Polyvinyl acetal resin

Abstract

The present invention provides: a polyvinyl acetal resin with which a ceramic green sheet having high mechanical strength and excellent sheet attack resistance can be obtained, and with which a multilayer ceramic capacitor having excellent reliability can be produced; and a slurry for a ceramic green sheet, ceramic green sheet, and multilayer ceramic capacitor that use the polyvinyl acetal resin. The present invention is a polyvinyl acetal resin that has one or more LS intensity peaks in a retention time region of 7-10 minutes in a chromatogram measured using GPC-MALS, and that has an IR absorption spectrum measured using an infrared spectrophotometer, where when X (%) is the minimum transmittance of a peak in the wavenumber range of 3050-3750 cm-1, and among the wavenumbers that satisfy the equation [100-(100-X) / 2], A is the wavenumber on the lower wavenumber side and B is the wavenumber on the higher wavenumber side, the hydroxyl group amount conversion wavenumber width is 8.31 or more using A, B, and the hydroxyl group amount measured by 1H-NMR. (1): Hydroxyl group amount converted wavenumber width (cm-1 / mol%) = [(B-A) / hydroxyl group amount]

Description

Polyvinyl acetal resin

[0001] The present invention relates to a polyvinyl acetal resin, a slurry for a ceramic green sheet, a ceramic green sheet, and a multilayer ceramic capacitor.

[0002] In recent years, electronic components mounted in various electronic devices have become increasingly miniaturized and multilayered, resulting in widespread use of multilayer electronic components such as multilayer circuit boards, laminated coils, and multilayer ceramic capacitors. Multilayer ceramic capacitors, among others, are generally manufactured through the following process. First, a plasticizer, dispersant, etc. are added to a solution of a binder resin, such as polyvinyl butyral resin or poly(meth)acrylate resin, dissolved in an organic solvent. Then, ceramic raw material powder is added and uniformly mixed using a mixing device such as a bead mill or ball mill. After degassing, a ceramic slurry composition with a constant viscosity is obtained. This slurry composition is cast onto a support surface, such as a release-treated polyethylene terephthalate film or SUS plate, using a doctor blade or reverse roll coater. The resulting ceramic green sheets are then heated to remove volatiles such as the solvent, and the sheets are peeled off from the support to obtain ceramic green sheets. Next, multiple sheets of the resulting ceramic green sheets, each coated with a conductive paste for internal electrodes by screen printing, are alternately stacked and heated and pressed together to form a laminate. Thereafter, the laminate is subjected to a process of thermally decomposing and removing binder resin components and the like contained in the laminate, a so-called degreasing process, and then external electrodes are sintered onto the end faces of the ceramic sintered body obtained by firing, to obtain a multilayer ceramic capacitor.

[0003] For example, Patent Document 1 describes a polyvinyl acetal resin suitable as a ceramic binder, which has a predetermined degree of polymerization, vinyl ester unit content, and degree of acetalization, and in which the molar ratio of the portion acetalized with acetaldehyde to the portion acetalized with butylaldehyde is within a predetermined range. Also, Patent Document 2 describes a polyvinyl acetal resin having a predetermined degree of polymerization, vinyl ester unit content, and degree of acetalization, and having specific structural units.

[0004] JP 2011-236304 A International Publication No. 2012 / 023517

[0005] On the other hand, in recent years, with the increasing functionality and miniaturization of electronic devices, multilayer ceramic capacitors are required to have higher capacitance and be smaller, and ceramic green sheets are also required to be thinner. However, when the polyvinyl acetal resins described in Patent Documents 1 and 2 are used, the strength of the resulting ceramic green sheets is insufficient, and there is a problem that they tear when peeled from the release sheet due to insufficient strength, resulting in a decrease in yield. There is also a problem that the sheet attack resistance of the resulting ceramic green sheets is insufficient, which causes a decrease in the electrical properties of the multilayer ceramic capacitor and an increase in the defect rate.

[0006] The present invention aims to provide a polyvinyl acetal resin that can produce ceramic green sheets having high mechanical strength and excellent sheet attack resistance, and that can be used to fabricate highly reliable multilayer ceramic capacitors; and to provide a ceramic green sheet slurry, a ceramic green sheet, and a multilayer ceramic capacitor that use the polyvinyl acetal resin.

[0007] The present disclosure 1 is a compound having one or more LS intensity peaks in the retention time region of 7 to 10 minutes in a chromatogram measured using GPC-MALS, and having a wave number of 3050 to 3750 cm in an IR absorption spectrum measured using an infrared spectrophotometer. －１ When the minimum transmittance of the peak within the range is X (%), among the wave numbers showing transmittance a (%) that satisfies [100-(100-X) / 2], the wave number on the low wave number side is A and the wave number on the high wave number side is B, １ The polyvinyl acetal resin has a hydroxyl group amount converted wavenumber width of 8.31 or more, which is calculated by the formula (1) using the amount of hydroxyl groups measured by H-NMR. －１ / mol%)=[(B-A) / amount of hydroxyl groups] (1) Disclosure 2 is the polyvinyl acetal resin according to Disclosure 1, which has three or more LS intensity peaks in a region of retention times of 7 to 17 minutes in a chromatogram measured using GPC-MALS. Disclosure 3 is the polyvinyl acetal resin according to Disclosure 1 or 2, which has a z-average radius of gyration measured using GPC-MALS of 55 nm or more. Disclosure 4 is the polyvinyl acetal resin according to any one of Disclosures 1 to 3, which has a hydroxyl group amount converted wavenumber width calculated by formula (1) of 8.45 or more. Disclosure 5 is the polyvinyl acetal resin according to any one of Disclosures 1 to 3, which has a hydroxyl group amount converted wavenumber width calculated by formula (1) of 8.45 or more in a chromatogram measured using GPC-MALS. １ The polyvinyl acetal resin according to any one of Disclosures 1 to 4, wherein the hydroxyl group-acetyl group amount converted wavenumber width calculated by the following formula (2) using the hydroxyl group amount and the acetyl group amount measured by H-NMR is 6.5 to 18.0: －１ / mol% / mol%)=[(B-A) / amount of hydroxyl groups / amount of acetyl groups] (2) The present disclosure 6 is the polyvinyl acetal resin according to any one of the present disclosures 1 to 5, wherein Mz(THF) / Mz(NMP) is 1.2 to 1.93, where Mz(THF) is the z-average molecular weight obtained using THF as the mobile phase and Mz(NMP) is the z-average molecular weight obtained using NMP as the mobile phase in GPC measurement using a differential refractive index detector. The present disclosure 7 is the polyvinyl acetal resin according to any one of the present disclosures 1 to 6, wherein a 5% by mass solution of the polyvinyl acetal resin in a 1:1 mixed solvent of ethanol and toluene has a solution viscosity of 30 mPa s or more and 200 mPa s or less, as measured using a Brookfield viscometer at a solution temperature of 20°C. Disclosure 8 is a slurry for a ceramic green sheet containing the polyvinyl acetal resin according to any one of Disclosures 1 to 7, an organic solvent, and a ceramic powder. Disclosure 9 is a ceramic green sheet obtained using the slurry for a ceramic green sheet according to Disclosure 8. Disclosure 10 is a multilayer ceramic capacitor obtained using the ceramic green sheet according to Disclosure 9. The present invention will be described in detail below.

[0008] As a result of extensive investigations, the present inventors have found that a compound having a predetermined number of peaks or more in a chromatogram measured using GPC-MALS and a peak having a wavelength of 3050 to 3750 cm in an IR absorption spectrum measured using an infrared spectrophotometer is －１ The present inventors have found that a polyvinyl acetal resin having a hydroxyl group amount equivalent wavenumber width within a predetermined range, calculated based on peaks within the above range, can provide a ceramic green sheet having high mechanical strength and excellent sheet attack resistance, and can also produce a multilayer ceramic capacitor having excellent reliability, and have completed the present invention.

[0009] The polyvinyl acetal resin of the present invention has one or more LS intensity peaks in the retention time region of 7 to 10 minutes in a chromatogram measured using GPC-MALS. By using such a polyvinyl acetal resin, a ceramic green sheet with high strength and excellent sheet attack resistance can be obtained. The number of peaks in the chromatogram measured using GPC-MALS is preferably one or more. Furthermore, the number of peaks is preferably three or less. In the present invention, the number of peaks observed in the retention time region of 7 to 10 minutes is an indicator of the number of associations formed by multiple polyvinyl acetal resins. Furthermore, the polyvinyl acetal resin of the present invention preferably has three or more LS intensity peaks in the retention time region of 7 to 17 minutes in a chromatogram measured using GPC-MALS. The number of peaks in the chromatogram measured using GPC-MALS can be measured by GPC-MALS using a multi-angle light scattering detector. Tetrahydrofuran can be used as the elution solvent (mobile phase). The types and conditions of use of columns, detectors, etc. can be determined by the methods described in the Examples below. Furthermore, the number of peaks can be counted using a predetermined data processing system (analysis software, etc.).

[0010] The LS Intensity peak height in the chromatogram measured using the GPC-MALS is preferably 0.001 V or more, more preferably 0.002 V or more. Furthermore, the peak height is preferably 0.006 V or less, more preferably 0.005 V or less. When multiple peaks are detected in the retention time region of 7 to 10 minutes, the peak height refers to the peak with the largest peak height. The LS Intensity peak position in the chromatogram measured using the GPC-MALS is preferably at a retention time of 7.5 minutes or more and 9.7 minutes or less, more preferably 8.0 minutes or more and 9.5 minutes or less. In the chromatogram measured using the GPC-MALS, the peak width at an LS Intensity value that is half the LS Intensity peak value is preferably 2 minutes or less in elution time, more preferably 1.5 minutes or less.

[0011] The polyvinyl acetal resin of the present invention preferably has a z-average radius of 55 nm or more in a measurement of the slope of light scattering intensity measured using GPC-MALS. By using such a polyvinyl acetal resin, a ceramic green sheet with high strength and excellent sheet attack resistance can be obtained. The z-average radius of gyration is preferably 59 nm or more, more preferably 65 nm or more. Furthermore, the z-average radius of gyration is preferably 75 nm or less, more preferably 70 nm or less. The z-average radius of gyration can be calculated using analysis software based on a chromatogram measured using GPC-MALS.

[0012] The number of peaks and z-average radius of gyration can be adjusted, for example, by changing the average degree of polymerization and degree of saponification of the raw material polyvinyl alcohol resin, and the temperature and time conditions of the acetalization reaction, and by appropriately setting the amount of acetal groups, amount of hydroxyl groups, amount of acetyl groups, etc. of the polyvinyl acetal resin. In particular, the number of peaks can be adjusted by changing the aldehyde introduction temperature, number of introductions, introduction interval, temperature rise time, temperature rise rate, reaction temperature, reaction time, holding (aging) temperature, and holding (aging) time during the acetalization reaction described below, and particularly by changing the aldehyde introduction temperature, number of introductions, introduction interval, holding (aging) temperature, and holding (aging) time.

[0013] The polyvinyl acetal resin of the present invention has an IR absorption spectrum measured by an infrared spectrophotometer, and has a wave number of 3050 to 3750 cm －１ When the minimum transmittance of the peak within the range is X (%), among the wave numbers showing transmittance a (%) that satisfies [100-(100-X) / 2], the wave number on the low wave number side is A and the wave number on the high wave number side is B, １ Using the amount of hydroxyl groups measured by H-NMR, the hydroxyl group amount converted wavenumber width calculated by the above formula (1) is 8.31 or more. By setting the value within the above range, a ceramic green sheet with high strength and excellent sheet attack resistance can be obtained. The preferred lower limit of the hydroxyl group amount converted wavenumber width is 8.45, more preferably 8.70, even more preferably 8.84, and the preferred upper limit is 10.00, even more preferably 9.70. In the present invention, the hydroxyl group amount converted wavenumber width serves as an indicator of the continuity of the positions of hydroxyl groups. The IR absorption spectrum can be measured by a transmission method using a Fourier transform infrared spectrophotometer (such as the FT-720 manufactured by HORIBA or the FT / IR-4000 manufactured by JASCO Corporation) at 20°C, for example.

[0014] The polyvinyl acetal resin of the present invention is １Using the hydroxyl and acetyl group amounts measured by H-NMR, the hydroxyl-acetyl group amount equivalent wavenumber width calculated by the above formula (2) is preferably 6.5 to 18.0. By setting the value within this range, a ceramic green sheet with high strength and excellent sheet attack resistance can be obtained. The lower limit of the hydroxyl-acetyl group amount equivalent wavenumber width is more preferably 10.5, even more preferably 11.0, and the upper limit is more preferably 16.0, even more preferably 14.0.

[0015] In the analysis of the polyvinyl acetal resin using the infrared spectrophotometer, a spectrum derived from the stretching vibration of the C—H bond of the polyvinyl acetal resin was observed at 2980 cm －１ The above peak analysis firstly revealed that the minimum transmittance of the peak due to the stretching vibration of the C-H bond is around 2500 cm －１ and 3050 cm －１ The film thickness of the measurement sample is adjusted so that it is 20 to 25% of the baseline when the line connecting the lines is connected. －１ A baseline is drawn for the peaks that appear within this range, and the data is corrected so that the transmittance at both ends of the peak is 100%.

[0016] The hydroxyl group amount-equivalent wavenumber width and the hydroxyl / acetyl group amount-equivalent wavenumber width can be adjusted, for example, by changing the average degree of polymerization and degree of saponification of the raw material polyvinyl alcohol resin, and the temperature and time conditions of the acetalization reaction, and appropriately setting the amount of acetal groups, amount of hydroxyl groups, amount of acetyl groups, etc. of the polyvinyl acetal resin. In particular, the wavenumber width can be adjusted by changing the aldehyde introduction temperature, number of introductions, introduction interval, temperature rise time, temperature rise rate, reaction temperature, reaction time, holding (aging) temperature, and holding (aging) time during the acetalization reaction described below, and in particular, by changing the aldehyde introduction temperature, number of introductions, and introduction interval.

[0017] An example of the IR absorption spectrum of the polyvinyl acetal resin of the present invention measured by an infrared spectrophotometer at 20°C is shown in Figure 1. In Figure 1, the vertical axis represents transmittance and the horizontal axis represents wavenumber. In the IR absorption spectrum shown in Figure 1, the minimum transmittance X is 65.7%. Furthermore, the transmittance a (%) satisfying [100 - (100 - X) / 2] is 82.85%, and the wavenumber A on the low wavenumber side is 3297 cm. －１ , the wave number B on the high wave number side is 3557 cm －１ In the above case, １ If the amount of hydroxyl groups measured by H-NMR is 30 mol%, the wavenumber width converted to the amount of hydroxyl groups [(B−A) / amount of hydroxyl groups] is 8.67 (cm －１ / mol%). The wave number A is 3250 cm －１ More than 3270 cm is preferable. －１ More than 3350 cm is more preferable. －１ Preferably, 3330 cm －１ The wave number B is preferably 3500 cm or less. －１ More than 3530 cm is preferable. －１ More preferably, 3600 cm －１ Preferably, 3580 cm or less －１ The following is more preferable: The transmittance a is preferably 81% or more and 85% or less.

[0018] In the polyvinyl acetal resin of the present invention, when measured by GPC using a differential refractive index detector, Mz(THF) is the z-average molecular weight obtained using THF as the mobile phase, and Mz(NMP) is the z-average molecular weight obtained using NMP as the mobile phase. The Mz(THF) / Mz(NMP) ratio is preferably 1.2 to 1.93. By maintaining the ratio within this range, a ceramic green sheet with high strength can be obtained. The Mz(THF) / Mz(NMP) ratio is preferably 1.40 or more, more preferably 1.50 or more. Furthermore, the Mz(THF) / Mz(NMP) ratio is preferably 1.80 or less, more preferably 1.70 or less. In the present invention, the Mz(THF) / Mz(NMP) ratio serves as an indicator of the intermolecular interactions of the polyvinyl acetal resin. The above Mz(THF) / Mz(NMP) can be calculated by measuring Mz(THF) obtained by gel permeation chromatography (GPC) measurement using tetrahydrofuran as a mobile phase and a solvent and a refractive index detector as a detector, and then measuring Mz(NMP) obtained by GPC measurement using N-methylpyrrolidone as a mobile phase and a solvent and a refractive index detector as a detector, and calculating Mz(THF) / Mz(NMP).

[0019] The Mz(THF) is preferably 500,000 or more, more preferably 700,000 or more, and even more preferably 800,000 or more. Also, it is preferably 2,000,000 or less, more preferably 1,400,000 or less, and even more preferably 1,000,000 or less. The Mz(NMP) is preferably 200,000 or more, more preferably 400,000 or more, and even more preferably 480,000 or more. Also, it is preferably 1,700,000 or less, more preferably 1,100,000 or less, and even more preferably 700,000 or less.

[0020] The above Mz(THF) / Mz(NMP) can be adjusted, for example, by changing the average degree of polymerization and degree of saponification of the raw material polyvinyl alcohol resin, and the temperature and time conditions of the acetalization reaction, and by appropriately setting the amount of acetal groups, amount of hydroxyl groups, amount of acetyl groups, etc. of the polyvinyl acetal resin. In particular, the above Mz(THF) / Mz(NMP) can be adjusted by changing the aldehyde introduction temperature, number of introductions, introduction interval, temperature rise time, temperature rise rate, reaction temperature, reaction time, holding (aging) temperature, and holding (aging) time during the acetalization reaction described below, and in particular, it can be adjusted by changing the aldehyde introduction temperature, number of introductions, introduction interval, holding (aging) temperature, and holding (aging) time.

[0021] The polyvinyl acetal resin of the present invention preferably has a solution viscosity of 30 mPa·s or more and 200 mPa·s or less when a 5% by mass solution dissolved in a 1:1 mixed solvent of ethanol and toluene is measured using a Brookfield viscometer at a solution temperature of 20°C. From the viewpoint of improving tensile strength, the viscosity is more preferably 50 mPa·s or more, and even more preferably 72 mPa·s or more. From the viewpoint of improving the viscosity stability of the ceramic slurry composition, the viscosity is more preferably 180 mPa·s or less, and even more preferably 150 mPa·s or less. As the Brookfield viscometer, for example, a TVB-10 viscometer manufactured by Toki Sangyo Co., Ltd. can be used. Furthermore, the rotor and rotation speed during viscosity measurement are preferably adjusted appropriately depending on the solution viscosity. For example, it is preferable to measure using SPINDLE Nos. M1 to M4 at a rotation speed in the range of 0.3 to 100 rpm.

[0022] The viscosity can be adjusted, for example, by changing the average degree of polymerization and degree of saponification of the raw material polyvinyl alcohol resin, and the temperature and time conditions of the acetalization reaction, and by appropriately setting the amount of acetal groups, hydroxyl groups, acetyl groups, etc. of the polyvinyl acetal resin.

[0023] The polyvinyl acetal resin of the present invention preferably has a structural unit having an acetal group represented by the following formula (3), a structural unit having a hydroxyl group represented by the following formula (4), and a structural unit having an acetyl group represented by the following formula (5).

[0024]

[0025] In the above formula (3), R １ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0026] In the above formula (3), R １ is an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, an octadecyl group, etc. Of these, a methyl group and an n-propyl group are preferred.

[0027] In the polyvinyl acetal resin of the present invention, the content of the structural unit having an acetal group represented by formula (3) (hereinafter also referred to as the "acetal group amount") is preferably 50 mol% at the lower limit and 83 mol% at the upper limit. When the acetal group amount is 50 mol% or more, the solubility in organic solvents can be improved. When the acetal group amount is 83 mol% or less, the polyvinyl acetal resin can have excellent tensile strength. The acetal group amount is more preferably 52 mol% at the lower limit, more preferably 81 mol% at the upper limit, even more preferably 55 mol% at the lower limit, even more preferably 80 mol% at the upper limit, even more preferably 61 mol% at the lower limit, even more preferably 77 mol% at the upper limit, particularly preferably 67 mol% at the lower limit, and particularly preferably 77 mol% at the upper limit. That is, the amount of acetal groups is preferably 50 to 83 mol%, more preferably 52 to 81 mol%, even more preferably 55 to 80 mol%, even more preferably 61 to 77 mol%, and particularly preferably 67 to 73 mol%. When the polyvinyl acetal resin of the present invention is acetalized using butyraldehyde and acetaldehyde, the amount of butyral groups is preferably 27 to 80 mol%, more preferably 35 to 78 mol%, even more preferably 44 to 72 mol%, and particularly preferably 52 to 65 mol%, and the amount of acetoacetal groups is preferably 1 to 25 mol%, more preferably 2 to 20 mol%, even more preferably 5 to 17 mol%, and particularly preferably 8 to 15 mol%. The amount of acetal groups can be, for example, １ The amount of acetal groups can be measured by H-NMR. Since the acetal groups of the polyvinyl acetal resin are obtained by acetalizing two hydroxyl groups of polyvinyl alcohol, the amount of acetal groups is calculated by counting the two acetalized hydroxyl groups.

[0028] In the polyvinyl acetal resin of the present invention, the content of the hydroxyl group-containing structural unit represented by the general formula (4) (hereinafter also referred to as the "hydroxyl group amount") is preferably 18 mol% at the lower limit and 40 mol% at the upper limit. When the hydroxyl group amount is 18 mol% or more, the polyvinyl acetal resin can have high toughness. When the hydroxyl group amount is 40 mol% or less, the solubility in organic solvents can be sufficiently improved. The hydroxyl group amount is more preferably 22 mol% at the lower limit and 38 mol% at the upper limit, and even more preferably 26 mol% at the lower limit and 32 mol% at the upper limit. That is, the hydroxyl group amount is preferably 18 to 40 mol%, more preferably 22 to 38 mol%, and even more preferably 26 to 32 mol%. By setting the hydroxyl group amount in the above range, the hydroxyl group amount equivalent wavenumber width and the hydroxyl group amount equivalent wavenumber width can be set within a predetermined range. The hydroxyl group amount can be, for example, １ It can be measured by H-NMR.

[0029] In the polyvinyl acetal resin of the present invention, the content of the structural unit having an acetyl group represented by the general formula (5) (hereinafter also referred to as the "acetyl group amount") is preferably 0.1 mol% at the lower limit and 22.0 mol% at the upper limit. When the acetyl group amount is 0.1 mol% or more, it is possible to suppress the increase in viscosity of the slurry composition for a ceramic green sheet due to intramolecular and intermolecular hydrogen bonding of hydroxyl groups in the polyvinyl acetal resin. When the acetyl group amount is 22.0 mol% or less, it is possible to improve the handleability without excessively increasing the flexibility of the polyvinyl acetal resin. The acetyl group amount is more preferably 0.5 mol% at the lower limit and 15.0 mol% at the upper limit. That is, the acetyl group amount is preferably 0.1 to 22.0 mol%, and more preferably 0.5 to 15 mol%. By setting the acetyl group amount in this range, the hydroxyl group amount-acetyl group amount conversion wavenumber width can be set within a predetermined range. The acetyl group amount can be, for example, １ It can be measured by H-NMR.

[0030] From the viewpoint of maintaining mechanical strength when preparing a thin film ceramic green sheet, the polyvinyl acetal resin of the present invention has an average degree of polymerization of preferably 500, more preferably 600, even more preferably 700, and particularly preferably 1000, at its lower limit. From the viewpoint of solubility in organic solvents and dissolution viscosity, the average degree of polymerization is preferably 10,000, more preferably 5,000, even more preferably 3500, and particularly preferably 2000. That is, the average degree of polymerization is preferably 500 to 10,000, more preferably 600 to 5,000, even more preferably 700 to 3500, and particularly preferably 1000 to 2000. The average degree of polymerization of the polyvinyl acetal resin is the same as that of the raw material polyvinyl alcohol. The average degree of polymerization can be measured in accordance with JIS K 6726. When a plurality of raw material polyvinyl alcohols are used, the average degree of polymerization of each polyvinyl alcohol resin is multiplied by the proportion of the added amount, and the sum of these values ​​is taken as the average degree of polymerization of the polyvinyl acetal resin.

[0031] The polyvinyl acetal resin of the present invention can usually be produced by acetalizing a polyvinyl alcohol resin.

[0032] The polyvinyl alcohol resin can be, for example, a conventionally known polyvinyl alcohol resin, such as a resin produced by saponifying a polyvinyl acetate resin with an alkali, an acid, aqueous ammonia, or the like. The polyvinyl alcohol resin can be fully saponified, but it does not need to be fully saponified as long as it has at least one unit having two consecutive hydroxyl groups at the meso and racemo positions at at least one location on the main chain; it can also be a partially saponified polyvinyl alcohol resin. Furthermore, the polyvinyl alcohol resin can also be a copolymer of vinyl alcohol and a monomer copolymerizable with vinyl alcohol, such as an ethylene-vinyl alcohol copolymer resin or a partially saponified ethylene-vinyl alcohol copolymer resin. Examples of the polyvinyl acetate resin include ethylene-vinyl acetate copolymers.

[0033] The polyvinyl alcohol resin preferably has a degree of saponification of 75 mol% or more. The degree of saponification is more preferably 76 mol% or more and 99.5 mol% or less, and even more preferably 78 mol% or more and 99.4 mol% or less. That is, the degree of saponification is preferably 76 to 99.5 mol%, and more preferably 78 to 99.4 mol%. By using the polyvinyl alcohol resin, the Mz can be set within a predetermined range.

[0034] The acetalization is preferably carried out in an aqueous solvent, a mixed solvent of water and a water-compatible organic solvent, or an organic solvent. Examples of the water-compatible organic solvent include alcohol-based organic solvents. Examples of the organic solvent include alcohol-based organic solvents, aromatic organic solvents, aliphatic ester-based solvents, ketone-based solvents, lower paraffin-based solvents, ether-based solvents, amide-based solvents, and amine-based solvents. Examples of the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, and methyl benzoate. Examples of the aliphatic ester-based solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, and ethyl acetoacetate. Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone. Examples of the lower paraffin solvents include hexane, pentane, octane, cyclohexane, and decane. Examples of the ether solvents include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol diethyl ether. Examples of the amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and acetanilide. Examples of the amine solvents include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline, and pyridine. These solvents can be used alone or in combination of two or more. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferred from the viewpoints of solubility in the resin and ease of purification.

[0035] The acetalization is preferably carried out in the presence of an acid catalyst. The acid catalyst is not particularly limited, and examples thereof include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, carboxylic acids such as formic acid, acetic acid, and propionic acid, and sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and paratoluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more compounds. Among these, hydrochloric acid, nitric acid, and sulfuric acid are preferred, and hydrochloric acid is particularly preferred.

[0036] Examples of the aldehyde used in the acetalization include aldehydes having a chain aliphatic group, a cyclic aliphatic group, or an aromatic group having 1 to 10 carbon atoms. Conventionally known aldehydes can be used as these aldehydes. The aldehyde used in the acetalization reaction is not particularly limited, and examples include aliphatic aldehydes and aromatic aldehydes. Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, 2-ethylhexylaldehyde, n-heptylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, and amylaldehyde. Examples of the aromatic aldehyde include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, and β-phenylpropionaldehyde. These aldehydes may be used alone or in combination of two or more. Among these, preferred aldehydes are formaldehyde, acetaldehyde, butylaldehyde, 2-ethylhexylaldehyde, and n-nonylaldehyde, which have excellent acetalization reactivity and can provide a sufficient internal plasticizing effect to the resulting resin, thereby imparting good flexibility. Furthermore, formaldehyde, acetaldehyde, and butylaldehyde are more preferred because they can provide an adhesive composition that is particularly excellent in impact resistance and adhesion to metals.

[0037] The amount of the aldehyde to be added can be appropriately determined depending on the amount of acetal groups in the target polyvinyl acetal resin. In particular, it is preferable to add the aldehyde in an amount of from 50 mol % to 95 mol %, more preferably from 55 mol % to 90 mol %, based on 100 mol % of polyvinyl alcohol, because this allows the acetalization reaction to proceed efficiently and makes it easy to remove unreacted aldehyde.

[0038] In the acetalization, the aldehyde is preferably added in multiple portions. The number of times the aldehyde is added is preferably two. When the aldehyde is added in multiple portions, the temperature during the first addition is preferably 35°C or higher and 60°C or lower, more preferably 40°C or higher and 55°C or lower, and even more preferably 45°C or higher and 50°C or lower. By adjusting the temperature during the first addition, the Mz(THF) and viscosity can be adjusted to a predetermined range. Furthermore, the temperature during the final addition is preferably 19°C or higher and 30°C or lower, more preferably 20°C or higher and 27°C or lower. Furthermore, the interval between the first and final additions is preferably 4 hours or higher and 12 hours or lower, and more preferably 6 hours or higher and 8 hours or lower. By adjusting the interval between the first and final additions, the number of peaks in a chromatogram measured using GPC-MALS, the z-average radius of gyration, and Mz(THF) can be adjusted to a predetermined range.

[0039] In the acetalization, it is preferable to add the aldehyde at a predetermined temperature, then raise the temperature and carry out the reaction for a predetermined time (reaction step), and maintain the temperature at the predetermined temperature (aging step). The time from the addition of the final aldehyde to the start of the temperature rise (temperature rise start time or reaction time) is preferably 150 minutes or more and 400 minutes or less, more preferably 155 minutes or more and 360 minutes or less, and even more preferably 180 minutes or more and 300 minutes or less. By setting the temperature rise start time as described above, the number of peaks and the z-average radius of gyration in the chromatogram measured using GPC-MALS can be within a predetermined range. Furthermore, the temperature rise time is preferably 330 minutes or more and 485 minutes or less, more preferably 340 minutes or more and 420 minutes or less.

[0040] Furthermore, when the temperature at the time of adding the final aldehyde is less than 35°C, it is preferable to change the temperature increase rate (temperature increase rate 1) from the temperature at the time of adding the final aldehyde to 35°C and the temperature increase rate (temperature increase rate 2) from 35°C to the holding temperature of the aging step. The temperature increase rate 1 is preferably 0.01°C / min or more and 0.08°C / min or less, and more preferably 0.02°C / min or more and 0.06°C / min or less. By setting the temperature increase rate 1 within the above range, the number of peaks and the z-average radius of gyration in the chromatogram measured using GPC-MALS can be set within predetermined ranges. The temperature increase rate 2 is preferably 0.05°C / min or more and 0.30°C / min or less, and more preferably 0.10°C / min or more and 0.25°C / min or less. By setting the temperature increase rate 2 within the above range, the hydroxyl group amount equivalent wavenumber width and the hydroxyl group amount / acetyl group amount equivalent wavenumber width can be set within predetermined ranges.

[0041] The retention time in the aging step is preferably 1 hour or more and 5 hours or less, and more preferably 2.5 hours or more and 3 hours or less. The retention temperature in the aging step is preferably 50° C. or more and 70° C. or less, and more preferably 55° C. or more and 65° C. or less. By setting the retention time and retention temperature as described above, the hydroxyl group amount equivalent wavenumber width and the hydroxyl group amount / acetyl group amount equivalent wavenumber width can be set within a predetermined range.

[0042] The polyvinyl acetal resin of the present invention and a plasticizer can be contained in a resin composition for a ceramic green sheet. The resin composition for a ceramic green sheet of the present invention may contain components such as an antioxidant, a surfactant, an ultraviolet absorber, and an antifoaming agent, as long as the effects of the present invention are not impaired.

[0043] As a method for producing the resin composition for a ceramic green sheet, for example, a plasticizer and other additives that are added as needed can be added to a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin with an aldehyde, and then mixed to obtain a resin composition for a ceramic green sheet.

[0044] The resin composition for ceramic green sheets contains a plasticizer. Addition of the plasticizer can significantly improve the mechanical strength and flexibility of the resulting ceramic green sheet. Examples of the plasticizer include phthalate diesters such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP), adipic acid diesters such as dioctyl adipate, and alkylene glycol diesters such as triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-heptanoate, and triethylene glycol-di-heptanoate.

[0045] In the resin composition for a ceramic green sheet, the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin is preferably 7 parts by weight in lower limit, more preferably 8.5 parts by weight in lower limit, and preferably 18 parts by weight in upper limit, more preferably 13.5 parts by weight in upper limit.

[0046] A slurry for ceramic green sheets can be prepared by mixing the polyvinyl acetal resin of the present invention with an organic solvent and ceramic powder.

[0047] The organic solvent is not particularly limited as long as it can dissolve the polyvinyl acetal resin, and examples thereof include ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone. Other examples include alcohols such as methanol, ethanol, isopropanol, and butanol, and aromatic hydrocarbons such as toluene and xylene. Further examples include esters such as methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, 2-ethylhexyl acetate, and 2-ethylhexyl butyrate. Other examples include methyl cellosolve, ethyl cellosolve, butyl cellosolve, terpineol, dihydroterpineol, butyl cellosolve acetate, butyl carbitol acetate, terpineol acetate, and dihydroterpineol acetate. In particular, alcohols, ketones, aromatic hydrocarbons and mixed solvents thereof are preferred in terms of coating and drying properties, with a mixed solvent of ethanol and toluene and a mixed solvent of methyl ethyl ketone and toluene being more preferred.

[0048] The content of the organic solvent in the ceramic green sheet slurry is determined depending on the type of polyvinyl acetal resin used and is not particularly limited, but if it is too low, the solubility required for kneading is difficult to exhibit. On the other hand, if it is too high, the viscosity of the ceramic green sheet slurry composition becomes too low, which can result in poor handling when producing ceramic green sheets. Therefore, the content of the organic solvent is preferably 20% by weight or more and 80% by weight or less.

[0049] Examples of the ceramic powder include powders of metal or nonmetal oxides or non-oxides used in ceramic production. These powders may be single compositions, compounds, or mixtures. The constituent elements of the metal oxides or non-oxides, both cations and anions, may be single elements or multiple elements, and may further contain additives added to improve the properties of the oxides or non-oxides. Specific examples include oxides, carbides, nitrides, borides, sulfides, etc. of Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanides, actinides, Ti, Zr, Hf, Bi, V, Nb, Ta, W, Mn, Fe, Co, Ni, etc. Specific examples of oxide powders containing multiple metal elements, commonly referred to as double oxides, can be classified based on their crystal structure, such as NaNbO, which has a perovskite structure. ３ , SrZrO ３ , PbZrO ３ , SrTiO ３ , BaZrO ３ , PbTiO ３ , BaTiO ３ Examples of materials that have a spinel structure include MgAl ２ O ４ , ZnAl ２ O ４ , CoAl ２ O ４ , NiAl ２ O4, MgFe ２ O ４ Examples of materials with an ilmenite structure include MgTiO ３ , MnTiO ３ , FeTiO ３ As a material having a garnet structure, GdGa ５ O １２ , Y ６ Fe ５ O １２ Among these, the modified polyvinyl acetal resin of the present invention is BaTiO ３ It exhibits high properties compared to ceramic green sheets mixed with powder.

[0050] The average particle size of the ceramic powder is not particularly limited, but for example, for producing a thin ceramic green sheet (thickness of 5 μm or less), it is preferably 0.5 μm or less.

[0051] The ceramic green sheet slurry may contain other polyvinyl acetal resins other than the polyvinyl acetal resin of the present invention, as well as other resins such as acrylic resins and ethyl cellulose, within the range that does not impair the effects of the present invention. In such cases, the content of the polyvinyl acetal resin of the present invention relative to the total binder resins is preferably 50% by weight or more.

[0052] If necessary, a dispersant, an antioxidant, an ultraviolet absorber, a surfactant, a filler, etc. may be added appropriately to the above-mentioned slurry for the ceramic green sheet, and in some cases, a small amount of other resin such as an acrylic resin or a urethane resin may also be added.

[0053] The method for producing the slurry for the ceramic green sheet is not particularly limited, and examples thereof include a method in which the polyvinyl acetal resin of the present invention, an organic solvent, a ceramic powder, and various additives to be added as needed are mixed using various mixers such as a ball mill, a blender mill, and a three-roll mill.

[0054] The ceramic green sheet slurry is applied, followed by heating and drying to obtain a ceramic green sheet. A ceramic electronic component can be manufactured using the ceramic green sheet. For example, a ceramic electronic component can be manufactured by carrying out a step of applying an electrode layer paste to the surface of the ceramic green sheet, and a step of stacking the ceramic green sheets on which the electrode layers have been formed, thermocompression bonding the resulting laminate, and then degreasing and firing the resulting laminate.

[0055] The method for applying the slurry for the ceramic green sheet is not particularly limited, and examples thereof include methods using a roll coater, a die coater, a curtain coater, etc. As for other specific methods, conventionally known methods can be used.

[0056] The ceramic electronic component is not particularly limited, and examples thereof include a multilayer ceramic capacitor, a multilayer ceramic inductor, a capacitor, a piezoelectric actuator, a multilayer varistor, a multilayer thermistor, an EMI filter, an aluminum nitride multilayer substrate, an alumina multilayer substrate, etc. Such a multilayer ceramic capacitor also constitutes one aspect of the present invention.

[0057] The method for producing the ceramic electronic component includes a step of applying an electrode layer paste to the surface of the ceramic green sheet. The electrode layer paste can be obtained by dissolving, for example, a polyvinyl acetal resin, ethyl cellulose, or acrylic resin as a binder resin in an organic solvent and dispersing a conductive powder or the like. These resins may be used alone or in combination. An electrode layer paste containing a polyvinyl acetal resin is preferred because it exhibits excellent adhesion to the ceramic green sheet during the thermocompression bonding step.

[0058] In the method for producing a ceramic electronic component, the ceramic green sheets having electrode layers formed thereon are prepared as described above, and then ceramic green sheets having electrode layers formed thereon that are prepared in the same manner are stacked and thermocompression-bonded to obtain a laminate, which is then degreased and fired, thereby obtaining a multilayer ceramic electronic component that solves problems such as sheet attack and cracking. Note that the thermocompression-bonding step and the steps of degreasing and firing the laminate are not particularly limited, and conventionally known methods can be used.

[0059] According to the present invention, it is possible to provide a polyvinyl acetal resin that can produce ceramic green sheets with high mechanical strength and excellent sheet attack resistance, and that can produce highly reliable multilayer ceramic capacitors, as well as a ceramic green sheet slurry, ceramic green sheets, and multilayer ceramic capacitors using the polyvinyl acetal resin. In particular, the present invention can achieve high breaking strain and breaking stress even in thin ceramic green sheets. Furthermore, while the polyvinyl acetal resin is fully soluble in the slurry for the ceramic green sheet when it is prepared, its solubility in organic solvents can be reduced when it is made into a ceramic green sheet.

[0060] FIG. 1 is a diagram showing an example of an IR absorption spectrum of a polyvinyl acetal resin of the present invention measured with an infrared spectrophotometer at 20° C.

[0061] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0062] Example 1 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 340 minutes). The reaction was completed by maintaining the temperature at 55°C for 2.5 hours, and the mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin. The temperature rise time is the time from the start of temperature rise until the temperature reaches the holding temperature.

[0063] (Preparation of Ceramic Green Sheets) (Preparation of Inorganic Powder Dispersion) 1 part by weight of polyvinyl acetal resin (BL-1, manufactured by Sekisui Chemical Co., Ltd.) was added to a mixed solvent of 20 parts by weight of toluene and 20 parts by weight of ethanol and stirred to dissolve. Next, 100 parts by weight of barium titanate powder (BT01, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the resulting solution and stirred for 180 minutes using a bead mill (Ready Mill, manufactured by Imex Co., Ltd.) to prepare an inorganic powder dispersion. (Preparation of Resin Solution) 8 parts by weight of polyvinyl acetal resin and 2.1 parts by weight of plasticizer (G260, manufactured by Sekisui Chemical Co., Ltd.) were added to a mixed solvent of 45 parts by weight of ethanol and 45 parts by weight of toluene and stirred to dissolve, to prepare a resin solution. (Preparation of Slurry for Ceramic Green Sheets) The resin solution was added to the resulting inorganic powder dispersion and stirred for 90 minutes using a bead mill to obtain a slurry for ceramic green sheets.

[0064] Example 2 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 340 minutes). The reaction was completed by maintaining the temperature at 55°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0065] Example 3 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 363 minutes). The reaction was completed by maintaining the temperature at 60°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0066] Example 4 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 30°C, and 4 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.02°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 363 minutes). The reaction was completed by maintaining the temperature at 55°C for 3 hours, and the mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0067] Example 5 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 25°C, and 6 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.04°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 340 minutes). The reaction was completed by maintaining the temperature at 55°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0068] Example 6 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 98.7 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 363 minutes). The reaction was completed by maintaining the temperature at 60°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0069] Example 7 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.4 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 50°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 12 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.15°C / min (temperature increase time 420 minutes). The reaction was completed by maintaining the temperature at 60°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0070] Example 8 3,000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1,700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 30°C, and 4 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 300 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.02°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 340 minutes). The reaction was completed by maintaining the temperature at 55°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0071] Example 9 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 145 g of n-butylaldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.04°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 460 minutes). The reaction was completed by maintaining the temperature at 55°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0072] Example 10 5000 g of pure water was added to 130 g of a first polyvinyl alcohol resin (average degree of polymerization 3300, degree of saponification 91.7 mol%) and 130 g of a second polyvinyl alcohol resin (average degree of polymerization 3300, degree of saponification 88.5 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 50°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 12 hours after the first addition, 12 g of acetaldehyde and 150 g of n-butylaldehyde were further added thereto (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.15°C / min (temperature increase time 420 minutes). The mixture was maintained at 60°C for 3 hours to complete the reaction, and the mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0073] Example 11 3,000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 800, degree of saponification 98.0 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 50°C, and 200 g of 35 wt% hydrochloric acid and 2 g of n-butyl aldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 12 hours after the first addition, 125 g of n-butyl aldehyde was further added (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.06°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.15°C / min (temperature increase time 420 minutes). The reaction was completed by maintaining the temperature at 60°C for 3 hours, followed by neutralization, water washing, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0074] Example 12 6000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization: 4000, degree of saponification: 99.1 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 2 g of n-butylaldehyde were added thereto (first addition). The solution was then cooled to 20°C, and 8 hours after the first addition, 15 g of acetaldehyde and 120 g of n-butylaldehyde were further added thereto (second addition). Thereafter, 180 minutes after the second addition, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.04°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.22°C / min (temperature increase time 460 minutes). The mixture was maintained at 55°C for 3 hours to complete the reaction, and the mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0075] Comparative Example 1 3100 g of pure water was added to 300 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 98.0 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 160 g of n-butyl aldehyde were added thereto. The mixture was then maintained at 40°C for 3 hours to carry out an acetalization reaction, followed by neutralization, washing with water, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0076] Comparative Example 2 3,000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization: 1,700, degree of saponification: 99.2 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 147 g of n-butyl aldehyde were added thereto. 30 minutes after the addition, the temperature was increased at a rate of 0.22°C / min (temperature increase time: 45 minutes), and the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction. The resulting mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0077] Comparative Example 3 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization: 1700, degree of saponification: 99.1 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 147 g of n-butyl aldehyde were added thereto. 60 minutes after the addition, the temperature was increased at a rate of 0.3°C / min (temperature increase time: 150 minutes), and the mixture was maintained at 60°C for 2 hours to carry out an acetalization reaction. The resulting mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0078] Comparative Example 4 3100 g of pure water was added to 300 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 98.7 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 40°C, and 200 g of hydrochloric acid with a concentration of 35 wt% and 160 g of n-butyl aldehyde were added thereto. The mixture was then maintained at 40°C for 3 hours to carry out an acetalization reaction, followed by neutralization, washing with water, and drying in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0079] Comparative Example 5 3,000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 800, degree of saponification 93.5 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 10°C, and 200 g of 35 wt% hydrochloric acid and 100 g of n-butyl aldehyde were added thereto. After 120 minutes, the mixture was heated to 35°C at a heating rate [heating rate 1] of 0.1°C / min, and then heated from 35°C at a heating rate [heating rate 2] of 0.02°C / min (heating time 500 min). The mixture was maintained at 40°C for 3 hours to complete the reaction. The mixture was then neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0080] Comparative Example 6 260 g of polyvinyl alcohol resin (average degree of polymerization 800, degree of saponification 98.0 mol%) was added to 3,000 g of pure water and stirred at 90°C for approximately 2 hours to dissolve. This solution was cooled to 20°C, and 200 g of 35 wt% hydrochloric acid and 185 g of n-butyl aldehyde were added thereto. After 60 minutes, the temperature was increased to 35°C at a temperature increase rate [temperature increase rate 1] of 0.6°C / min, and then increased from 35°C at a temperature increase rate [temperature increase rate 2] of 0.2°C / min (temperature increase time 225 minutes). The reaction was completed by maintaining the temperature at 75°C for 1 hour, and the mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0081] Comparative Example 7 3000 g of pure water was added to 260 g of polyvinyl alcohol resin (average degree of polymerization 1700, degree of saponification 77.0 mol%), and the mixture was stirred at 90°C for approximately 2 hours to dissolve the resin. This solution was cooled to 20°C, and 200 g of 35 wt% hydrochloric acid and 125 g of n-butyl aldehyde were added thereto. After 60 minutes, the mixture was heated to 35°C at a heating rate [heating rate 1] of 0.22°C / min, and then heated from 35°C at a heating rate [heating rate 2] of 0.22°C / min (heating time 114 minutes). The mixture was maintained at 45°C for 6 hours to complete the reaction. The mixture was then neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.

[0082] (Evaluation) The polyvinyl acetal resins obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2.

[0083] (1) Evaluation of Polyvinyl Acetal Resin (1-1) Amount of Acetal Group, Amount of Hydroxyl Group, and Amount of Acetyl Group The obtained polyvinyl acetal resin was measured using an AV400 spectrometer (manufactured by Bruker). １ H-NMR measurement was carried out to calculate the amount of acetal groups, hydroxyl groups, and acetyl groups. ６ The solution was dissolved in water to a concentration of 1.6% by weight to prepare a measurement solution. １ H-NMR measurements were carried out at 80°C.

[0084] (1-2) Number of Peaks in Chromatogram Measured by GPC-MALS and z-Average Radius of Gyration 5 ml of tetrahydrofuran (THF) was added to 3 mg of the obtained polyvinyl acetal resin, and the mixture was gently stirred at 40° C. Thereafter, the mixture was filtered using a 0.5 μm filter to prepare a sample for GPC-MALS. Measurements were performed using a gel permeation chromatography system [pump (Shimadzu Corporation, LC-20AD), autosampler (Shimadzu Corporation, SIL-10AXL), column oven (Shimadzu Corporation, CTO-20AC)], a multi-angle light scattering detector (Wyatt Technology, DAWN HELEOS II), and a differential refractive index detector (Wyatt Technology, Optilab T-rEX) with a mobile phase of tetrahydrofuran at 1 mL / min, two PLgel 20 μm MIXED-A columns (7.5 mm square × 30 cm, Polymer Laboratories), a column temperature of 40°C, a detector temperature of 25°C, and a sample injection volume of 0.2 mL. Using a Wyatt Technology data processing system (ASTRA), dn / dc was calculated from the RI curve and the measurement results at θ = 90°, and the z-average radius of gyration was determined. In addition, the number of LS intensity peaks was counted for the LS detection peaks observed in the elution time region of 7 to 10 minutes and the elution time region of 10 to 17 minutes from the chromatogram using the following procedure.

[0085] The LS detection peaks are designated P1, P2, ... Px in order from the shortest elution time, and the LS detection peak value of Px is designated Sx. The maximum value of the LS intensity at elution times of 4.9 to 5.1 minutes is designated LSI. Ｍａｘ and minimum LSI Ｍｉｎ In this case, N was calculated using the following formula (6), and then peaks that satisfied formula (7) were determined to be LS intensity peaks, and the number of peaks was counted. Ｍａｘ |-|LSI Ｍｉｎ (6) Sx / N≧50 (7) When calculating the z-average radius of gyration, the data processing system is used to calculate the P Ｌ and the peak P seen on the largest side Ｈ In this case, PＬ The peak value of the LS Intensity is 2 / 3 of the peak value of the LS Intensity. ＬＸ From P Ｈ The peak value of the LS Intensity is 2 / 3 of the peak value of the LS Intensity. ＨＹ The z-average radius of gyration was calculated by setting the range.

[0086] (1-3) IR absorption spectrum The obtained polyvinyl acetal resin was dissolved in a mixed solution of ethanol and toluene in a weight ratio of 1:1, and then coated on a PET film. －１ The film thickness of the measurement sample was adjusted so that the minimum transmittance of the peak appearing around 1000 nm was 20%, and a polyvinyl acetal resin sheet was obtained. The IR absorption spectrum of the obtained polyvinyl acetal resin sheet was measured using an infrared spectrophotometer (FT-720, manufactured by HORIBA) at 20°C. The measurement results showed that the IR absorption spectrum was measured at wavenumbers of 3050 to 3750 cm. －１ A baseline was drawn for the peaks that appeared within this range, and peak analysis was performed on data corrected so that the transmittances at both ends of the peak were 100%, to measure the minimum transmittance X, the transmittance a that satisfies [100-(100-X) / 2], and the wavenumbers A and B that indicate the transmittance a (the wavenumber on the low wavenumber side is A, and the wavenumber on the high wavenumber side is B). １ Using the amount of hydroxyl groups determined by H-NMR measurement, the hydroxyl group amount converted wavenumber width (cm －１ / mol%)=[(B−A) / amount of hydroxyl groups] was calculated. １ Using the amount of acetyl groups determined by H-NMR measurement, the wave number width of hydroxyl groups converted into the amount of acetyl groups=[(B−A) / amount of hydroxyl groups / acetyl groups] was calculated.

[0087] (1-4) Viscosity Measurement The obtained polyvinyl acetal resin was dissolved in a 1:1 weight ratio ethanol / toluene mixed solution to a concentration of 5% by mass to prepare a sample for viscosity measurement. The viscosity of the obtained sample for viscosity measurement was measured using a Brookfield viscometer at a solution temperature of 20°C. The Brookfield viscometer used was a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.), and the rotation speed and rotor were as follows: Examples 1 to 12, Comparative Examples 1 to 7: rotation speed 30 rpm, SPINDLE No. M1

[0088] (1-5) Measurement of z-average molecular weight [Mz(THF), Mz(NMP)] The obtained polyvinyl acetal resin was dissolved in tetrahydrofuran (THF) at a concentration of 0.2 wt%, passed through a PTFE filter with a pore size of 0.45 μm, and measured at a flow rate of 0.35 mL / min using a GPC apparatus HLC-8420 (manufactured by Tosoh Corporation), THF as the mobile phase, a Bryce-type double-pass refractive index detector (manufactured by Tosoh Corporation) as the detector, and a TSKgel Super HZM-H column (manufactured by Tosoh Corporation). The obtained measurement results were calibrated using a molecular weight calibration curve prepared using monodisperse polystyrene standard samples to obtain the z-average molecular weight Mz(THF). Similarly, the obtained polyvinyl acetal resin was dissolved in N-methylpyrrolidone (NMP) at a concentration of 0.2 wt %, passed through a PTFE filter with a pore size of 0.45 μm, and measured at a flow rate of 0.5 mL / min using a GPC-101 (Shodex) GPC apparatus, NMP as the mobile phase, a differential refractive index detector RI-715 (Shodex) as the detector, and an LF-804 (Shodex) column. The obtained measurement results were calibrated using a molecular weight calibration curve prepared using monodisperse polystyrene standard samples to obtain the z-average molecular weight Mz(NMP). From the obtained Mz(THF) and Mz(NMP), "Mz(THF) / Mz(NMP)" was calculated.

[0089] (2) Evaluation of Ceramic Green Sheets (Preparation of Inorganic Dispersion) 1 part by weight of polyvinyl acetal resin (BL-1, manufactured by Sekisui Chemical Co., Ltd.) was added to a mixed solvent of 20 parts by weight of toluene and 20 parts by weight of ethanol, and dissolved by stirring. Next, 100 parts by weight of barium titanate powder (BT01, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred for 180 minutes using a bead mill (Ready Mill, manufactured by Imex Co., Ltd.) to prepare an inorganic dispersion.

[0090] (Preparation of Resin Solution) 8 parts by weight of the obtained polyvinyl acetal resin and 2 parts by weight of DOP were added to a mixed solvent of 45 parts by weight of ethanol and 45 parts by weight of toluene, and dissolved with stirring to prepare a resin solution.

[0091] (Preparation of ceramic green sheets) The resin solution was added to the inorganic dispersion and stirred for 90 minutes in a bead mill to obtain a ceramic green sheet composition. The obtained ceramic green sheet composition was applied to a release-treated PET film using a coater so that the thickness after drying would be 20 μm, and then heated and dried to prepare a ceramic green sheet.

[0092] (2-1) Sheet attack resistance The obtained ceramic green sheet was cut into a 5 cm x 5 cm square. Then, 70 μL of dihydroterpineol acetate at 23°C was dripped onto the test piece, and the dripping time was set to 0. Then, the ceramic green sheet was visually observed, and the time until wrinkles appeared on the ceramic green sheet was measured and evaluated according to the following evaluation criteria. Note that the longer the time until wrinkles appeared, the better the sheet attack resistance. AA: 100 seconds or more A: 80 seconds or more but less than 100 seconds B: 60 seconds or more but less than 80 seconds C: Less than 60 seconds

[0093] (2-2) Stress at Break and Strain at Break The obtained ceramic green sheet was cut into a size of 5 cm x 1 cm to prepare a test piece. Using a tensile tester (Shimadzu Corporation, AUTOGRAPH AGS-J), the sheet was pulled at a pulling rate of 500% / min at a measurement temperature of 20°C, and the breaking tensile strength (kg / cm ２) was measured. A stress σ (MPa) - strain ε (%) curve was calculated from the obtained values. Note that 500% / min means the speed at which the test piece is moved a distance five times the distance between the chucks in one minute. The stress at break and strain at break were calculated from the obtained stress-strain curve and evaluated according to the following evaluation criteria. (Stress at break) AA: 34 MPa or more A: 33 MPa or more and less than 34 MPa B: 30 MPa or more and less than 33 MPa C: Less than 30 MPa (Strain at break) AA: 22% or more A: 21% or more and less than 22% B: 17% or more and less than 21% C: Less than 17%

[0094]

[0095]

[0096] According to the present invention, it is possible to provide a polyvinyl acetal resin that can produce a ceramic green sheet having high mechanical strength and excellent sheet attack resistance, and that can produce a highly reliable multilayer ceramic capacitor, as well as a ceramic green sheet slurry, a ceramic green sheet, and a multilayer ceramic capacitor that use the polyvinyl acetal resin.

Claims

1. In a chromatogram measured using GPC-MALS, there is one or more LS intensity peaks in the retention time region of 7 to 10 minutes, and in an IR absorption spectrum measured using an infrared spectrophotometer, there is a peak in the wave number region of 3050 to 3750 cm －１ When the minimum transmittance of the peak within the range is X (%), among the wave numbers showing transmittance a (%) that satisfies [100-(100-X) / 2], the wave number on the low wave number side is A and the wave number on the high wave number side is B, １ The polyvinyl acetal resin has a hydroxyl group amount converted wavenumber width of 8.31 or more, which is calculated by the formula (1) using the amount of hydroxyl groups measured by H-NMR. －１ / mol%) = [(B - A) / amount of hydroxyl groups] (1) 2. The polyvinyl acetal resin according to claim 1, which has three or more LS intensity peaks in the retention time region of 7 to 17 minutes in a chromatogram measured using GPC-MALS.

3. The polyvinyl acetal resin according to claim 1 or 2, which has a z-average radius of gyration of 55 nm or more as measured by GPC-MALS.

4. The polyvinyl acetal resin according to any one of claims 1 to 3, wherein the hydroxyl group amount converted wavenumber width calculated by formula (1) is 8.45 or more.

5. The above A, B and １ The polyvinyl acetal resin according to any one of claims 1 to 4, wherein the hydroxyl group-acetyl group amount converted wavenumber width calculated by the following formula (2) using the hydroxyl group amount and the acetyl group amount measured by H-NMR is 6.5 to 18.0: －１ / mol% / mol%) = [(B - A) / amount of hydroxyl groups / amount of acetyl groups] (2) 6. The polyvinyl acetal resin according to any one of claims 1 to 5, wherein Mz(THF) / Mz(NMP) is 1.2 to 1.93, where Mz(THF) is the z-average molecular weight obtained using THF as the mobile phase and Mz(NMP) is the z-average molecular weight obtained using NMP as the mobile phase in GPC measurement using a differential refractive index detector.

7. The polyvinyl acetal resin according to any one of claims 1 to 6, wherein a 5% by weight solution of the polyvinyl acetal resin in a 1:1 mixed solvent of ethanol and toluene has a solution viscosity of 30 mPa·s or more and 200 mPa·s or less when measured using a Brookfield viscometer at a solution temperature of 20°C.

8. A slurry for ceramic green sheets, comprising the polyvinyl acetal resin according to any one of claims 1 to 7, an organic solvent, and ceramic powder.

9. A ceramic green sheet obtained by using the slurry for ceramic green sheet according to claim 8.

10. A multilayer ceramic capacitor obtained using the ceramic green sheet according to claim 9.

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