TW202506764A - (Meth)acrylic resin, vehicle composition, slurry composition and electronic component - Google Patents

Abstract

The present invention provides a (meth) acrylic resin that can take into account the excellent low-temperature decomposition of the slurry composition and the high strength of the ceramic green sheet, and can produce a ceramic laminate that can be further thinned. In addition, a medium composition, a slurry composition and an electronic component containing the (meth) acrylic resin are provided. The (meth) acrylic resin of the present invention has a structural unit derived from a (meth) acrylic ester monomer, and the above-mentioned (meth) acrylic ester monomer includes a (meth) acrylic ester monomer A and a (meth) acrylic ester monomer B. When the carbon number of the ester substituent of the above-mentioned (meth) acrylic ester monomer A is set to X, the carbon number of the ester substituent of the above-mentioned (meth) acrylic ester monomer B is 4X.

Description

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

The present invention relates to a (meth)acrylic resin.

As for the multilayer ceramic capacitor, it is known that the multilayer body 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 body. The external electrodes are formed by applying the external electrode with a conductive paste on the surface of the multilayer body and sintering the resultant.

In recent years, in order to reduce the energy required for ceramic firing, the degreasing step of removing the binder resin has been required to be lowered in temperature. In addition, the demand for lightweight and high-performance ceramic parts has been increasing, requiring the ceramic green sheet to be thinner and more multi-layered during the manufacturing process.

Patent document 1 describes the use of acrylic resin, polyvinyl butyral resin, polyvinyl acetal resin, ethyl cellulose resin, etc. as such a binder resin for ceramic molding. In particular, it is described that polyvinyl butyral resin or polyvinyl acetal resin is used for thinning the sheet. In addition, patent document 2 describes a methacrylate copolymer obtained by copolymerizing isobutyl methacrylate, 2-ethylhexyl methacrylate, and methacrylate having a hydroxyl group at a specific ratio. It is also stated that by using such a binder resin, good molding properties or degreasing properties can be achieved. Prior art documents Patent document

Patent document 1: Japanese Patent Publication No. 2011-84433 Patent document 2: Japanese Patent Publication No. 10-167836

[The problem that the invention wants to solve]

In order to make the ceramic green sheet into a thin film, the binder resin needs to have sufficient strength. In order to improve the strength, it is usually 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, the dispersibility of the inorganic particles deteriorates, and foreign matter is generated in the ceramic green sheet, which becomes a cause of reduced strength. Although as described in Patent Document 1, it is possible to make a thin film by using polyvinyl butyral resin, there is a problem that the decomposition temperature is relatively high and it cannot be degreased at low temperatures. In addition, although the methacrylate copolymer described in Patent Document 2 can be degreased at low temperatures, there is a problem that the resin itself is brittle and cannot be made into a thin film. Therefore, an adhesive resin is required that can take into account both lowering the degreasing temperature and thinning the film.

The purpose of the present invention is to provide a (meth) acrylic resin that can take into account the excellent low-temperature decomposition of the slurry composition and the high strength of the ceramic green sheet, and can produce a ceramic laminate that can be further thinned. In addition, it is intended to provide a medium composition, a slurry composition and an electronic component containing the (meth) acrylic resin. [Technical means to solve the problem]

The present invention (1) is a (meth)acrylic resin having a structural unit derived from a (meth)acrylic ester monomer, wherein the (meth)acrylic ester monomer comprises a (meth)acrylic ester monomer A and a (meth)acrylic ester monomer B, and when the carbon number of the ester substituent possessed by the (meth)acrylic ester monomer A is set to X, the carbon number of the ester substituent possessed by the (meth)acrylic ester monomer B is 4X. The present invention (2) is a (meth)acrylic resin as in the present invention (1), wherein the ratio of the content of the structural unit derived from the (meth)acrylic ester monomer B to the content of the structural unit derived from the (meth)acrylic ester monomer A (monomer B/monomer A) is 3 or more and 12 or less. The present invention (3) is a (meth)acrylic resin as in the present invention (1) or (2), wherein the (meth)acrylic ester monomer is a methacrylic ester monomer. The present invention (4) is a (meth) acrylic resin in any combination with any one of the present inventions (1) to (3), wherein the Ti value of the resin solution formed by dissolving it in butyl acetate is 1.5 or more and 2.5 or less. The present invention (5) is a (meth) acrylic resin in any combination with any one of the present inventions (1) to (4), wherein the (meth) acrylic ester monomers include a (meth) acrylic ester monomer having a branched ester substituent and a (meth) acrylic ester monomer having a straight ester substituent, wherein the carbon number of the ester substituent is the same. The present invention (6) is a (meth) acrylic resin as described in the present invention (5), wherein the ratio of the content of structural units derived from (meth) acrylic ester monomers having branched ester substituents and having the same carbon number of ester substituents to the content of structural units derived from (meth) acrylic ester monomers having straight ester substituents ((meth) acrylic ester monomers having branched ester substituents/(meth) acrylic ester monomers having straight ester substituents (the ester substituents have the same carbon number)) is 0.5 or more and 2.0 or less. The present invention (7) is a vehicle composition comprising the (meth) acrylic resin of any one of the present inventions (1) to (6) and an organic solvent. The present invention (8) is a vehicle composition as described in the present invention (7), further comprising water, wherein the water content is 10 ppm by weight or more and 12,000 ppm by weight or less. The present invention (9) is a slurry composition, which contains the vehicle composition of the present invention (7), inorganic particles, and a dispersant. The present invention (10) is a slurry composition, which contains the vehicle composition of the present invention (8), inorganic particles, and a dispersant. The present invention (11) is an electronic component, which is formed using the slurry composition of the present invention (9). The present invention (12) is an electronic component, which is formed using 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 when the carbon number of the ester substituent of the (meth)acrylate monomer A is set to X, a slurry composition that can exhibit excellent low-temperature decomposition properties can be obtained by combining "a plurality of (meth)acrylate monomers that satisfy the relationship that the carbon number of the ester substituent of the (meth)acrylate monomer B is 4X". In addition, it has been found that when such a (meth)acrylate resin is used as a binder for dispersing inorganic particles, a high-strength ceramic green sheet can be obtained, and the film can be further reduced. In addition, it has been found that by using such a (meth)acrylate resin, a ceramic laminate with excellent properties can be manufactured, thereby completing the present invention.

The above-mentioned (meth)acrylic resin has a structural unit derived from a (meth)acrylic ester monomer. The above-mentioned (meth)acrylic ester monomer includes a (meth)acrylic ester monomer A and a (meth)acrylic ester monomer B. When the carbon number of the ester substituent of the above-mentioned (meth)acrylic ester monomer A is set to X, the carbon number of the ester substituent of the above-mentioned (meth)acrylic ester monomer B is 4X. By preparing a (meth)acrylic resin having the above-mentioned structure, it is not easy to form a 6-membered ring of carbon during the decomposition process during sintering, and the slag during sintering can be reduced, thereby being able to produce a product with excellent low-temperature decomposition properties. In addition, the molecular chain of the ester substituent derived from the (meth)acrylate monomer A in the (meth)acrylate resin is shorter, and the Van der Waals force acts more strongly. The molecular chain of the ester substituent derived from the (meth)acrylate monomer B in the (meth)acrylate resin is longer, and the Van der Waals force acts less strongly. By mixing these two parts, a molded product with good tensile properties can be obtained.

The above-mentioned (meth) acrylic resin has a structural unit derived from the above-mentioned (meth) acrylic ester monomer. Examples of the (meth)acrylate monomer include alkyl (meth)acrylates having a linear or branched alkyl group such as 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, 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, isolauryl (meth)acrylate, n-tetradecyl (meth)acrylate, n-stearyl (meth)acrylate, and isostearyl (meth)acrylate. In addition, as the above-mentioned (meth)acrylate monomer, there can be cited: 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, methoxypropylene glycol-polybutylene glycol monomethacrylate and other (meth)acrylates having a polyoxyalkylene structure. Furthermore, as the above-mentioned (meth)acrylate monomer, there can be cited: (meth)acrylate 2-hydroxyethyl (meth)acrylate, (meth)acrylate hydroxypropyl, (meth)acrylic acid, (meth)acrylic acid glycidyl (meth)acrylate, mono(meth)acrylate glyceryl and the like having polar groups. Among them, as the above-mentioned (meth)acrylate monomer, alkyl (meth)acrylate is preferred, and methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-lauryl (meth)acrylate are more preferred. In addition, in terms of being able to reduce the residue during sintering and further improving the low-temperature decomposition property, the above-mentioned (meth)acrylate monomer is preferably a methacrylate monomer.

The (meth)acrylate monomers are preferably (meth)acrylate monomers having a straight-chain ester substituent (hereinafter also referred to as "straight-chain monomers") or (meth)acrylate monomers having a branched-chain ester substituent (hereinafter also referred to as "branched-chain monomers"). From the viewpoint of improving the strength of the obtained ceramic green sheet, it is preferred to include (meth)acrylate monomers having a straight-chain ester substituent and (meth)acrylate monomers having a branched-chain ester substituent.

From the viewpoint of improving the strength of the obtained ceramic green sheet, the ratio of the content of the structural unit derived from the (meth)acrylate monomer having a branched ester substituent to the content of the structural unit derived from the (meth)acrylate monomer having a straight ester substituent in the above-mentioned (meth)acrylic resin (branched monomer/straight monomer) is preferably 0.5 or more and preferably 2.0 or less, more preferably 0.6 or more and more preferably 1.6 or less.

The carbon number of the ester substituent of the (meth)acrylate monomer is preferably 1-18, more preferably 1-14, and even more preferably 1-12.

The (meth)acrylate monomer is preferably a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 4. As the (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 4, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate are preferred, and methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate are more preferred. As the (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 4, a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 3 is more preferred, and a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 2 is further preferred.

The content of the structural unit derived from the (meth)acrylate monomer having 1 to 4 carbon atoms in the ester substituent in the (meth)acrylate resin is preferably 20 wt % or more, preferably 100 wt % or less, and more preferably 30 wt % or more.

Furthermore, as the (meth)acrylate monomer having 1 to 4 carbon atoms in the ester substituent, a (meth)acrylate monomer having 1 to 4 carbon atoms in a straight chain ester substituent (hereinafter also referred to as "C1 to 4 straight chain monomer") and a (meth)acrylate monomer having 3 to 4 carbon atoms in a branched chain ester substituent (hereinafter also referred to as "C3 to 4 branched chain monomer") can be used in combination. The ratio of the content of the structural unit derived from the (meth)acrylate monomer having 3 to 4 carbon atoms in the (meth)acrylate resin to the content of the structural unit derived from the (meth)acrylate monomer having 1 to 4 carbon atoms in a straight chain ester substituent (C3 to 4 branched chain monomer/C1 to 4 straight chain monomer) is preferably 0 or more, preferably 12 or less, and more preferably 3 or less.

Furthermore, the content of the structural unit of the (meth)acrylate monomer in which the carbon number of the ester substituent is 1 to 3 in the above-mentioned (meth)acrylate resin is preferably 0% by weight or more, more preferably 3% by weight or more, further preferably 5% by weight or more, preferably 70% by weight or less, and further preferably 50% by weight or less. Furthermore, the content of the structural unit of the (meth)acrylate monomer in which the carbon number of the ester substituent is 1 to 2 in the above-mentioned (meth)acrylate resin is preferably 0% by weight or more, more preferably 3% by weight or more, further preferably 5% by weight or more, preferably 70% by weight or less, and further preferably 50% by weight or less.

The (meth)acrylate monomer is preferably a (meth)acrylate monomer having 4 to 16 carbon atoms in an ester substituent. Examples of the (meth)acrylate monomer having 4 to 16 carbon atoms in an ester substituent include n-butyl (meth)acrylate, tert-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, isolauryl (meth)acrylate, and the like. Among them, preferred are n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-lauryl (meth)acrylate, and more preferred are n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. As the (meth)acrylate monomer having 4 to 16 carbon atoms in the ester substituent, a (meth)acrylate monomer having 4 to 12 carbon atoms in the ester substituent is more preferred, and a (meth)acrylate monomer having 4 to 8 carbon atoms in the ester substituent is further preferred.

The content of the structural unit derived from the (meth)acrylate monomer having 4 to 16 carbon atoms in the ester substituent in the (meth)acrylate resin is preferably 30 wt % or more, preferably 100 wt % or less, more preferably 50 wt % or more, more preferably 97 wt % or less, and further preferably 95 wt % or less.

Furthermore, as the (meth)acrylate monomer having 4 to 16 carbon atoms in the ester substituent, a (meth)acrylate monomer having a straight chain ester substituent having 4 to 16 carbon atoms (hereinafter also referred to as a "C4 to 16 straight chain monomer") and a (meth)acrylate monomer having a branched chain ester substituent having 4 to 16 carbon atoms (hereinafter also referred to as a "C4 to 16 branched chain monomer") can be used in combination. The ratio of the content of the structural unit derived from the (meth)acrylate monomer having a branched ester substituent with a carbon number of 4 to 16 to the content of the structural unit derived from the (meth)acrylate monomer having a straight chain ester substituent with a carbon number of 4 to 16 in the above-mentioned (meth)acrylate resin (C4 to 16 branched monomer/C4 to 16 straight chain monomer) is preferably 0 or more, preferably 3.5 or less, more preferably 0.2 or more, and more preferably 2.5 or less.

Furthermore, the content of the structural unit of the (meth)acrylate monomer in which the carbon number of the ester substituent is 4 to 12 in the above-mentioned (meth)acrylate resin is preferably 30% by weight or more, preferably 100% by weight or less, more preferably 50% by weight or more, more preferably 97% by weight or less, and further preferably 95% by weight or less. Furthermore, the content of the structural unit of the (meth)acrylate monomer in which the carbon number of the ester substituent is 4 to 8 in the above-mentioned (meth)acrylate resin is preferably 25% by weight or more, preferably 95% by weight or less, and further preferably 50% by weight or more.

The above-mentioned (meth)acrylate monomer may include a (meth)acrylate monomer having an ester substituent with a carbon number of 17 or more, but preferably a (meth)acrylate monomer having no ester substituent with a carbon number of 17 or more. In addition, the above-mentioned (meth)acrylate monomer may include a (meth)acrylate monomer having an ester substituent with a carbon number of 13 or more, but preferably a (meth)acrylate monomer having no ester substituent with a carbon number of 13 or more.

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

From the viewpoint of improving the strength of the obtained ceramic green sheet, the (meth)acrylate monomer is preferably a linear monomer and a branched monomer having an ester substituent having the same carbon number as each other.

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

The (meth)acrylate monomers include (meth)acrylate monomer A (hereinafter also referred to as "monomer A") and (meth)acrylate monomer B (hereinafter also referred to as "monomer B"). When the carbon number of the ester substituent of the monomer A is set to X, the carbon number of the ester substituent of the monomer B is 4X. By adopting the above structure, excellent low-temperature decomposition can be exerted, and a high-strength ceramic green sheet can be obtained.

As the above-mentioned monomer A, it is preferably a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 4, more preferably a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 3, and further preferably a (meth)acrylate monomer having an ester substituent with a carbon number of 1 to 2. In addition, the above-mentioned monomer A may be a linear monomer or a branched monomer, and is preferably a linear monomer.

The content of the structural unit derived from the above-mentioned monomer A in the above-mentioned (meth) acrylic resin is preferably 2% by weight or more, preferably 70% by weight or less, more preferably 3% by weight or more, and more preferably 65% by weight or less. Furthermore, when there are two or more (meth) acrylic ester monomers belonging to the above-mentioned monomer A, the content of the structural unit derived from the above-mentioned monomer A refers to the total amount of the (meth) acrylic ester monomers belonging to the above-mentioned monomer A.

The monomer B may be a linear monomer or a branched monomer, or may include both linear monomers and branched monomers, as long as "when the number of carbon atoms in the ester substituent in the monomer A is X, the number of carbon atoms in the ester substituent in the monomer B is 4X".

The content of the structural unit derived from the above-mentioned monomer B in the above-mentioned (meth) acrylic resin is preferably 20% by weight or more, preferably 85% by weight or less, more preferably 25% by weight or more, and more preferably 80% by weight or less. Furthermore, when there are two or more (meth) acrylic ester monomers belonging to the above-mentioned monomer B, the content of the structural unit derived from the above-mentioned monomer B refers to the total amount of the (meth) acrylic ester monomers belonging to the above-mentioned monomer B.

When the above-mentioned monomer B contains a linear monomer and a branched monomer, the ratio of the content of the structural unit derived from the branched monomer in the structural unit derived from the above-mentioned monomer B to the content of the structural unit derived from the linear monomer (branched monomer/linear monomer) is preferably greater than 0.5, preferably less than 2.0, more preferably greater than 0.6, and more preferably less than 1.7.

From the viewpoint of improving decomposability, the ratio of the content of the structural unit derived from the above-mentioned monomer B to the content of the structural unit derived from the above-mentioned monomer A in the above-mentioned (meth) acrylic resin (monomer B/monomer A) is preferably 3 or more, preferably 12 or less, more preferably 4 or more, and more preferably 7 or less. Furthermore, in the above-mentioned monomer A and monomer B, when the carbon number X of the ester substituent is 2 or more, the above-mentioned ratio (monomer B/monomer A) is calculated by adding the ratio (monomer B/monomer A) of the same X and the total content of the same X, and dividing it by the total content of each monomer A and B of 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 above ratio (monomer B/monomer A) is (15/5×20+70/10×80)/(20+80)=6.2.

The content of the structural units derived from the (meth)acrylate monomers different from the structural units derived from the monomer A and the structural units derived from the monomer B in the (meth)acrylic resin may be 0 weight %, preferably 1 weight % or more, preferably 80 weight % or less, more preferably 5 weight % or more, and more preferably 70 weight % or less.

The content of the structural unit derived from the acrylic monomer in the above-mentioned (meth) acrylic resin has the advantage that the lower the content, the higher the low-temperature decomposition property. In this regard, 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 structural unit derived from the above-mentioned acrylic monomer is preferably 0-5% by weight, more preferably 0-1% by weight, and further preferably 0% by weight. Furthermore, the above-mentioned acrylic monomer refers to acrylic acid and acrylic ester.

The weight average molecular weight (Mw) of the above-mentioned (meth) acrylic resin is preferably 30,000 or more, and preferably 5,000,000 or less. If the weight average molecular weight is 30,000 or more, the tensile properties of the obtained resin sheet become higher. If the weight average molecular weight is 5,000,000 or less, it is difficult to produce undissolved (meth) acrylic resin in the obtained resin sheet, and the tensile properties become higher. Therefore, by setting it to the above range, the strength of the obtained ceramic green sheet can be further improved, so that a thinner green sheet can be manufactured. The above-mentioned weight average molecular weight (Mw) is preferably 200,000 or more, more preferably 4,500,000 or less, further preferably 300,000 or more, further preferably 4,000,000 or less, and particularly preferably 1,000,000 or more.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic resin is 1 or more, preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.5 or less. If it is within the above range, it is not easy to produce fine undissolved matter in the medium composition, which can further improve the strength of the ceramic green sheet and prevent the generation of voids in the ceramic laminate after firing. Furthermore, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are average molecular weights converted using polystyrene, which can be obtained by using, for example, column LF-804 (manufactured by Showa Denko K.K.) as a column for GPC measurement.

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

The CV value of the particle size of the (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 can be further improved. If the solubility is improved, the productivity is improved, and the tensile performance is improved by reducing the undissolved resin. The lower limit is not particularly limited, for example, 0%. The above CV value can be calculated based on the average value and standard deviation of the particle size of 100 particles by observing the (meth) acrylic resin particles using a scanning electron microscope. If a persulfate such as ammonium persulfate or potassium persulfate is used, the above CV value tends to decrease.

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

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

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

As a method for producing the above-mentioned (meth) acrylic resin, for example, the following method can be cited: adding an organic solvent to a raw material monomer mixture containing a (meth) acrylic ester monomer, etc. to prepare a monomer mixed solution, and then adding a polymerization initiator and a chain transfer agent to the obtained monomer mixed solution 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 used herein 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, hydroxyisopropylbenzene peroxide, t-butyl hydroxyperoxide, 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-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis-4-cyanovaleric acid; oxygen 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, etc.

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.

Examples of the chain transfer agent include 3-butyl-1,2-propanediol, 3-butyl-1-propanol, 3-butyl-2-butanol, 8-butyl-1-octanol, 2-butylbenzimidazole, butylsuccinic acid, and butylacetic acid.

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 0.01-10.0 parts by weight, more preferably 0.02-5.0 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, preferably 90°C or lower, more preferably 60°C or higher, and more preferably 80°C or lower.

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

The content of the (meth)acrylic resin in the vehicle composition is preferably 5 wt % or more, more preferably 10 wt % or more, and preferably 50 wt % or less, more preferably 40 wt % or less.

The above-mentioned vehicle composition contains a solvent including an organic solvent. As the above-mentioned organic solvent, for example, alcohols such as aliphatic alcohols, glycols, terpene alcohols, aromatic alcohols, aromatic hydrocarbons, esters, ketones, N-methylpyrrolidone, etc. can be cited. As the above-mentioned aliphatic alcohols, for example, ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecanol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, etc. can be cited. 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 pinene alcohol, dihydropinene alcohol, pinene alcohol acetate, dihydropinene alcohol 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 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 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, and butyl acetate is further preferred.

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

In the above-mentioned vehicle liquid composition, the solvent preferably further contains water. The content of the above-mentioned water in the above-mentioned vehicle liquid composition is preferably 10 weight ppm or more, preferably 12000 weight ppm or less. By containing water within the above-mentioned range, the affinity with the dispersant becomes good, and the low-temperature decomposition property is further improved. The content of the above-mentioned water in the above-mentioned vehicle liquid composition is more preferably 300 weight ppm or more, more preferably 1000 weight ppm or less, further preferably 400 weight ppm or more, further preferably 700 weight ppm or less.

The content of the above-mentioned solvent in the above-mentioned vehicle liquid composition is not particularly limited, and is preferably 50 weight % or more, preferably 95 weight % or less, more preferably 60 weight % or more, and more preferably 90 weight % or less.

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

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

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

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

The water content in the above-mentioned slurry composition is preferably 5 wtppm or more, preferably 15000 wtppm or less, more preferably 10 wtppm or more, more preferably 12000 wtppm or less, further preferably 50 wtppm or more, further preferably 10000 wtppm or less, further preferably 7500 wtppm or less.

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

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 aluminum oxide, 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, zirconium lead 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, FTO, niobium oxide, vanadium oxide, tungsten oxide, strontium manganite, strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium doped ceria, nickel oxide, chromium oxide, 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. that are known as fluorescent materials for displays can be used. As the blue fluorescent substance, for example, _MgAl10O17 :Eu system, _{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, the metal particles can use various carbon blacks, carbon nanotubes, etc. in addition to metal complexes.

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 benium 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/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, lithium aluminum 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, preferably 5 μm or less, more preferably 0.05 μm or more, more preferably 3 μm or less, further preferably 0.1 μm or more, 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, 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 20% by weight or more, preferably 90% by weight or less. If it is within the above range, it can be made into a product having sufficient viscosity and excellent coating properties, and further, it can be made into a product having excellent dispersibility of inorganic particles. The content of the above-mentioned inorganic particles is more preferably 25% by weight or more, more preferably 70% by weight or less, more preferably 30% by weight or more, more preferably 60% by weight or less, more preferably 40% by weight or more, and more preferably 55% by weight or less.

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 and the like may also be mixed. As the fatty acid, there is no particular limitation, and examples thereof include: saturated fatty acids such as lauric 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 fatty acid. 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, preferably 1.5 wt % or less, more preferably 0.15 wt % or more, and more preferably 1.0 wt % or less.

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, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dicaproate, triethyl acetyl citrate, tributyl acetyl citrate, diethyl acetyl citrate, dibutyl 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. The above-mentioned nonionic surfactant is not particularly limited, and preferably a nonionic surfactant with an HLB value of 10 to 20. Here, the HLB value is used as an index to indicate the hydrophilicity and lipophilicity of the surfactant, and several calculation methods are proposed. For example, for ester-based surfactants, there is a definition that 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, the preferred non-ionic surfactant is a polyethylene oxide formed 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, if added in large quantities, the thermal decomposition properties of the inorganic particle dispersion slurry composition may sometimes decrease, so the preferred upper limit of the content is 5% by weight.

The viscosity of the slurry composition is not particularly limited, and preferably the viscosity measured at 25°C using a B-type viscometer is 200 mPa∙s or more, more preferably 500 mPa∙s or more, preferably 100000 mPa∙s or less, and 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, the inorganic particle dispersion sheet obtained after coating by a die-spraying printing method can maintain a specific shape. In addition, it can prevent the undesirable situation that the coating marks of the die-spraying 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, the following method may be cited: the vehicle composition, the inorganic particles, the dispersant, and other components such as additional solvents and plasticizers added as needed are stirred by a three-roll mill or the like. The order of adding the components of the slurry composition may be appropriately set.

Electronic components can be made by using the above slurry composition. Electronic components made by using the above slurry composition are also one of the present inventions. Examples of the above electronic components include: die attach paste (ACP), die attach film (ACF), through-hole electrodes for TSV/TGV, touch panels, various circuits of RFID or sensor substrates, various die adhesives, sealants for MEMS devices, solar cells, multilayer ceramic capacitors, LTCC, silicon capacitors, electrode materials for all-solid batteries, etc. In addition, in addition to the above electrode circuit uses, it can also be used for antibacterial components or electromagnetic wave shielding, catalysts, fluorescent materials, etc.

For example, the above-mentioned slurry composition can be applied to a support film subjected to a single-sided demolding treatment, and the organic solvent is dried and formed to produce an inorganic particle dispersed molded product. The shape of the above-mentioned 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 sheet form, the support film used to manufacture the inorganic particle dispersion molded product is preferably a resin film that is heat-resistant and solvent-resistant and flexible. 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-up 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 enabling the support film to be easily peeled off during the transfer step.

The above-mentioned slurry composition can be applied and dried to produce an inorganic particle dispersed molded product. In addition, the above-mentioned slurry composition and inorganic particle dispersed molded product can be used as a conductive paste for an external electrode to produce a "multilayer ceramic capacitor for electronic parts".

As a method for manufacturing the above-mentioned multilayer ceramic capacitor, there can be cited a manufacturing method having the following steps: printing a conductive paste on the above-mentioned inorganic particle dispersion molded product and drying it to prepare a dielectric sheet; and 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 is a conductive material, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.

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

In the manufacturing method of the multilayer ceramic capacitor, a dielectric sheet layer printed with the conductive paste is formed into an unprocessed ceramic multilayer body, and then the unprocessed ceramic multilayer body is sintered in a reducing environment at a temperature of 300 to 1500° C. to obtain a plurality of component blanks.

Then, the conductive paste containing the (meth) acrylic resin is applied to both end surfaces of each of the component blanks by an impregnation method, and then, after being dried at 100-200°C, it is sintered at 300-800°C in a reducing environment to form external electrodes at both ends of the component blank.

Then, 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 can be provided, which can take into account the excellent low-temperature decomposition of the slurry composition and the high strength of the ceramic green sheet, and can produce a ceramic laminate that can be further thinned. In addition, a medium composition, a slurry composition and an electronic component containing the (meth) acrylic resin can be provided.

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

(Examples 1 to 19, Comparative Examples 1 to 9) (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 was mixed to obtain a monomer mixed liquid. In addition, the following monomers were used. MMA: Methyl methacrylate (carbon number of ester substituent: 1) EMA: Ethyl methacrylate (carbon number of ester substituent: 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 (carbon number of ester substituent: 8) LMA: n-lauryl methacrylate (carbon number of ester substituent: 12) MA: Methyl acrylate (carbon number of ester substituent: 1) BA: Butyl acrylate (carbon number of ester substituent: 4)

The obtained monomer mixture was bubbled with nitrogen for 20 minutes to remove dissolved oxygen, and then the separable flask system was replaced with nitrogen, and the temperature was raised to 80°C in a hot water bath while stirring. Then, the chain transfer agent and polymerization initiator were added in the amounts shown in Table 1 to start polymerization. After 7 hours from the start of polymerization, the polymerization was terminated by cooling to room temperature. Thereafter, the resin solution obtained in an oven at 100°C was dried 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.)

(Preparation of a medium liquid composition for dispersing inorganic particles) Add 90 parts by weight of a solvent having the composition shown in Table 2 to 10 parts by weight of the obtained (meth) acrylic resin particles, stir until uniform, and obtain a medium liquid composition for dispersing inorganic particles.

(Preparation of inorganic particle dispersion slurry composition) The obtained inorganic particle dispersion medium composition was added with a solvent, a dispersant, and inorganic particles in a manner to form the composition shown in Table 2, and kneaded using a high-speed stirrer to obtain an inorganic particle dispersion slurry composition. The solvent used in the preparation of the inorganic particle dispersion medium 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 Industries, Ltd.) <Inorganic particles> Barium titanium oxide (BT-02, manufactured by Sakai Chemical Industries, 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 1 and 3.

(1) Ti value 85 parts by weight of butyl acetate were added to 15 parts by weight of the obtained (meth) acrylic resin particles, and the temperature was raised to 80°C while stirring. The mixture was stirred at 80°C for 12 hours and kept warm. The mixture was then cooled to obtain a resin solution. The viscosity of the obtained resin solution was measured at 25°C and 2 rpm using a BH type viscometer with rotor No. 5. The viscosity was also measured 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)

(2) Average value D of particle size and CV value of particle size 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

(3) Weight average molecular weight (Mw) For the obtained (meth) acrylic resin particles, the weight average molecular weight (Mw) converted to polystyrene was measured by gel permeation chromatography using LF-804 (manufactured by SHOKO) as a column.

(4) Low-temperature decomposition (TGDTA) The obtained inorganic particle dispersion slurry composition was placed in a TGDTA pot 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.

(5) Sintering residue (TGDTA) The obtained (meth) acrylic resin particles were placed in a TGDTA pot, and the temperature was raised from 30°C to 350°C at 5°C/min in a nitrogen environment, and maintained for 2 hours to thermally decompose the (meth) acrylic resin particles. The ratio of the weight after the measurement to the weight before the measurement was set as the sintering residue, and the measurement was performed.

(6) Dispersibility (6-1) Filterability Take a syringe containing 2 mL to 2.5 mL of the obtained inorganic particle dispersion slurry composition, install a syringe needle with an outer diameter of 0.81 mm, an inner diameter of 0.51 mm, and a length of 38 mm at the front end of the syringe, and measure the time it takes for the slurry composition to flow out of the injection needle tip when a force of 5 kgf is applied. If the time it takes for the slurry composition to flow out of the injection needle tip is shorter, it can be said that the filterability is excellent. In the case of excellent filterability, it can be said that the inorganic particle aggregation inhibition effect is higher and the dispersibility is excellent.

(6-2) Surface roughness Using a screen printer, screen, and printed glass substrate, an inorganic particle dispersion slurry composition was printed at a temperature of 23°C and a humidity of 50%, and the solvent was dried in a forced air oven at 100°C for 30 minutes. The obtained printed pattern was measured at 10 locations using a surface roughness meter (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.). In addition, the following were used as a screen printer, screen, and printed glass substrate. Screen printer (MT-320TV, manufactured by MICROTEK) Screen (manufactured by Tokyo Process Service, ST500, emulsion 2 μm, 2012 pattern, screen frame 320 mm×320 mm) Printing glass substrate (sodium glass, 150 mm×150 mm, thickness 1.5 mm) If the surface roughness is small, it can be said that the dispersion of inorganic particles is excellent.

(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 became 2% by weight, and the particle size distribution of the polyvinyl acetal resin in 10 mL of the solution was measured using a particle counter ("KL-11A", manufactured by RION). The number of particles with a particle size of 0.5 to 1.0 μm or more per 1 mL of the solution was confirmed. In addition, for particles with a particle size of 0.5 to 1.0 μm, the volume of the particles was calculated assuming a true sphere with a particle size of 0.75 μm, and the ratio of particles with a particle size of 0.5 to 1.0 μm (10 ^-8 volume %) was calculated based on the obtained measurement results. If there are fewer particles, the voids in the ceramic laminate will be reduced, so it can be considered excellent.

(8) Tensile test The resin solution obtained by dissolving the obtained (meth) acrylic resin particles in butyl acetate was applied to a demolded PET film using an applicator and dried in a 100°C air-flow oven for 10 minutes to prepare a resin sheet with a thickness of 20 μm. A grid paper was used as a cover film, and a short strip of test piece with a width of 1 cm was prepared using scissors. The obtained test piece was subjected to a tensile test at 23°C and 50 RH using an Autograph AG-IS (manufactured by Shimadzu Corporation) with a chuck distance of 3 cm and a tensile speed of 10 mm/min to confirm the stress-strain characteristics (yield stress, elongation at break, tensile properties (yield stress × elongation at break)). Furthermore, as long as the strength of the resin sheet is high, it can be predicted that the strength of the obtained ceramic sheet will also be high.

(9) Thin film test The obtained inorganic particle dispersion slurry composition was applied to a PET film that had been subjected to a demolding treatment using an applicator, and dried in a 100°C air-flow oven for 10 minutes to produce green sheets with a thickness 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. 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 set as the evaluation result.

[Table 1] (Meth) acrylic resin particles Monomer (parts by weight) Chain transfer agent (parts by weight) Polymerization initiator (parts by weight) Monomer B/Monomer A Branch chain/straight chain Branch chain/straight chain (same as C) Ti value Average particle size D (μm) CV value of particle size (%) Mw (million) MMA EMA nP nB iBMA OMA 2EHMA LMA MA BA Monomer A Monomer B CT-1 KPS Carbon number of ester substituent 1 2 3 4 4 8 8 12 1 4 - - - - - - - - - - - Embodiment 1 50 0 0 50 0 0 0 0 0 0 50 50 0.5 1.0 1.0 - - 1.2 0.10 15.0 20 Embodiment 2 3 0 0 48 0 49 0 0 0 0 3 48 0.5 1.0 16.0 - - 2.8 0.10 15.0 20 Embodiment 3 0 4 0 0 48 0 48 0 0 0 4 48 3 1.0 12.0 24.0 - 2.5 0.50 10.0 3 Embodiment 4 20 0 0 0 60 0 20 0 0 0 20 60 0.5 1.0 3.0 4.0 - 1.5 0.50 10.0 20 Embodiment 5 8 0 0 64 0 28 0 0 0 0 8 64 0.5 1.0 8.0 - - 2.2 0.50 10.0 20 Embodiment 6 14 6 0 28 0 36 0 16 0 0 20 64 0.5 1.0 4.0 - - 1.6 0.50 10.0 20 Embodiment 7 6.2 62.8 0 10 twenty one 0 0 0 0 0 6.2 31 0.5 1.0 5.0 0.3 2.1 1.7 0.50 10.0 20 Embodiment 8 60 5 0 0 0 25 10 0 0 0 5 35 0.5 1.0 7.0 0.1 0.4 1.8 0.50 10.0 20 Embodiment 9 0 12 0 0 28 20 40 0 0 0 12 60 0.5 1.0 5.0 2.1 2.0 1.7 0.50 10.0 20 Embodiment 10 12 28 0 40 20 0 0 0 0 0 12 60 0.5 1.0 5.0 0.3 0.5 1.7 0.50 10.0 20 Embodiment 11 0 15.6 0 6.4 0 30 48 0 0 0 15.6 78 0.5 1.0 5.0 0.9 1.6 1.7 0.50 10.0 20 Embodiment 12 5 0 0 25 0 40 28 2 0 0 5 25 0.4 1.0 5.0 0.4 0.7 1.7 0.50 10.0 30 Embodiment 13 5 0 0 25 0 40 28 2 0 0 5 25 0 1.0 5.0 0.4 0.7 1.7 0.50 10.0 500 Embodiment 14 5 0 0 25 0 40 28 2 0 0 5 25 0.2 1.0 5.0 0.4 0.7 1.7 0.50 10.0 100 Embodiment 15 5 0 0 25 0 40 28 2 0 0 5 25 0.1 1.0 5.0 0.4 0.7 1.7 0.50 10.0 300 Embodiment 16 5 0 0 25 0 40 28 2 0 0 5 25 0.1 1.0 5.0 0.4 0.7 1.7 0.50 10.0 300 Embodiment 17 5 0 0 25 0 40 28 2 0 0 5 25 0.1 1.0 5.0 0.4 0.7 1.7 0.50 10.0 300 Embodiment 18 0 0 4 0 0 0 48 48 0 0 4 48 3 1.0 12.0 24.0 - 2.5 0.50 10.0 3 Embodiment 19 0 0 0 0 0 49 0 0 3 48 3 48 0.5 1.0 16.0 - - 2.8 0.10 15.0 20 Comparison Example 1 50 50 0 0 0 0 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparison Example 2 3 0 0 0 0 49 0 48 0 0 - - 0.5 1.0 - - - 2.8 0.10 15.0 20 Comparison Example 3 50 0 50 0 0 0 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparison Example 4 50 0 0 0 0 50 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparison Example 5 50 0 0 0 0 0 0 50 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparative Example 6 0 50 50 0 0 0 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparison Example 7 0 50 0 0 0 0 0 50 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparative Example 8 0 0 50 50 0 0 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20 Comparative Example 9 0 0 50 0 0 50 0 0 0 0 - - 0.5 1.0 - - - 1.2 0.10 15.0 20

[Table 2] Inorganic particle dispersion medium composition Inorganic particle dispersion slurry composition (Meth) acrylic resin particles (wt%) Solvent (Meth) acrylic resin particles (wt%) Solvent (weight %) Dispersant (wt%) Inorganic particles (weight %) Organic solvent (weight %) Water (wt%) Butyl acetate Embodiment 1 10 90 0 4 55 1 40 Embodiment 2 10 90 0 4 55 1 40 Embodiment 3 10 90 0 4 55 1 40 Embodiment 4 10 90 0 4 55 1 40 Embodiment 5 10 90 0 4 55 1 40 Embodiment 6 10 90 0 4 55 1 40 Embodiment 7 10 90 0 4 55 1 40 Embodiment 8 10 90 0 4 55 1 40 Embodiment 9 10 90 0 4 55 1 40 Embodiment 10 10 90 0 4 55 1 40 Embodiment 11 10 90 0 4 55 1 40 Embodiment 12 10 90 0 4 55 1 40 Embodiment 13 10 90 0 4 55 1 40 Embodiment 14 10 90 0 4 55 1 40 Embodiment 15 10 88.85 1.15 4 55 1 40 Embodiment 16 10 89.5 0.5 4 55 1 40 Embodiment 17 10 90.0 0.001 4 55 1 40 Embodiment 18 10 90 0 4 55 1 40 Embodiment 19 10 90 0 4 55 1 40 Comparison Example 1 10 90 0 4 55 1 40 Comparison Example 2 10 90 0 4 55 1 40 Comparison Example 3 10 90 0 4 55 1 40 Comparison Example 4 10 90 0 4 55 1 40 Comparison Example 5 10 90 0 4 55 1 40 Comparative Example 6 10 90 0 4 55 1 40 Comparison Example 7 10 90 0 4 55 1 40 Comparative Example 8 10 90 0 4 55 1 40 Comparative Example 9 10 90 0 4 55 1 40

[Table 3] Evaluation of (meth)acrylic resin/paste compositions Evaluation of Resin Sheets/Ceramic Sheets TGDTA Dispersibility Particles Tensile test Thin film Decomposition time (minutes) Sintering residue (%) Filterability (seconds) Surface roughness (μm) The number of particles with a diameter of 0.5 to 1.0 μm Ratio of particles with a diameter of 0.5 to 1.0 μm (10 ^-8 volume %) Yield stress (N/mm ² ) Elongation at break (%) Tensile properties (yield stress × elongation at break) Thickness (μm) Embodiment 1 59 0.51 219 0.088 17100 3.78 42 75 3150 8.0 Embodiment 2 59 0.51 222 0.089 16400 3.62 43 80 3440 8.0 Embodiment 3 58 0.47 204 0.086 15600 3.45 42 89 3738 7.0 Embodiment 4 58 0.46 204 0.086 14700 3.25 43 91 3913 6.0 Embodiment 5 57 0.41 190 0.075 14200 3.14 46 94 4324 5.0 Embodiment 6 57 0.4 188 0.078 14200 3.14 46 95 4370 5.0 Embodiment 7 56 0.36 168 0.074 13800 3.05 48 98 4704 4.0 Embodiment 8 55 0.31 164 0.075 13700 3.03 49 98 4802 4.0 Embodiment 9 54 0.27 147 0.072 12800 2.83 53 102 5406 3.0 Embodiment 10 54 0.26 143 0.071 12600 2.79 54 103 5562 3.0 Embodiment 11 53 0.21 124 0.07 11900 2.64 57 107 6099 3.0 Embodiment 12 52 0.16 124 0.07 9900 2.19 57 108 6156 3.0 Embodiment 13 51 0.1 103 0.068 8900 1.97 59 114 6726 2.0 Embodiment 14 50 0.07 105 0.067 8400 1.86 58 115 6670 2.0 Embodiment 15 50 0.06 81 0.068 7600 1.68 61 119 7259 2.0 Embodiment 16 50 0.05 81 0.068 7400 1.63 61 119 7259 1.0 Embodiment 17 50 0.05 80 0.068 6400 1.41 62 120 7440 1.0 Embodiment 18 58 0.47 204 0.086 15600 3.45 42 89 3738 7.0 Embodiment 19 59 0.51 222 0.089 16400 3.62 43 80 3440 8.0 Comparison Example 1 63 1.8 415 0.205 24200 5.35 35 55 1925 9.0 Comparison Example 2 62 1.85 420 0.204 22200 4.90 34 55 1870 10.0 Comparison Example 3 62 1.81 416 0.205 24300 5.34 33 56 1848 9.0 Comparison Example 4 64 1.82 416 0.205 22500 5.32 33 54 1782 10.0 Comparison Example 5 62 1.81 415 0.205 24500 5.35 35 55 1925 10.0 Comparative Example 6 63 1.83 418 0.204 24100 5.30 33 53 1749 10.0 Comparison Example 7 63 1.84 419 0.205 24000 5.29 34 53 1802 10.0 Comparative Example 8 63 1.81 415 0.205 23100 5.29 35 51 1785 9.0 Comparative Example 9 62 1.84 415 0.205 24200 5.25 33 53 1749 9.0 [Industrial Availability]

According to the present invention, a (meth) acrylic resin can be provided, which can take into account the excellent low-temperature decomposition of the slurry composition and the high strength of the ceramic green sheet, and can produce a ceramic laminate that can be further thinned. In addition, a medium composition, a slurry composition and an electronic component containing the (meth) acrylic resin can be provided.

without

without

Claims (12)

A (meth)acrylic resin having a structural unit derived from a (meth)acrylate monomer, The (meth)acrylate monomer comprises a (meth)acrylate monomer A and a (meth)acrylate monomer B, When the carbon number of the ester substituent possessed by the (meth)acrylate monomer A is set to X, the carbon number of the ester substituent possessed by the (meth)acrylate monomer B is 4X. The (meth)acrylic resin of claim 1, wherein the ratio of the content of the structural unit derived from the (meth)acrylate monomer B to the content of the structural unit derived from the (meth)acrylate monomer A (monomer B/monomer A) is 3 to 12. The (meth)acrylic resin of claim 1 or 2, wherein the (meth)acrylate monomer is a methacrylate monomer. The (meth)acrylic resin of claim 1, 2 or 3, wherein the Ti value of the resin solution obtained by dissolving the resin in butyl acetate is not less than 1.5 and not more than 2.5. The (meth)acrylic resin of claim 1, 2, 3 or 4, wherein the (meth)acrylate monomers include (meth)acrylate monomers having branched ester substituents and (meth)acrylate monomers having straight ester substituents, wherein the carbon numbers of the ester substituents are the same. The (meth)acrylate resin of claim 5, wherein the ratio of the content of structural units derived from (meth)acrylate monomers having branched ester substituents and having the same number of carbon atoms in the ester substituents to the content of structural units derived from (meth)acrylate monomers having straight-chain ester substituents ((meth)acrylate monomers having branched ester substituents/(meth)acrylate monomers having straight-chain ester substituents (the ester substituents have the same number of carbon atoms)) is not less than 0.5 and not more than 2.0. A vehicle composition comprising the (meth)acrylic resin of claim 1, 2, 3, 4, 5 or 6 and an organic solvent. The medium liquid composition of claim 7 further contains water, and the content of the water is greater than 10 ppm by weight and less than 12000 ppm by weight. A slurry composition comprises the vehicle composition of claim 7, inorganic particles, and a dispersant. A slurry composition comprises the vehicle composition of claim 8, inorganic particles, and a dispersant. An electronic component is made using the slurry composition of claim 9. An electronic component is made using the slurry composition of claim 10.