(Meth)acrylic resin, vehicle composition, slurry composition and electronic component

Abstract

To provide a (meth)acrylic resin capable of producing a ceramic laminate which can achieve both excellent low-temperature decomposability of a slurry composition and high strength of a ceramic green sheet and can be further thinned and further to provide a vehicle composition, a slurry composition and an electronic component containing the (meth)acrylic resin.SOLUTION: There is provided a (meth)acrylic resin which has a constituent unit derived from a (meth) acrylic acid ester monomer, wherein the (meth) acrylic acid ester monomer includes a (meth) acrylic acid ester monomer A and a (meth) acrylic acid ester monomer B, when the number of carbon atoms of an ester substituent group possessed by the (meth) acrylic acid ester monomer A is defined as X, the number of carbon atoms of an ester substituent group possessed by the (meth) acrylic acid ester monomer B is 4X.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a (meth)acrylic resin. [Background technology]

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

[0003] In recent years, there has been a demand to lower the temperature of the degreasing process to remove binder resin in order to reduce the energy required for firing ceramics. In addition, there is an increasing demand for lightweight, high-performance ceramic parts, and there is a demand to make ceramic green sheets thinner and more multi-layered during the manufacturing process.

[0004] Patent Document 1 describes the use of acrylic resin, polyvinyl butyral resin, polyvinyl acetal resin, ethyl cellulose resin, and the like as binder resins for such ceramic molding, and in particular describes the use of polyvinyl butyral resin or polyvinyl acetal resin to make the sheet thinner. Patent Document 2 describes a methacrylate copolymer obtained by copolymerizing isobutyl methacrylate, 2-ethylhexyl methacrylate, and a methacrylate having a hydroxyl group in a predetermined ratio, and claims that the use of such a binder resin provides good moldability and degreasing properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2011-84433 A [Patent Document 2] Japanese Patent Application Publication No. 10-167836 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to thin the ceramic green sheet, the binder resin needs to have sufficient strength, and in order to increase the strength, it is generally necessary to increase the molecular weight. However, when the molecular weight is increased, the viscosity of the slurry composition in which the inorganic particles and the binder are dispersed becomes too high, which deteriorates the dispersibility of the inorganic particles, and foreign matter is generated in the ceramic green sheet, which causes a decrease in strength. As described in Patent Document 1, although it is possible to thin the sheet by using polyvinyl butyral resin, there is a problem that the decomposition temperature is high and degreasing cannot be performed at low temperatures. In addition, as described in Patent Document 2, although the methacrylic acid ester copolymer can be degreased at low temperatures, there is a problem that the resin itself is brittle and cannot be thinned. For this reason, there is a demand for a binder resin that can achieve both low degreasing temperature and thinning.

[0007] The present invention aims to provide a (meth)acrylic resin that can provide both excellent low-temperature decomposition of a slurry composition and high strength of a ceramic green sheet, and can be used to produce a ceramic laminate that can be made thinner, and also aims to provide a vehicle composition, a slurry composition, and an electronic device that contain the (meth)acrylic resin. [Means for solving the problem]

[0008] The present disclosure (1) is a (meth)acrylic resin having a constitutional unit derived from a (meth)acrylic acid ester monomer, the (meth)acrylic acid ester monomer including a (meth)acrylic acid ester monomer A and a (meth)acrylic acid ester monomer B, wherein when the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer A is X, the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer B is 4X. The present disclosure (2) is the (meth)acrylic resin of the present disclosure (1), in which the ratio of the content of the constituent units derived from the (meth)acrylic acid ester monomer B to the content of the constituent units derived from the (meth)acrylic acid ester monomer A (monomer B / monomer A) is 3 or more and 12 or less. The present disclosure (3) is the (meth)acrylic resin of the present disclosure (1) or (2), in which the (meth)acrylic acid ester monomer is a methacrylic acid ester monomer. The present disclosure (4) is a (meth)acrylic resin in any combination with any of the present disclosures (1) to (3), in which the Ti value of the resin solution dissolved in butyl acetate is 1.5 or more and 2.5 or less. The present disclosure (5) is a (meth)acrylic resin in any combination with any of the present disclosures (1) to (4), in which the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer having a branched chain ester substituent and a (meth)acrylic acid ester monomer having a linear chain ester substituent, the ester substituents having the same number of carbon atoms. The present disclosure (6) is a (meth)acrylic resin according to the present disclosure (5), in which the ratio of the content of constitutional units derived from (meth)acrylic ester monomers having branched-chain ester substituents to the content of constitutional units derived from (meth)acrylic ester monomers having linear ester substituents, in which the ester substituents have the same number of carbon atoms, ((meth)acrylic ester monomers having branched-chain ester substituents / (meth)acrylic ester monomers having linear ester substituents (the ester substituents have the same number of carbon atoms)) is 0.5 or more and 2.0 or less. The present disclosure (7) is a vehicle composition containing the (meth)acrylic resin of any one of the present disclosures (1) to (6) and an organic solvent. The present disclosure (8) is the vehicle composition of the present disclosure (7), further comprising water, wherein the content of the water is 10 ppm by weight or more and 12,000 ppm by weight or less. The present disclosure (9) is a slurry composition containing the vehicle composition of the present disclosure (7), inorganic particles, and a dispersant. The present disclosure (10) is a slurry composition containing the vehicle composition of the present disclosure (8), inorganic particles, and a dispersant. The present disclosure (11) is an electronic component formed using the slurry composition of the present disclosure (9). The present disclosure (12) is an electronic component formed using the slurry composition of the present disclosure (10). The present invention will be described in detail below.

[0009] The present inventors have found that a slurry composition capable of exhibiting excellent low-temperature decomposition properties can be obtained by combining and using a plurality of (meth)acrylic acid ester monomers that satisfy the relationship that when the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer A is X, the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer B is 4X. In addition, it has been found that when such a (meth)acrylic resin is used as a binder for dispersing inorganic particles, a ceramic green sheet with high strength can be obtained, and further thinning is possible. In addition, it has been found that a ceramic laminate having excellent properties can be manufactured by using such a (meth)acrylic resin, and the present invention has been completed.

[0010] The (meth)acrylic resin has a structural unit derived from a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A and a (meth)acrylic acid ester monomer B. When the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer A is X, the number of carbon atoms of the ester substituent of the (meth)acrylic acid ester monomer B is 4X. By making the (meth)acrylic resin have the above-mentioned structure, six-membered ring carbon is less likely to be formed during the decomposition process during sintering, so that the residue during sintering can be reduced, and furthermore, the resin can be made excellent in low-temperature decomposition properties. In addition, the part of the (meth)acrylic resin derived from (meth)acrylic acid ester monomer A has a short molecular chain of the ester substituent, and van der Waals forces act strongly, while the part of the (meth)acrylic resin derived from (meth)acrylic acid ester monomer B has a long molecular chain of the ester substituent, and van der Waals forces act weakly, and by mixing these two parts, a molded product with good tensile properties can be obtained.

[0011] The (meth)acrylic resin has structural units derived from the (meth)acrylic acid ester monomer. Examples of the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, and n-octyl (meth)acrylate.

[0113] Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having a straight chain alkyl group or a branched chain alkyl group, such as n-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-tetradecyl (meth)acrylate, n-stearyl (meth)acrylate, and isostearyl (meth)acrylate. Furthermore, examples of the (meth)acrylic acid ester monomer include (meth)acrylates having a polyoxyalkylene structure, such as polytetramethylene glycol monomethacrylate, poly(ethylene glycol-polytetramethylene glycol) monomethacrylate, poly(propylene glycol-tetramethylene glycol) monomethacrylate, propylene glycol-polybutylene glycol monomethacrylate, methoxypolytetramethylene glycol monomethacrylate, methoxypoly(ethylene glycol-polytetramethylene glycol) monomethacrylate, methoxypoly(propylene glycol-tetramethylene glycol) monomethacrylate, and methoxypropylene glycol-polybutylene glycol monomethacrylate. Furthermore, examples of the (meth)acrylic acid ester monomer include (meth)acrylates having a polar group, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, and glycerol mono(meth)acrylate. Among these, the (meth)acrylic acid ester monomer is preferably an alkyl (meth)acrylate, and more preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-lauryl (meth)acrylate. Moreover, the (meth)acrylic acid ester monomer is preferable because it can reduce residues during sintering and can further improve low-temperature decomposition properties.

[0012] The (meth)acrylic acid ester monomer is preferably a (meth)acrylic acid ester monomer having a straight-chain ester substituent (hereinafter also referred to as a "straight-chain monomer") or a (meth)acrylic acid ester monomer having a branched-chain ester substituent (hereinafter also referred to as a "branched monomer"), and from the viewpoint of improving the strength of the obtained ceramic green sheet, it preferably contains a (meth)acrylic acid ester monomer having a straight-chain ester substituent and a (meth)acrylic acid ester monomer having a branched-chain ester substituent.

[0013] From the viewpoint of improving the strength of the obtained ceramic green sheet, the ratio of the content of structural units derived from (meth)acrylic acid ester monomers having branched-chain ester substituents to the content of structural units derived from (meth)acrylic acid ester monomers having linear ester substituents in the above-mentioned (meth)acrylic resin (branched monomer / linear monomer) is preferably 0.5 or more and is preferably 2.0 or less, more preferably 0.6 or more and more preferably 1.6 or less.

[0014] The ester substituent of the (meth)acrylic acid ester monomer preferably has 1 to 18 carbon atoms, more preferably 1 to 14 carbon atoms, and even more preferably 1 to 12 carbon atoms.

[0015] The (meth)acrylic acid ester monomer preferably includes a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms. As the (meth)acrylic acid ester monomer having an ester substituent having 1 to 4 carbon atoms, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and isobutyl (meth)acrylate are preferred, and methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate are more preferred. The (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms is preferably a (meth)acrylic acid ester monomer having an ester substituent with 1 to 3 carbon atoms, and more preferably a (meth)acrylic acid ester monomer having an ester substituent with 1 to 2 carbon atoms.

[0016] The content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 1 to 4 carbon atoms in the (meth)acrylic resin is preferably 20% by weight or more, preferably 100% by weight or less, and more preferably 30% by weight or more.

[0017] In addition, as the (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms, a (meth)acrylic acid ester monomer having a straight-chain ester substituent with 1 to 4 carbon atoms (hereinafter also referred to as a "C1-4 straight-chain monomer") and a (meth)acrylic acid ester monomer having a branched-chain ester substituent with 3 to 4 carbon atoms (hereinafter also referred to as a "C3-4 branched monomer") may be used in combination. In the (meth)acrylic resin, the ratio of the content of constitutional units derived from (meth)acrylic acid ester monomers having a branched chain ester substituent having 3 to 4 carbon atoms to the content of constitutional units derived from (meth)acrylic acid ester monomers having a linear ester substituent having 1 to 4 carbon atoms (C3-4 branched monomer / C1-4 linear monomer) is preferably 0 or more, preferably 12 or less, and more preferably 3 or less.

[0018] Furthermore, the content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 1 to 3 carbon atoms in the (meth)acrylic resin is preferably 0% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and is preferably 70% by weight or less, and more preferably 50% by weight or less. Furthermore, the content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 1 to 2 carbon atoms in the (meth)acrylic resin is preferably 0% by weight or more, more preferably 3% by weight or more, and even more preferably 5% by weight or more, and is preferably 70% by weight or less, and more preferably 50% by weight or less.

[0019] The (meth)acrylic acid ester monomer preferably includes a (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms. Examples of the (meth)acrylic acid ester monomer having an ester substituent having 4 to 16 carbon atoms include n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, and isolauryl (meth)acrylate. Of these, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-lauryl (meth)acrylate are preferred, and n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate are more preferred. The (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms is more preferably a (meth)acrylic acid ester monomer having an ester substituent with 4 to 12 carbon atoms, and even more preferably a (meth)acrylic acid ester monomer having an ester substituent with 4 to 8 carbon atoms.

[0020] The content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 4 to 16 carbon atoms in the (meth)acrylic resin is preferably 30% by weight or more, and preferably 100% by weight or less, more preferably 50% by weight or more, more preferably 97% by weight or less, and even more preferably 95% by weight or less.

[0021] In addition, as the (meth)acrylic acid ester monomer having an ester substituent with 4 to 16 carbon atoms, a (meth)acrylic acid ester monomer having a straight-chain ester substituent with 4 to 16 carbon atoms (hereinafter also referred to as a "C4-16 straight-chain monomer") and a (meth)acrylic acid ester monomer having a branched-chain ester substituent with 4 to 16 carbon atoms (hereinafter also referred to as a "C4-16 branched monomer") may be used in combination. The ratio of the content of constitutional units derived from (meth)acrylic acid ester monomers having a branched chain ester substituent having 4 to 16 carbon atoms to the content of constitutional units derived from (meth)acrylic acid ester monomers having a linear ester substituent having 4 to 16 carbon atoms in the (meth)acrylic resin (C4-16 branched monomer / C4-16 linear monomer) is preferably 0 or more and 3.5 or less, more preferably 0.2 or more and more preferably 2.5 or less.

[0022] Furthermore, the content of structural units derived from (meth)acrylic acid ester monomers having an ester substituent with 4 to 12 carbon atoms in the (meth)acrylic resin is preferably 30% by weight or more, and preferably 100% by weight or less, more preferably 50% by weight or more, more preferably 97% by weight or less, and even more preferably 95% by weight or less. Furthermore, the content of structural units derived from (meth)acrylic acid ester monomers in which the ester substituent has 4 to 8 carbon atoms in the (meth)acrylic resin is preferably 25% by weight or more, preferably 95% by weight or less, and more preferably 50% by weight or more.

[0023] The (meth)acrylic acid ester monomer may include a (meth)acrylic acid ester monomer having an ester substituent with 17 or more carbon atoms, but preferably does not include a (meth)acrylic acid ester monomer having an ester substituent with 17 or more carbon atoms. In addition, the above (meth)acrylic acid ester monomer may contain a (meth)acrylic acid ester monomer having an ester substituent with 13 or more carbon atoms, but it is more preferable that the (meth)acrylic acid ester monomer does not contain a (meth)acrylic acid ester monomer having an ester substituent with 13 or more carbon atoms.

[0024] The (meth)acrylic acid ester monomer is preferably an alkyl (meth)acrylate. The (meth)acrylic acid ester monomer may contain a (meth)acrylic acid ester monomer other than the alkyl (meth)acrylate (hereinafter also referred to as "other monomer"), but more preferably does not contain other monomers.

[0025] From the viewpoint of improving the strength of the resulting ceramic green sheet, the (meth)acrylic acid ester monomer preferably has a linear monomer and a branched monomer in which the number of carbon atoms in the ester substituents is the same.

[0026] In the (meth)acrylic resin, the ratio of the content of structural units derived from branched monomers to the content of structural units derived from linear monomers having the same number of carbon atoms in their ester substituents (branched monomer / linear monomer (having the same number of carbon atoms in their ester substituents)) is preferably 0.5 or more and 2.0 or less, more preferably 0.6 or more and more preferably 1.7 or less, from the viewpoint of improving the strength of the obtained ceramic green sheet.

[0027] The (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A (hereinafter also referred to as "monomer A") and a (meth)acrylic acid ester monomer B (hereinafter also referred to as "monomer B"). When the number of carbon atoms of the ester substituent possessed by the monomer A is X, the number of carbon atoms of the ester substituent possessed by the monomer B is 4X. By employing the above-mentioned constitution, it is possible to obtain a ceramic green sheet having excellent low-temperature decomposition property and high strength.

[0028] The monomer A is preferably a (meth)acrylic acid ester monomer having an ester substituent with 1 to 4 carbon atoms, more preferably a (meth)acrylic acid ester monomer having an ester substituent with 1 to 3 carbon atoms, and even more preferably a (meth)acrylic acid ester monomer having an ester substituent with 1 to 2 carbon atoms. Moreover, the monomer A may be a straight-chain monomer or a branched monomer, and is preferably a straight-chain monomer.

[0029] The content of the constituent units derived from the monomer A in the (meth)acrylic resin is preferably 2% by weight or more, and preferably 70% by weight or less, more preferably 3% by weight or more, and more preferably 65% ​​by weight or less. When there are two or more types of (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer A, the content of the constitutional units derived from the above-mentioned monomer A means the total amount of the (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer A.

[0030] The monomer B may be a linear monomer, a branched monomer, or a monomer containing a linear monomer and a branched monomer, so long as the number of carbon atoms of the ester substituent possessed by the monomer A is 4X, where X is the number of carbon atoms of the ester substituent possessed by the monomer B.

[0031] The content of the structural units derived from the monomer B in the (meth)acrylic resin is preferably 20% by weight or more and preferably 85% by weight or less, more preferably 25% by weight or more and more preferably 80% by weight or less. When there are two or more types of (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer B, the content of the constitutional units derived from the above-mentioned monomer B means the total amount of the (meth)acrylic acid ester monomers corresponding to the above-mentioned monomer B.

[0032] When the monomer B contains a linear monomer and a branched monomer, the ratio of the content of the structural units derived from the branched monomer to the content of the structural units derived from the linear monomer in the structural units derived from the monomer B (branched monomer / linear monomer) is preferably 0.5 or more and preferably 2.0 or less, more preferably 0.6 or more, and more preferably 1.7 or less.

[0033] From the viewpoint of improving decomposition property, the ratio of the content of the structural units derived from the monomer B to the content of the structural units derived from the monomer A in the (meth)acrylic resin (monomer B / monomer A) is preferably 3 or more and 12 or less, more preferably 4 or more and more preferably 7 or less. In addition, in the above-mentioned monomer A and monomer B, when the number of carbon atoms X of the ester substituent is two or more, the above-mentioned ratio (monomer B / monomer A) is calculated by summing the product of the ratio (monomer B / monomer A) in the monomers having the same X and the total content of the monomers having the same X, and dividing the product by the sum of the total content of monomers A and B for each monomer having the same X. For example, when the (meth)acrylic resin contains 5% by weight and 15% by weight of structural units derived from monomer A and monomer B where X is 1, respectively, and 10% by weight and 70% by weight of structural units derived from monomer A and monomer B where X is 2, respectively, the ratio (monomer B / monomer A) is (15 / 5×20+70 / 10×80) / (20+80)=6.2.

[0034] In the (meth)acrylic resin, the content of the constituent units derived from the (meth)acrylic acid ester monomer different from the constituent units derived from the monomer A and the constituent units derived from the monomer B may be 0% by weight, is preferably 1% by weight or more, is preferably 80% by weight or less, is more preferably 5% by weight or more, and is more preferably 70% by weight or less.

[0035] The content of the structural unit derived from the acrylic monomer in the (meth)acrylic resin is preferably 5% by weight or less, more preferably 1% by weight or less, since the lower 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 structural unit derived from the acrylic monomer is preferably 0 to 5% by weight, more preferably 0 to 1% by weight, and even more preferably 0% by weight. The acrylic monomer means acrylic acid and acrylic esters.

[0036] The weight average molecular weight (Mw) of the (meth)acrylic resin is preferably 30,000 or more, and preferably 5,000,000 or less. When the weight average molecular weight is 30,000 or more, the tensile performance of the resulting resin sheet is high. When the weight average molecular weight is 5,000,000 or less, the resulting resin sheet is less likely to have undissolved (meth)acrylic resin, and the tensile performance is high. For this reason, by setting the weight average molecular weight in the above range, the strength of the resulting ceramic green sheet can be further increased, and a thinner green sheet can be manufactured. The weight average molecular weight (Mw) is more preferably 200,000 or more, more preferably 4,500,000 or less, even more preferably 300,000 or more, still more preferably 4,000,000 or less, and particularly preferably 1,000,000 or more.

[0037] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (meth)acrylic resin is at least 1, and is preferably at most 5.0, more preferably at most 4.0, and even more preferably at most 3.5. When it is within the above range, fine undissolved matter is less likely to be generated in the vehicle composition, the strength of the ceramic green sheet can be further increased, and the generation of voids in the ceramic laminate after firing can be prevented. The weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights calculated based on polystyrene standards, and can be obtained by GPC measurement using, for example, column LF-804 (manufactured by Showa Denko KK).

[0038] When the (meth)acrylic resin is in a particulate form, the average particle size of the resin particles is preferably 0.1 μm or more and preferably 1.0 μm or less, more preferably 0.2 μm or more, more preferably 0.9 μm or less, even more preferably 0.3 μm or more, and even more preferably 0.8 μm or less, from the viewpoint of solubility. The average particle size can be determined, for example, by measuring the volume average particle size using a laser diffraction / scattering type particle size distribution measuring device.

[0039] 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 content within the above range, the solubility of the (meth)acrylic resin can be further improved. The improved solubility leads to increased productivity, and the reduced amount of undissolved resin leads to improved tensile properties. The lower limit is not particularly limited, and is, for example, 0%. The CV value can be calculated from the average particle size and standard deviation of 100 particles by observing the (meth)acrylic resin particles using a scanning electron microscope. The CV value tends to be smaller when a persulfate such as ammonium persulfate or potassium persulfate is used.

[0040] The (meth)acrylic resin preferably has a Ti value of 1.5 or more and 2.5 or less in a resin solution dissolved in butyl acetate. By setting the Ti value in the above range, the dispersibility of the inorganic particles can be improved, and the strength of the ceramic green sheet can be increased. The Ti value is more preferably 1.6 or more and more preferably 2.2 or less. The Ti value can be determined by calculating the ratio (viscosity (2 rpm) / viscosity (20 rpm)) of the viscosity measured at 25°C and 2 rpm using a BH type viscometer to the viscosity measured at 25°C and 20 rpm. As the resin solution, for example, a butyl acetate solution containing 15% by weight of a (meth)acrylic resin can be used. The Ti value can be adjusted to a preferred range by adjusting the ratio of the content of the structural unit derived from the monomer A to the content of the structural unit derived from the monomer B.

[0041] The (meth)acrylic resin preferably has a glass transition temperature (Tg) of 30° C. or higher and preferably 85° C. or lower, more preferably 32° C. or higher and more preferably 80° C. or lower, even more preferably 42° C. or higher and still more preferably 75° C. or lower. By setting the content within the above range, the amount of plasticizer added can be reduced, and low-temperature decomposition properties can be further improved. The glass transition temperature (Tg) can be measured, for example, by using a differential scanning calorimeter (DSC).

[0042] The (meth)acrylic resin preferably has a 90% by weight 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 5° C. / min. The lower limit is not particularly limited, and is 30° C. or higher, and the lower the better. The 90% by weight decomposition temperature is preferably 30 to 280° C., more preferably 30 to 270° C., and even more preferably 30 to 260° C.

[0043] Examples of a method for producing the (meth)acrylic resin include a method in which an organic solvent is added to a raw material monomer mixture containing a (meth)acrylic acid ester monomer or the like to prepare a monomer mixture, and 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 thereof include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, solution polymerization, etc. Among these, emulsion polymerization is preferred.

[0044] 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 them, 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.

[0045] 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. In addition, 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], etc. water-soluble azo compounds such as 2,2'-azobis[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); peroxides such as hydrogen peroxide, peracetic acid, performic acid, and perpropionic acid.

[0046] The amount of the polymerization initiator 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 monomer. The amount of the polymerization initiator is preferably 0.03 to 4.0 parts by weight and more preferably 0.05 to 3.6 parts by weight, relative to 100 parts by weight of the raw material monomer.

[0047] Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, 2-mercaptobenzimidazole, mercaptosuccinic acid, and mercaptoacetic acid.

[0048] 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, 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 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.

[0049] The temperature during polymerization is preferably 50° C. or higher and 90° C. or lower, more preferably 60° C. or higher and more preferably 80° C. or lower.

[0050] A vehicle composition can be prepared using the above (meth)acrylic resin and a solvent containing an organic solvent. The present invention also includes a vehicle composition containing the above-mentioned (meth)acrylic resin and a solvent containing an organic solvent.

[0051] The content of the (meth)acrylic resin 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.

[0052] The vehicle composition contains a solvent including 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. The aromatic alcohols include benzyl alcohol. The aromatic hydrocarbons include toluene and the like. 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, ethyl acetate, butyl acetate and hexyl acetate being even more preferred, and butyl acetate being even more preferred.

[0053] The content of the organic solvent in the vehicle composition is not particularly limited, but is preferably 50% by weight or more and 95% by weight or less, more preferably 55% by weight or more and more preferably 88.8% by weight or less.

[0054] In the above vehicle composition, the solvent preferably further contains water. The content of the water in the vehicle composition is preferably 10 ppm by weight or more and 12,000 ppm by weight or less. By including water in the above range, compatibility with the dispersant improves and low-temperature decomposition properties are further improved. The content of the water in the vehicle composition is more preferably 300 ppm by weight or more, more preferably 1000 ppm by weight or less, even more preferably 400 ppm by weight or more, and even more preferably 700 ppm by weight or less.

[0055] The content of the solvent in the vehicle composition is not particularly limited, but is preferably 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more and more preferably 90% by weight or less.

[0056] The vehicle composition may be produced, for example, by adding an organic solvent, water, etc. to the (meth)acrylic resin obtained by the above method and mixing with stirring.

[0057] A slurry composition can be prepared using the vehicle composition, inorganic particles and dispersant. The present invention also includes a slurry composition containing the above vehicle composition, inorganic particles, and a dispersant.

[0058] The content of the (meth)acrylic resin in the slurry composition is preferably 3% by weight or more, and preferably 10% by weight or less, more preferably 5% by weight or more, and more preferably 8% by weight or less.

[0059] The content of the organic solvent in the slurry composition is preferably 25% by weight or more and 70% by weight or less, more preferably 30% by weight or more and more preferably 60% by weight or less.

[0060] The water content in the above slurry composition is preferably 5 ppm by weight or more, preferably 15,000 ppm by weight or less, more preferably 10 ppm by weight or more, more preferably 12,000 ppm by weight or less, even more preferably 50 ppm by weight or more, even more preferably 10,000 ppm by weight or less, and even more preferably 7,500 ppm by weight or less.

[0061] The content of the solvent in the slurry composition is preferably 25% by weight or more and 70% by weight or less, more preferably 30% by weight or more and more preferably 60% by weight or less.

[0062] The slurry composition contains inorganic particles. The inorganic particles are not particularly limited, and examples thereof include glass powder, ceramic powder, phosphor particles, silicon oxide particles, metal particles, and the like.

[0063] 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 suitable glass powders include those based on various silicon oxides. In addition, the above glass powder may be SnO-B 2 O 3 -P 2 O 5 -Al 2 O 3 mixture, PbO-B 2 O 3 -SiO 2 Mixture, BaO-ZnO-B 2 O 3 -SiO 2 Mixture, ZnO-Bi 2 O 3 -B 2 O 3 -SiO 2 mixture, Bi 2 O 3 -B 2 O 3 -BaO-CuO mixture, Bi 2 O 3 -ZnO-B 2 O 3 -Al 2 O 3 -SrO mixture, ZnO-Bi2 O 3 -B 2 O 3 Mixture, Bi 2 O 3 -SiO 2 Mixture, P 2 O 5 -Na 2 O-CaO-BaO-Al 2 O 3 -B 2 O 3 Mixture, P 2 O 5 -SnO mixture, P 2 O 5 -SnO-B 2 O 3 Mixture, P 2 O 5 -SnO-SiO 2 Mixture, CuO-P 2 O 5 -RO mixture, SiO 2 -B 2 O 3 -ZnO-Na 2 O-Li 2 O-NaF-V 2 O 5 Mixture, P 2 O 5 -ZnO-SnO-R 2 O-RO mixture, B 2 O 3 -SiO 2 -ZnO mixture, B 2 O 3 -SiO 2 -Al 2 O 3 -ZrO 2 Mixture, SiO 2 -B 2 O 3 -ZnO-R 2 O-RO mixture, SiO 2 -B 2 O 3 -Al 2 O 3 -RO-R 2 O mixture, SrO-ZnO-P 2 O 5 Mixture, SrO-ZnO-P 2 O 5Mixture, BaO-ZnO-B 2 O 3 -SiO 2 A glass powder of a mixture thereof can also be used. Here, 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 of 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.

[0064] 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, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, and forsterite. In addition, ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium stabilized zirconia, gadolinium doped ceria, nickel oxide, lanthanum chromite, and the like can also be used. The phosphor particles are not particularly limited, and for example, a blue phosphor material, a red phosphor material, a green phosphor material, etc., which are conventionally known as phosphor materials for displays, can be used as the phosphor material. As the blue phosphor material, for example, MgAl 10 O 17 :Eu series, Y 2 SiO 5 : Ce-based, CaWO 4 : Pb-based, BaMgAl14 O 23 :Eu series, BaMgAl 16 O 27 :Eu series, BaMg 2 Al 14 O 23 :Eu series, BaMg 2 Al 14 O 27 The red phosphor material is, for example, Y:Eu-based or ZnS:(Ag,Cd)-based. 2 O 3 :Eu series, Y 2 SiO 5 :Eu series, Y 3 Al 5 O 12 :Eu series, Zn 3 (PO 4 ) 2 :Mn series, YBO 3 :Eu-based, (Y,Gd)BO 3 :Eu series, GdBO 3 :Eu-based, ScBO 3 :Eu series, LuBO 3 The green phosphor material is, for example, Zn. 2 SiO 4 :Mn series, BaAl 12 O 19 :Mn-based, SrAl 13 O 19 :Mn-based, CaAl 12 O 19 :Mn series, YBO 3 :Tb series, BaMgAl 14 O 23 :Mn series, LuBO 3 :Tb series, GdBO 3 :Tb series, ScBO 3 :Tb series, Sr6Si 3 O 3 Cl 4 Others include ZnO:Zn, ZnS:(Cu,Al), ZnS:Ag, and Y 2 O 2 S:Eu series, ZnS:Zn series, (Y,Cd)BO 3 :Eu series, BaMgAl 12 O 23 :Eu-based materials can also be used.

[0065] 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. In addition, metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be preferably used. These metal particles may be used alone or in combination of two or more kinds. As the metal particles, various carbon blacks, carbon nanotubes, etc. may be used in addition to metal complexes.

[0066] 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 S y (M=B, Si, Ge, P) and other lithium-sulfur glasses, 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 S 0.5 P 0.5 O 4 ), lithium titanium phosphate (LiTi 2 (PO 4 ) 3 ), lithium titanate (Li 4 Ti 5 O 12 ), Li 4 / 3 Ti 5 / 3 O 4 , LiCoO 2 , lithium germanium phosphate (LiGe 2 (PO 4 ) 3 ), Li 2 -SiS-based glass, Li 4 GeS4 -Li 3 P.S. 4 Glasses, LiSiO 3 , LiMn 2 O 4 , Li 2 SP 2 S 5 Glass and ceramics, Li 2 O-SiO 2 , Li 2 O.V. 2 O 5 -SiO 2 , LiS-SiS 2 -Li 4 SiO 4 Li-based glasses, ion-conductive oxides such as LiPON, Li 2 OP 2 O 5 -B 2 O 3 , Li 2 O-GeO 2 Lithium oxide compounds such as Ba, Li x Al y Ti z (PO 4 ) 3 Glasses based on La x Li y TiO z Glasses containing Li x Ge y P z O 4 Glasses containing Li 7 La 3 Zr 2 O 12 Glasses containing Li v S w P x S y Cl z Glasses, 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.

[0067] 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 type particle size distribution measuring device.

[0068] The content of the inorganic particles in the slurry composition is preferably 20% by weight or more and 90% by weight or less, and within this range, the composition has sufficient viscosity, excellent coatability, and excellent dispersibility of the inorganic particles. The content of the inorganic particles is more preferably 25% by weight or more, more preferably 70% by weight or less, even more preferably 30% by weight or more, even more preferably 60% by weight or less, even more preferably 40% by weight or more, and even more preferably 55% by weight or less.

[0069] The slurry composition contains a dispersant. Suitable examples of the dispersant include fatty acids, aliphatic amines, alkanolamides, and phosphoric esters. Silane coupling agents may also be used. The fatty acid is not particularly limited, and examples thereof include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, coconut fatty acid, etc., and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, sorbic acid, beef tallow fatty acid, and hardened castor fatty acid, etc. Among these, lauric acid, stearic acid, oleic acid, etc. are preferred. The aliphatic amine is not particularly limited, and examples thereof include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl(coconut)amine, alkyl(hardened beef tallow)amine, alkyl(beef tallow)amine, and alkyl(soybean)amine. The alkanolamide is not particularly limited, and examples thereof include coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide. The phosphate ester is not particularly limited, and examples thereof include polyoxyethylene alkyl ether phosphate ester and polyoxyethylene alkyl allyl ether phosphate ester.

[0070] The content of the dispersant in the slurry composition is preferably 0.1% by weight or more and preferably 1.5% by weight or less, more preferably 0.15% by weight or more and more preferably 1.0% by weight or less.

[0071] The above-mentioned slurry composition may further contain additives such as a plasticizer and a surfactant. Examples of the plasticizer include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, triethyl acetyl citrate, tributyl acetyl citrate, diethyl acetyl citrate, dibutyl acetyl citrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, and diethyl ethoxymalonate.

[0072] 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 or more and 20 or less. 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, a nonionic surfactant having a polyethylene oxide in which an alkylene ether is added to an aliphatic chain is suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. The nonionic surfactant has good thermal decomposition properties, but if added in large quantities, the thermal decomposition properties of the inorganic particle dispersion slurry composition may decrease, so the preferred upper limit of the content is 5% by weight.

[0073] The viscosity of the slurry composition is not particularly limited, but the viscosity measured at 25° C. using a Brookfield viscometer is preferably 200 mPa·s or more, more preferably 500 mPa·s or more, and is 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 content within the above range, it becomes possible for the obtained inorganic particle-dispersed sheet to maintain a predetermined shape after coating by a die coat printing method or the like. In addition, problems such as indelible die coating marks can be prevented, and the sheet can have excellent printability.

[0074] 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 such as additional solvents and plasticizers added as necessary are stirred with a three-roll mill, etc. The order of addition of the components of the slurry composition can be appropriately set.

[0075] By using the above slurry composition, electronic components can be produced. The present invention also includes an electronic part obtained by using the above-mentioned slurry composition. Examples of the electronic components include die attach paste (ACP), die attach film (ACF), via electrodes for TSV and TGV, touch panels, various circuits for RFID and sensor substrates, various die bonding agents, sealing agents for MEMS devices, solar cells, multilayer ceramic capacitors, LTCC, silicon capacitors, electrode materials for all-solid-state batteries, etc. In addition to the above-mentioned electrode circuit applications, the material can also be used for antibacterial materials, electromagnetic shields, catalysts, fluorescent materials, etc.

[0076] For example, the slurry composition is applied onto a support film which has been subjected to a release treatment on one side, the organic solvent is dried, and the film is molded to produce an inorganic particle dispersion molded product. The shape of the inorganic particle dispersion molded product is not particularly limited, but may be, for example, a sheet.

[0077] Examples of a method for producing the above-mentioned inorganic particle dispersion molding include a method in which the above-mentioned 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.

[0078] For example, when the inorganic particle-dispersed molding is in the form of a sheet, the support film used in producing the inorganic particle-dispersed molding is preferably a resin film having heat resistance and solvent resistance as well as flexibility. Since the support film has flexibility, the inorganic particle-dispersed slurry composition can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the obtained inorganic particle-dispersed sheet-forming film can be stored and supplied in a rolled state.

[0079] Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorine-containing resins such as polyfluoroethylene, nylon, cellulose, and the like. 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 allows the support film to be easily peeled off in the transfer step.

[0080] The above slurry composition can be applied and dried to produce a molded product in which inorganic particles are dispersed. Furthermore, by using the above-mentioned slurry composition and inorganic particle dispersion molding for an external electrode conductive paste, a multilayer ceramic capacitor, which is an electronic component, can be produced.

[0081] The method for producing the multilayer ceramic capacitor may include a method including the steps of printing and drying a conductive paste on the inorganic particle dispersion molding to produce a dielectric sheet, and laminating the dielectric sheets.

[0082] The conductive paste contains a conductive powder. The material of the conductive powder is not particularly limited as long as it is a material having conductivity, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof, etc. These conductive powders may be used alone or in combination of two or more kinds.

[0083] The method for printing the conductive paste is not particularly limited, and examples thereof include screen printing, die coat printing, offset printing, gravure printing, and inkjet printing.

[0084] In the method for manufacturing the multilayer ceramic capacitor, dielectric sheets on which the conductive paste is printed are stacked to produce a raw 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 bodies.

[0085] Next, a conductive paste for external electrodes containing the above-mentioned (meth)acrylic resin is applied to both end surfaces of each of these component elements by a dipping method, and then this 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.

[0086] 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. Effect of the Invention

[0087] According to the present invention, there is provided a (meth)acrylic resin capable of producing a ceramic laminate that can be further thinned by achieving both excellent low-temperature decomposition of a slurry composition and high strength of a ceramic green sheet, and a vehicle composition, a slurry composition, and an electronic component that contain the (meth)acrylic resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0088] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0089] Example 9~17, Reference Examples 1~ 8、18、 19. Comparative Examples 1 to 9) (Preparation of (meth)acrylic resin particles) A 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a water bath, and a nitrogen gas inlet was prepared, and 100 parts by weight of monomers in total were added to the 2 L separable flask so as to obtain the composition shown in Table 1. Furthermore, 900 parts by weight of water was mixed to obtain a monomer mixture liquid. The following monomers were used: MMA: Methyl methacrylate (ester substituent carbon number: 1) EMA: Ethyl methacrylate (ester substituent carbon number: 2) nPMA: n-propyl methacrylate (carbon number of ester substituent: 3) nBMA: n-butyl methacrylate (carbon number of ester substituent: 4) iBMA: isobutyl methacrylate (carbon number of ester substituent: 4) OMA: n-octyl methacrylate (carbon number of ester substituent: 8) 2EHMA: 2-ethylhexyl methacrylate (number of carbon atoms in ester substituent: 8) LMA: n-lauryl methacrylate (carbon number of ester substituent: 12) MA: Methyl acrylate (ester substituent carbon number: 1) BA: Butyl acrylate (ester substituent carbon number: 4)

[0090] 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 and the water bath was heated to 80° C. with stirring. Thereafter, a chain transfer agent and a polymerization initiator were added in the amounts shown in Table 1 to initiate polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature. The resin solution obtained was then dried in an oven at 100° C. to remove water. As a result, (meth)acrylic resin particles were obtained. The chain transfer agent and polymerization initiator used were as follows: <Chain transfer agent> CT-1: 3-mercapto-1,2-propanediol <Polymerization initiator> KPS: Potassium persulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0091] (Preparation of vehicle composition for dispersing inorganic particles) To 10 parts by weight of the obtained (meth)acrylic resin particles, 90 parts by weight of a solvent having the composition shown in Table 2 was added, and the mixture was stirred until homogenous, to obtain a vehicle composition for dispersing inorganic particles.

[0092] (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 in the proportions shown in Table 2, and the mixture was kneaded with a high-speed stirrer to obtain an inorganic particle dispersion slurry composition. The solvents used in the preparation of the vehicle composition for dispersing inorganic particles were used in the same proportions. The dispersants and inorganic particles used were as follows: <Dispersant> Nopcosperse 092 (manufactured by Sanyo Chemical Industries, Ltd.) <Inorganic particles> Barium titanate (BT-02, Sakai Chemical Industry Co., Ltd., average particle size 0.2 μm)

[0093] <Evaluation> Working Example 、Reference example The (meth)acrylic resin particle / inorganic particle dispersion slurry compositions obtained in the Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1 and 3.

[0094] (1) Ti value 85 parts by weight of butyl acetate was added to 15 parts by weight of the obtained (meth)acrylic resin particles, and the mixture was heated to 80°C while stirring, and kept at 80°C for 12 hours while stirring, and then cooled to obtain a resin solution. The viscosity of the obtained resin solution was measured using a BH type viscometer with a rotor No. 5 at 25°C and 2 rpm. The viscosity was also measured in the same manner at 25°C and 20 rpm, and the Ti value was calculated based on the following formula. Ti value = viscosity (2 rpm) / viscosity (20 rpm)

[0095] (2) Average particle size D and CV value of particle size The obtained (meth)acrylic resin particles were observed using a scanning electron microscope (Regulus8220 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

[0096] (3) Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the obtained (meth)acrylic resin particles was measured in terms of polystyrene by gel permeation chromatography using an LF-804 (manufactured by SHOKO Corporation) as a column.

[0097] (4) Low temperature decomposition (TGDTA) The obtained inorganic particle dispersion slurry composition was packed in a platinum pan of TGDTA, and the temperature was raised from 30°C at 5°C / min under a nitrogen atmosphere to evaporate the solvent and pyrolyze the resin and dispersant. Then, the time (min) until 90% by weight degreasing was completed (the weight was 40.4% by weight) was measured.

[0098] (5) Sintering residue (TGDTA) The obtained (meth)acrylic resin particles were packed in a platinum pan of TGDTA, and the temperature was raised from 30°C to 350°C at 5°C / min in a nitrogen atmosphere, and the temperature was maintained for 2 hours to thermally decompose the (meth)acrylic resin particles. The ratio of the weight after measurement to the weight before measurement was measured as the sintering residue.

[0099] (6) Dispersibility (6-1) Filterability 2 ml of the obtained inorganic particle dispersion slurry composition was placed in a 2.5 ml syringe, and a needle having an outer diameter of 0.81 mm, an inner diameter of 0.51 mm, and a length of 38 mm was attached to the tip of the syringe. A force of 5 kgf was applied, and the time it took for all of the slurry composition to come out of the tip of the needle was measured. When the time it takes for the slurry composition to completely come out of the tip of the syringe needle is short, it can be said that the composition has excellent filterability. When the filterability is excellent, it can be said that the effect of inhibiting aggregation of inorganic particles is high and the composition has excellent dispersibility.

[0100] (6-2) Surface roughness Using a screen printer, a screen plate, and a printed glass substrate, an inorganic particle dispersion slurry composition was printed in an environment of 23° C. and 50% humidity, and the solvent was dried in a fan oven for 30 minutes at 100° C. Using the obtained printed pattern, the surface roughness was measured at 10 points using a surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.). The following screen printing machine, screen plate, and printing glass substrate were used. Screen printing machine (MT-320TV, manufactured by Microtec) Screen plate (Tokyo Process Services, ST500, emulsion 2μm, 2012 patterns, screen frame 320mm x 320mm) Printing glass substrate (soda glass, 150mm x 150mm, thickness 1.5mm) A small surface roughness indicates excellent dispersibility of inorganic particles.

[0101] (7) Particles The obtained (meth)acrylic resin particles were diluted with a mixed solvent of ethanol and toluene (weight ratio 1:1) so that the resin amount was 2% by weight, and the particle size distribution of the polyvinyl acetal resin in 10 mL of this solution was measured using a particle counter ("KL-11A", manufactured by Rion Co., Ltd.). The number of particles with a particle size of 0.5 to 1.0 μm or more per 1 mL of solution was confirmed. In addition, for particles with a particle size of 0.5 to 1.0 μm, the particle volume was calculated assuming that the particles were true spheres with a particle size of 0.75 μm, and the proportion of particles with a particle size of 0.5 to 1.0 μm (10 -8 The volume percent of the ceramic laminate was calculated. Fewer particles means fewer voids in the ceramic laminate, which is therefore considered to be superior.

[0102] (8) Tensile test The (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, and then dried for 10 minutes in a 100°C air-blowing oven to produce a 20μm-thick resin sheet. Using graph paper as a cover film, a 1cm-wide rectangular test piece was cut with scissors. Tensile tests were performed on the obtained test pieces using an autograph AG-IS (Shimadzu Corporation) at 23°C and 50 RH with a chuck distance of 3 cm and a tensile speed of 10 mm / min to confirm the stress-strain characteristics (yield stress, fracture elongation, and tensile performance (yield stress x fracture elongation)). If the strength of the resin sheet is high, it can be predicted that the strength of the obtained ceramic green sheet will also be high.

[0103] (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-blowing oven to produce green sheets with 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 after drying. When the green sheets were peeled off from the PET film, they were checked for tears, and the one without tears and with the smallest thickness was regarded as the evaluation result.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3] [Industrial Applicability]

[0107] According to the present invention, there is provided a (meth)acrylic resin capable of producing a ceramic laminate that can be further thinned by achieving both excellent low-temperature decomposition of a slurry composition and high strength of a ceramic green sheet, and a vehicle composition, a slurry composition, and an electronic component that contain the (meth)acrylic resin.

Claims

1. Having a structural unit derived from a (meth)acrylic acid ester monomer, the (meth)acrylic acid ester monomer has an ester substituent having 1 to 12 carbon atoms; The (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer A and a (meth)acrylic acid ester monomer B, When the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer A is X, the number of carbon atoms of an ester substituent possessed by the (meth)acrylic acid ester monomer B is 4X; The monomer A is a (meth)acrylic acid ester monomer having an ester substituent having 1 to 2 carbon atoms, The content of the structural unit derived from the monomer A is 5% by weight or more, The content of the structural unit derived from the monomer B is 25% by weight or more, a ratio of the content of the structural unit derived from the (meth)acrylic acid ester monomer B to the content of the structural unit derived from the (meth)acrylic acid ester monomer A (monomer B / monomer A) is 3 or more and 12 or less; the (meth)acrylic acid ester monomer includes a (meth)acrylic acid ester monomer having a branched chain ester substituent and a (meth)acrylic acid ester monomer having a linear chain ester substituent, the ester substituents having the same number of carbon atoms; A (meth)acrylic resin in which the ratio of the content of structural units derived from (meth)acrylic ester monomers having branched-chain ester substituents to the content of structural units derived from (meth)acrylic ester monomers having straight-chain ester substituents, the ester substituents having the same number of carbon atoms, ((meth)acrylic ester monomers having branched-chain ester substituents / (meth)acrylic ester monomers having straight-chain ester substituents (the ester substituents have the same number of carbon atoms)) is 0.5 or more and 2.0 or less.

2. The (meth)acrylic resin of claim 1 , wherein the (meth)acrylic acid ester monomer is a methacrylic acid ester monomer.

3. The (meth)acrylic resin according to claim 1 or 2, wherein a Ti value of a resin solution dissolved in butyl acetate is 1.5 or more and 2.5 or less.

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

5. A slurry composition comprising the vehicle composition according to claim 4, inorganic particles, and a dispersant.

6. An electronic part, comprising the slurry composition according to claim 5 .

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