirring. Then, a chain transfer agent and a polymerization initiator were added in the amounts shown in Table 1 to start polymerization. 7 hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereafter, the obtained resin solution was dried in an oven at 100°C to remove water. Thus, (meth)acrylic resin particles were obtained. Furthermore, the following were used as chain transfer agents and polymerization initiators. <Chain transfer agent> CT-1: 3-hydroxy-1,2-propanediol <Polymerization initiator> KPS: Potassium persulfate (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) VA-086: 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.)

(Preparation of a carrier composition for dispersing inorganic particles) Add 90 parts by weight of a solvent having the composition shown in Table 3 to 10 parts by weight of the obtained (meth)acrylic resin particles, stir until uniform, and obtain a carrier composition for dispersing inorganic particles.

(Preparation of Inorganic Particle Dispersion Slurry Composition) The obtained inorganic particle dispersion carrier composition was added with a solvent, a dispersant, and inorganic particles so as to have the composition shown in Table 4, and kneaded with a high-speed stirrer to obtain an inorganic particle dispersion slurry composition. Regarding the solvent, the solvent used in the preparation of the inorganic particle dispersion carrier composition was used at the original ratio. In addition, the following were used as the dispersant and inorganic particles. <Dispersant> Nopcosperse 092 (manufactured by Sanyo Chemical Co., Ltd.) <Inorganic particles> Barium titanium oxide (BT-02, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.2 μm)

<Evaluation> The (meth)acrylic resin particles 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.

(1) Average carbon number Cp and Cs of ester substituents The average carbon number Cp of the ester substituents of the (meth)acrylic resin particles and the average carbon number Cs of the ester substituents of the organic solvent were calculated by the following method. Average carbon number Cp = cp1×wp1+cp2×wp2+…+cpn×wpn (cpn: the carbon number of the ester substituent in the chain segment of each (meth)acrylic ester constituting the (meth)acrylic resin; wpn: the weight fraction of the chain segment derived from each (meth)acrylic ester in the (meth)acrylic resin). Average carbon number Cs = cs1×ws1+cs2×ws2+…+csn×wsn (csn: the carbon number of the ester substituent in each organic solvent; wsn: the weight fraction of each organic solvent in the organic solvent).

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

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

(4) CV value The obtained (meth) acrylic resin particles were observed using a scanning electron microscope ("Regulus8220" manufactured by Hitachi Advanced Technologies Co., Ltd.), and the particle size of 100 particles was measured. The CV value was calculated using the following formula based on the average value D [μm] of the particle size and the standard deviation σ of the particle size. CV value of particle size [%] = σ/D × 100.

(5) Glass transition temperature (Tg) For the obtained (meth)acrylic resin particles, the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC).

(6) Average molecular weight For the obtained (meth) acrylic resin particles, the weight average molecular weight (Mw) and number average molecular weight (Mn) based on polystyrene conversion were measured by gel permeation chromatography using LF-804 (manufactured by SHOKO) as a column.

(7) Low-temperature decomposition (TGDTA) The obtained inorganic particle dispersion slurry composition was placed in a TG-DTA pan and heated from 30°C at 5°C/min in a nitrogen environment to evaporate the solvent and thermally decompose the resin and dispersant. Then, the time (minutes) for 90% by weight degreasing to be completed (weight display: 40.4% by weight) was measured.

(8) Tensile test Using an applicator, the obtained resin solution obtained by dissolving the obtained (meth) acrylic resin particles in butyl acetate was applied to the demolded PET film and dried in a 100°C air-flow oven for 10 minutes to prepare a resin sheet with a thickness of 20 μm. Using a grid paper as a cover film, a short strip of test piece with a width of 1 cm was prepared using scissors. For the obtained test piece, a tensile test was performed at 23°C and 50 RH using Autograph AG-IS (manufactured by Shimadzu Corporation) with a clamp distance of 3 cm and a tensile speed of 10 mm/min to confirm the stress-deformation characteristics (yield stress, elongation at break, tensile properties (yield stress × elongation at break)).

(9) Thin film test Use an applicator to apply the obtained inorganic particle dispersion slurry composition to a PET film that has been subjected to a demolding treatment, and dry it in a 100°C air-flow oven for 10 minutes. In this way, green sheets are prepared in such a way that the thickness after drying reaches 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. Check whether the green sheet is damaged when it is peeled off from the PET film, and the one with the smallest thickness among those without damage is used as the evaluation result.

(10) Solubility test Add 90 parts by weight of the solvent of the composition shown in Table 2 to 10 parts by weight of the obtained (meth)acrylic resin particles, heat to 50°C while stirring, and continue stirring until the resin particles are dissolved and the solution becomes uniform. Measure the time from the start of stirring to the end of stirring.

[Table 1] (Meth) acrylic resin particles Monomer (parts by weight) Chain transfer agent (parts by weight) Polymerization initiator (parts by weight) MMA EMA nB iBMA 2EHMA HEMA LMA CT-1 KPS VΑ-086 Carbon number of ester substituent 1 2 4 4 8 2 12 - - - S atom ratio (weight %) 0 0 0 0 0 0 0 29.65 23.72 0 Ratio of K atoms (wt%) 0 0 0 0 0 0 0 0 28.93 0 OH group ratio (weight %) 0 0 0 0 0 13.07 0 31.44 0 11.80 Embodiment 1 50 50 0 0 0 0 0 0.01 0 0.5 Embodiment 2 50 50 0 0 0 0 0 3.5 0 0.5 Embodiment 3 50 50 0 0 0 0 0 0 0.01 0 Embodiment 4 50 50 0 0 0 0 0 0 3.5 0 Embodiment 5 50 49.9 0 0 0 0.1 0 0 0.1 0 Embodiment 6 50 38.6 0 0 0 11.4 0 0 0.1 0 Embodiment 7 20 20 60 0 0 0 0 0 0.1 0 Embodiment 8 0 0 30 20 50 0 0 0 0.1 0 Embodiment 9 0 0 0 0 0 0 100 0 0.1 0 Embodiment 10 50 38.6 0 0 0 11.4 0 0 0.1 0 Embodiment 11 0 20 70 0 10 0 0 0 0.1 0 Embodiment 12 0 20 70 0 10 0 0 0 0.1 0 Embodiment 13 0 20 70 0 10 0 0 0 0.1 0 Embodiment 14 0 20 70 0 10 0 0 0 0.1 0 Embodiment 15 0 20 70 0 10 0 0 0 0.1 0 Embodiment 16 0 20 70 0 10 0 0 0.02 0.09 0 Embodiment 17 0 20 30 40 10 0 0 0.02 0.09 0 Embodiment 18 20 20 60 0 0 0 0 0 3.7 0 Comparison Example 1 50 50 0 0 0 0 0 1 3.5 0 Comparison Example 2 50 50 0 0 0 0 0 0.005 0 1 Comparison Example 3 50 50 0 0 0 0 0 0.01 0 0.3 Comparison Example 4 50 50 0 0 0 0 0 3.5 0 1

[Table 2] (Meth) acrylic resin particles Average carbon number of ester substituents Cp S atom weight concentration (wt%) Weight concentration of K atoms (wt%) OH group weight concentration (wt%) Particle size (µm) CV value (%) Tg（℃） Mw (million) Mn (million) Mw/Mn Embodiment 1 1.5 0.0030 0 0.062 1.00 15.0 85 500 100 5.0 Embodiment 2 1.5 0.9979 0 1.115 1.00 14.3 85 110 30 3.7 Embodiment 3 1.5 0.0024 0.0029 0 0.50 10.5 85 300 100 3.0 Embodiment 4 1.5 0.8023 0.9783 0 0.10 9.5 85 300 100 3.0 Embodiment 5 1.5 0.0237 0.0289 0.013 0.30 7.3 85 300 100 3.0 Embodiment 6 1.5 0.0237 0.0289 1.489 0.30 7.3 83 300 100 3.0 Embodiment 7 3 0.0237 0.0289 0 0.30 7.2 44 300 200 1.5 Embodiment 8 6 0.0237 0.0289 0 0.30 7.3 10 300 200 1.5 Embodiment 9 12 0.0237 0.0289 0 0.30 7.1 -65 300 200 1.5 Embodiment 10 1.5 0.0237 0.0289 1.489 0.30 7.1 8 300 200 1.5 Embodiment 11 4 0.0237 0.0289 0 0.30 7.1 30 300 75 4.0 Embodiment 12 4 0.0237 0.0289 0 0.30 7.2 30 300 75 4.0 Embodiment 13 4 0.0237 0.0289 0 0.30 7.0 30 300 75 4.0 Embodiment 14 4 0.0237 0.0289 0 0.30 7.2 30 300 75 4.0 Embodiment 15 4 0.0237 0.0289 0 0.30 7.0 30 300 75 4.0 Embodiment 16 4 0.0273 0.0260 0.006 0.30 6.9 30 300 150 2.0 Embodiment 17 4 0.0273 0.0260 0.006 0.30 6.9 34 300 100 3.0 Embodiment 18 3 0.8465 1.0322 0 0.10 7.2 44 300 100 3.0 Comparison Example 1 1.5 1.0783 0.9689 0.301 0.10 9.6 85 200 40 5.0 Comparison Example 2 1.5 0.0015 0 0.118 0.80 15.5 85 300 50 6.0 Comparison Example 3 1.5 0.0030 0 0.038 1.00 15.2 85 550 100 5.5 Comparison Example 4 1.5 0.9931 0 1.166 0.80 15.3 85 100 20 5.0

[Table 3] Solvent Organic solvent (weight %) Water (parts by weight) Content (parts by weight) Methyl acetate Ethyl acetate Butyl acetate Hexyl acetate Dodecyl acetate Average carbon number of ester substituents Cs Content (parts by weight) Embodiment 1 0 0 50 0 50 8 90 0 90 Embodiment 2 0 0 50 0 50 8 90 0 90 Embodiment 3 0 0 50 0 50 8 90 0 90 Embodiment 4 0 0 50 0 50 8 90 0 90 Embodiment 5 0 0 50 0 50 8 90 0 90 Embodiment 6 0 0 50 0 50 8 90 0 90 Embodiment 7 0 0 0 0 100 12 90 0 90 Embodiment 8 100 0 0 0 0 1 90 0 90 Embodiment 9 0 50 50 0 0 3 90 0 90 Embodiment 10 0 0 0 83.5 16.5 6.99 90 0 90 Embodiment 11 80 20 0 0 0 1.2 90 0 90 Embodiment 12 0 0 0 0 100 12 90 0 90 Embodiment 13 0 0 0 0 100 12 89 1 90 Embodiment 14 0 0 0 0 100 12 89.99 0.01 90 Embodiment 15 0 0 0 0 100 12 89.5 0.5 90 Embodiment 16 0 25 50 25 0 4 89.98 0.02 90 Embodiment 17 0 25 50 25 0 4 89.98 0.02 90 Embodiment 18 0 0 0 0 100 12 90 0 90 Comparison Example 1 0 0 50 0 50 8 90 0 90 Comparison Example 2 0 0 50 0 50 8 90 0 90 Comparison Example 3 0 0 50 0 50 8 90 0 90 Comparison Example 4 0 0 50 0 50 8 90 0 90

[Table 4] Carrier composition for dispersing inorganic particles Inorganic particle dispersion slurry composition (Meth) acrylic resin particles Solvent Cs/Cp (Meth) acrylic resin particles (wt%) Solvent (weight %) Dispersant (wt%) Inorganic particles (weight %) Content (parts by weight) Content (parts by weight) Embodiment 1 10 90 5.33 4 55 1 40 Embodiment 2 10 90 5.33 4 55 1 40 Embodiment 3 10 90 5.33 4 55 1 40 Embodiment 4 10 90 5.33 4 55 1 40 Embodiment 5 10 90 5.33 4 55 1 40 Embodiment 6 10 90 5.33 4 55 1 40 Embodiment 7 10 90 4.00 4 55 1 40 Embodiment 8 10 90 0.17 4 55 1 40 Embodiment 9 10 90 0.25 4 55 1 40 Embodiment 10 10 90 4.66 4 55 1 40 Embodiment 11 10 90 0.30 4 55 1 40 Embodiment 12 10 90 3.00 4 55 1 40 Embodiment 13 10 90 3.00 4 55 1 40 Embodiment 14 10 90 3.00 4 55 1 40 Embodiment 15 10 90 3.00 4 55 1 40 Embodiment 16 10 90 1.00 4 55 1 40 Embodiment 17 10 90 1.00 4 55 1 40 Embodiment 18 10 90 4.00 4 55 1 40 Comparison Example 1 10 90 5.33 4 55 1 40 Comparison Example 2 10 90 5.33 4 55 1 40 Comparison Example 3 10 90 5.33 4 55 1 40 Comparison Example 4 10 90 5.33 4 55 1 40

[Table 5] TGDTA Tensile test Thin film Solubility Decomposition time (min) Yield stress (N/mm ² ) Elongation at break (%) Tensile properties (yield stress × elongation at break) Thickness (μm) Dissolution time (minutes) Embodiment 1 59 50 62 3100 8 80 Embodiment 2 59 49 68 3332 8 83 Embodiment 3 58 50 75 3750 7 82 Embodiment 4 58 51 79 4029 6 81 Embodiment 5 57 52 85 4420 5 80 Embodiment 6 57 54 93 5022 5 80 Embodiment 7 56 44 126 5544 4 70 Embodiment 8 55 45 134 6030 4 70 Embodiment 9 54 33 190 6270 3 67 Embodiment 10 54 52 80 4160 3 73 Embodiment 11 53 49 154 7546 3 66 Embodiment 12 52 50 159 7950 3 64 Embodiment 13 51 51 165 8415 2 63 Embodiment 14 50 53 171 9063 2 64 Embodiment 15 50 54 177 9558 2 63 Embodiment 16 50 55 180 9900 1 60 Embodiment 17 48 55 181 9955 1 60 Embodiment 18 59 44 126 5544 4 70 Comparison Example 1 75 50 62 3100 9 72 Comparison Example 2 59 37 50 1850 10 80 Comparison Example 3 59 38 50 1900 10 95 Comparison Example 4 59 30 55 1650 10 82 [Industrial Availability]

According to the present invention, a (meth)acrylic resin particle can be provided, which exhibits excellent low-temperature decomposition and can obtain a high-strength molded product, and can achieve further multi-layering and thin-filming to manufacture a ceramic laminate with excellent characteristics. In addition, a carrier composition, a slurry composition and a manufacturing method of an electronic component containing the (meth)acrylic resin particle can be provided.

without

without

Claims (11)

A (meth) acrylic resin particle having a weight average molecular weight of 1.1 million to 5 million, wherein the weight concentration of S atoms is 0.0020 wt% to 1.0000 wt%. The (meth)acrylic resin particles of claim 1, wherein the weight concentration of K atoms is greater than or equal to 0.002 wt % and less than or equal to 1.000 wt %. The (meth)acrylic resin particles of claim 1 or 2, wherein the weight concentration of OH groups is not less than 0.00 wt % and not more than 1.50 wt %. The (meth)acrylic resin particles according to any one of claims 1 to 3, wherein the average particle size is not less than 0.1 μm and not more than 1.0 μm. The (meth) acrylic resin particles of any one of claims 1 to 4, wherein the average carbon number Cp of the ester substituent calculated by the following formula is 3 to 6, The average carbon number Cp of the ester substituent of the (meth) acrylic resin = cp1×wp1+cp2×wp2+…+cpn×wpn (cpn: the carbon number of the ester substituent in the chain segment derived from each (meth) acrylic ester constituting the (meth) acrylic resin; wpn: the weight fraction of the chain segment derived from each (meth) acrylic ester in the (meth) acrylic resin). A carrier composition comprising the (meth)acrylic resin particles according to any one of claims 1 to 5 and a solvent including an organic solvent. For example, in the carrier composition of claim 6, the average carbon number Cs of the ester substituent of the organic solvent calculated by the following formula is 3 to 7. The average carbon number Cs of the ester substituent of the organic solvent = cs1×ws1+cs2×ws2+…+csn×wsn (csn: the carbon number of the ester substituent in each organic solvent; wsn: the weight fraction of each organic solvent in the organic solvent). In the carrier composition of claim 6 or 7, the ratio (Cs/Cp) of the average carbon number Cs of the ester substituent of the organic solvent to the average carbon number Cp of the ester substituent of the (meth) acrylic resin particles is 0.3 to 3.0. A carrier composition as in any one of claims 6 to 8, wherein the solvent further contains water in an amount of not less than 100 ppm by weight and not more than 11500 ppm by weight. A slurry composition comprising the carrier composition of any one of claims 6 to 9, inorganic particles and a dispersant. A method for manufacturing electronic components, using the slurry composition of claim 10.