WO2024122519A1 - ポリビニルアセタール樹脂 - Google Patents

ポリビニルアセタール樹脂 Download PDF

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Publication number
WO2024122519A1
WO2024122519A1 PCT/JP2023/043374 JP2023043374W WO2024122519A1 WO 2024122519 A1 WO2024122519 A1 WO 2024122519A1 JP 2023043374 W JP2023043374 W JP 2023043374W WO 2024122519 A1 WO2024122519 A1 WO 2024122519A1
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Prior art keywords
polyvinyl acetal
acetal resin
mol
ceramic green
hours
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PCT/JP2023/043374
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English (en)
French (fr)
Japanese (ja)
Inventor
裕司 大東
貴之 前田
啓祐 竹中
剛史 織田
綾子 太田
春香 吉田
祥人 新井
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to CN202380040608.4A priority Critical patent/CN119213038A/zh
Priority to JP2024517176A priority patent/JP7813877B2/ja
Priority to KR1020247036520A priority patent/KR20250115906A/ko
Publication of WO2024122519A1 publication Critical patent/WO2024122519A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/38—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a polyvinyl acetal resin.
  • multilayer ceramic capacitors are generally manufactured through the following steps. First, a plasticizer, a dispersant, etc. are added to a solution in which a binder resin such as polyvinyl butyral resin or poly(meth)acrylic acid ester resin is dissolved in an organic solvent, and then a ceramic raw material powder is added and mixed uniformly with a mixing device such as a bead mill or a ball mill to obtain a slurry composition having a certain viscosity after defoaming.
  • a plasticizer, a dispersant, etc. are added to a solution in which a binder resin such as polyvinyl butyral resin or poly(meth)acrylic acid ester resin is dissolved in an organic solvent, and then a ceramic raw material powder is added and mixed uniformly with a mixing device such as a bead mill or a ball mill to obtain a slurry composition having a certain viscosity after defoaming.
  • This slurry composition is cast onto a support surface such as a release-treated polyethylene terephthalate film or a SUS plate using a doctor blade, reverse roll coater, etc., and the volatile matter such as the solvent is distilled off by heating, etc., and then peeled off from the support to obtain a ceramic green sheet.
  • a conductive paste that will become the internal electrodes is applied to the obtained ceramic green sheets by screen printing, and multiple sheets are alternately stacked and heated and pressed to produce a laminate.
  • a process to thermally decompose and remove the binder resin components and the like contained in the laminate that is, a so-called degreasing process, is performed, and external electrodes are sintered onto the end faces of the ceramic sintered body obtained by firing to obtain a multilayer ceramic capacitor.
  • Patent Document 1 proposes a polyvinyl acetal resin in which the reduction rate of the filtration flow rate is less than 10% when the polyvinyl acetal resin solution, which is dissolved in a 1:1 mixed solvent of methyl ethyl ketone and/or toluene and ethanol to prepare a 5 wt % solution, is filtered using a filter with a mesh size of 5 ⁇ m under conditions of a filtration temperature of 25° C. and a filtration pressure of 10 mmHg.
  • Patent Document 2 discloses a polyvinyl acetal resin in which the wave number A (cm ⁇ 1 ) of the peak in the wave number range of 3100 to 3700 cm ⁇ 1 in the IR absorption spectrum and the amount of hydroxyl groups (mol %) are controlled within specific ranges. It is said that by using such a polyvinyl acetal resin, when dissolved in an organic solvent, there is little undissolved matter, and the filtration time can be shortened, thereby improving productivity.
  • the present invention aims to provide a polyvinyl acetal resin that, particularly when used as a binder for ceramic green sheets, can produce ceramic green sheets with high uniformity in tensile strength and high stress at break.
  • the present disclosure (1) is a polyvinyl acetal resin in which the ratio of the peak integral value of the methine C atom shown in (a)' of a triad unit represented by the following formula (a) to the sum of the peak integral values of the methine C atoms shown in (a)', (b)', and (c)' of the triad units represented by the following formulas (a), (b), and (c) is less than 0.23, as determined by 13C-NMR (nuclear magnetic resonance) measurement, the weight-average molecular weight is 230,000 or more, and the half-width of a peak observed in a retention time range of 20 to 30 minutes is 0.50 or less in high performance liquid chromatography (HPLC) measurement.
  • HPLC high performance liquid chromatography
  • R in formula (b) and formula (c) is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the present disclosure (2) is the polyvinyl acetal resin according to the present disclosure (1), in which a solution viscosity of a 5 mass% solution dissolved in a 1:1 mixed solvent of ethanol and toluene is 30 mPa s or more and 600 mPa s or less, as measured using a B-type viscometer at a solution temperature of 20°C.
  • the present disclosure (3) is the polyvinyl acetal resin according to the present disclosure (1) or (2), in which the amount of hydroxyl groups is 23 mol % or more and 40 mol % or less.
  • the present disclosure (4) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (3), in which the amount of acetyl groups is 0.1 mol % or more and 5 mol % or less.
  • the present disclosure (5) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (4), in which the molecular weight distribution is 2.75 or less.
  • the present disclosure (6) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (5), which is used for a ceramic green sheet.
  • the present disclosure (7) is a slurry composition for a ceramic green sheet, comprising the polyvinyl acetal resin according to any one of the present disclosures (1) to (6), an organic solvent, and ceramic powder.
  • the present disclosure (8) is a ceramic green sheet obtained by using the slurry composition for a ceramic green sheet according to the present disclosure (7).
  • the present disclosure (9) is a multilayer ceramic capacitor obtained by using the ceramic green sheet according to the present disclosure (8). The present invention will be described in detail below.
  • a ceramic green sheet having a uniform tensile strength and a high breaking stress can be obtained by using a polyvinyl acetal resin in which the ratio of the peak integral value of the methine C atom shown in (a)' of the triad unit represented by the above formula (a) to the total of the peak integral values of the methine C atoms shown in (a)', (b)', and (c)' of the triad units represented by the above formulas (a), (b) and (c) measured by 13 C-NMR (the ratio of the peak integral value of a triad unit consisting of three chains of constitutional units having a hydroxyl group), the half width of the peak derived from polyvinyl acetal in high performance liquid chromatography analysis, and the weight average molecular weight satisfy a specific relationship, and thus have completed the present invention. Furthermore, when the polyvinyl acetal resin of the present invention is used as a slurry composition for
  • the ratio of the peak integral value of a triad unit consisting of three consecutive chains of constitutional units having a hydroxyl group measured by 13C -NMR is less than 0.23.
  • the ratio of the peak integral value of the triad unit consisting of three consecutive sequences of the structural units having a hydroxyl group is preferably 0.14 in the lower limit and 0.22 in the upper limit, more preferably 0.15 in the lower limit and even more preferably 0.21 in the upper limit.
  • the ratio of the peak integral value of the triad unit consisting of three consecutive sequences of the structural units having a hydroxyl group is preferably 0.14 to 0.22, and more preferably 0.15 to 0.21. If the ratio is less than 0.23, the solubility of the polyvinyl acetal resin and the dispersibility of the barium titanate are improved, and more uniform ceramic green sheets can be prepared, resulting in good uniformity in the tensile strength.
  • the ratio of the peak integral value of the "triad unit consisting of three consecutive chains of structural units having a hydroxyl group" is specified, which makes it possible to confirm the continuity of the hydroxyl groups more accurately compared to the case where the measurement is based on a diad unit consisting of two consecutive chains.
  • the ratio of the peak integral value of the triad unit consisting of three consecutive chains of constitutional units having the above hydroxyl group is the ratio of the sum of the peak integral values of the methine C atoms shown in (a)' of the triad unit represented by the above formula (a) to the sum of the peak integral values of the methine C atoms shown in (a)', (b)', and (c)' of the triad units represented by the above formulas (a), (b) and (c), and can be measured by 13C -NMR.
  • R 6 to R 9 in formulae (i), (j) and (m) are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the peak integral value [I(a)'] of the methine C atom shown in (a)' of the triad unit represented by the above formula (a) can be calculated by the sum of the integral value of the peak assigned to the methine C atom at the position (f)' of the triad unit represented by the above formula (f) in the 13C-NMR spectrum obtained by 13C-NMR (nuclear magnetic resonance) measurement as I(f)', the integral value of the peak assigned to the methine C atom at the position (g)' of the triad unit represented by the above formula (g) as I(g)', and the integral value of the peak assigned to the methine C atom at the position (k) '2 of the triad unit represented by the above formula (k), i.e., by the following formula (5).
  • I(a)' I(f)' + I(g)' + I(k)' 2 (5)
  • the ratio of the peak integral value of the triad unit represented by the above formula (a) to the sum of the peak integral values of the triad units represented by the above formulas (a), (b) and (c) [I(a)'/(I(a)'+I(b)'+I(c)')] can be calculated by the following formula (6).
  • I(a)'/(I(a)'+I(b)'+I(c)') (I(f)'+I(g)'+I(k)' 2 )/(I(f)'+I(g)'+I(k)' 2 +I(i)'+I(j)'+I(m)') (6)
  • I(f)' is the peak integral value in the range from 64.0 to 64.8 ppm
  • I(g)' is the peak integral value in the range from 65.8 to 66.7 ppm
  • I(i)' is the peak integral value in the range from 61.5 to 63.1 ppm
  • I(j)' is the peak integral value in the range from 64.8 to 65.8 ppm
  • I(m)' is the peak integral value in the range from 63.1 to 64.0 ppm.
  • the above I(k)' 2 is based on the peaks in the range of 66.7 to 70.5 ppm, but since it overlaps with peaks of other structures, it can be calculated from the difference with other peaks.
  • the peak integral value of the above I(k)' 2 can be calculated using the following formula (7).
  • I(t) is the peak integral value in the range of 66.7 to 70.5 ppm
  • I(d1)' is the peak integral value in the range of 98.5 to 101.5 ppm to which the methine C atom of the acetal portion of the 6-membered acetal ring having a meso type at the (d1)' position of the structural unit (d) belongs
  • I(e1)' is the peak integral value in the range of 91.5 to 101.5 ppm to which the methine C atom of the acetal portion of the 6-membered acetal ring having a racemo type at the (e1)' position of the structural unit (e) belongs.
  • I(d2)' is a peak integral value in the interval from 71.0 to 74.6 ppm to which the methine C atom of the main chain of a 6-membered acetal ring having a meso type at the (d2)' position of the structural unit (d) belongs
  • I(e2)' is a peak integral value in the interval from 66.7 to 70.5 ppm to which the methine C atom of the main chain of a 6-membered acetal ring having a racemo type at the (e2)' position of the structural unit (e) belongs.
  • I(k)' 2 I(t) - I(d1)' ⁇ I(e2)' ⁇ I(d2)' (7)
  • R 4 and R 5 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • the ratio of the peak integral value of the triplet unit consisting of three chains of structural units having the above-mentioned hydroxyl group can be adjusted by appropriately setting, for example, the degree of saponification of the raw material polyvinyl alcohol resin, the type of aldehyde, the conditions of the acetalization reaction, the amount of acetal groups, the amount of hydroxyl groups, the amount of acetyl groups, the weight average molecular weight, the number average molecular weight, the molecular weight distribution, etc. of the polyvinyl acetal resin.
  • the polyvinyl acetal resin of the present invention preferably has a solution viscosity of 30 mPa ⁇ s or more and 600 mPa ⁇ s or less, when a 5 mass % solution dissolved in a 1:1 mixed solvent of ethanol and toluene is measured using a B-type viscometer at a solution temperature of 20° C.
  • the viscosity is 30 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more, and particularly preferably 60 mPa ⁇ s or more.
  • the viscosity is 600 mPa ⁇ s or less, more preferably 400 mPa ⁇ s or less, and particularly preferably 200 mPa ⁇ s or less. That is, the viscosity is preferably 30 to 600 mPa ⁇ s, more preferably 50 to 400 mPa ⁇ s, and particularly preferably 60 to 200 mPa ⁇ s.
  • the B-type viscometer may be, for example, a TVB-10 viscometer manufactured by Toki Sangyo Co., Ltd.
  • the rotor and rotation speed during viscosity measurement are preferably adjusted appropriately depending on the solution viscosity, and for example, it is preferable to measure using SPINDLE No. M1 to M4 at a rotation speed in the range of 0.3 to 100 rpm.
  • the above viscosity can be adjusted by, for example, appropriately setting the degree of saponification and average degree of polymerization of the raw material polyvinyl alcohol resin, the conditions of the acetalization reaction, the amount of acetal groups, the amount of hydroxyl groups, the amount of acetyl groups, the weight average molecular weight, the number average molecular weight, the molecular weight distribution, etc. of the polyvinyl acetal resin.
  • the polyvinyl acetal resin of the present invention preferably has a structural unit having an acetal group represented by the following formula (1), a structural unit having a hydroxyl group represented by the following formula (2), and a structural unit having an acetyl group represented by the following formula (3).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • 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.
  • a methyl group and an n-propyl group are preferable.
  • the content of the structural unit having the acetal group represented by the above formula (1) (hereinafter also referred to as the "acetal group amount”) is preferably 55 mol % in lower limit and 75 mol % in upper limit.
  • the amount of acetal groups is 55 mol % or more, the solubility in organic solvents can be improved, and when the amount of acetal groups is 75 mol % or less, the polyvinyl acetal resin can have excellent tensile strength.
  • the lower limit of the acetal group content is more preferably 57 mol%, even more preferably 60 mol%, and the upper limit is more preferably 73 mol%.
  • the acetal group content is preferably 55 to 75 mol%, more preferably 57 to 73 mol%, and even more preferably 60 to 73 mol%.
  • the amount of acetal groups can be measured by 1 H-NMR.
  • the method for calculating the amount of acetal groups since the acetal groups of the polyvinyl acetal resin are obtained by acetalizing two hydroxyl groups of polyvinyl alcohol, the method of counting the two acetalized hydroxyl groups is adopted.
  • the content of the structural unit having a hydroxyl group represented by the above general formula (2) (hereinafter also referred to as the "hydroxyl group amount”) is preferably 23 mol % in lower limit and 40 mol % in upper limit.
  • the amount of hydroxyl groups is 23 mol % or more, the polyvinyl acetal resin can have high toughness, and when the amount of hydroxyl groups is 40 mol % or less, the solubility in organic solvents can be sufficiently improved.
  • the hydroxyl group amount is more preferably 25 mol %, still more preferably 27 mol %, particularly preferably 29 mol %, more preferably 35 mol %, and still more preferably 33 mol %.
  • the hydroxyl group amount is preferably 23 to 40 mol %, more preferably 25 to 35 mol %, still more preferably 27 to 33 mol %, and particularly preferably 29 to 33 mol %.
  • the amount of hydroxyl groups can be measured by 1 H-NMR.
  • the content of the structural unit having an acetyl group represented by the above general formula (3) (hereinafter also referred to as the "acetyl group amount”) is preferably 0.1 mol % in lower limit and 5 mol % in upper limit.
  • the amount of the acetyl group is 0.1 mol% or more, the increase in viscosity of the slurry composition for ceramic green sheets due to intramolecular and intermolecular hydrogen bonds of the hydroxyl groups in the polyvinyl acetal resin can be suppressed.
  • the amount of the acetyl group is 5 mol% or less, the flexibility of the polyvinyl acetal resin is not excessively increased, and the handleability can be improved.
  • the acetyl group amount is more preferably 0.3 mol% at the lower limit, even more preferably 0.5 mol% at the lower limit, more preferably 4 mol% at the upper limit, even more preferably 3 mol% at the upper limit, and particularly preferably 2 mol% at the upper limit.
  • the acetyl group amount is preferably 0.1 to 5 mol%, more preferably 0.3 to 4 mol%, even more preferably 0.5 to 3 mol%, and particularly preferably 0.5 to 2 mol%.
  • the amount of acetyl groups can be measured by 1 H-NMR.
  • the polyvinyl acetal resin of the present invention has a lower limit of the weight average molecular weight (Mw) of 230000.
  • Mw weight average molecular weight
  • the lower limit of the weight average molecular weight is preferably 270,000, more preferably 290,000, and even more preferably 330,000.
  • the upper limit is preferably 700,000, and more preferably 450,000. That is, the weight average molecular weight is preferably 270,000 to 700,000, more preferably 290,000 to 450,000, and even more preferably 330,000 to 450,000.
  • the polyvinyl acetal resin of the present invention has a number average molecular weight (Mn) of preferably 98,000 in lower limit, 250,000 in upper limit, and more preferably 160,000 in upper limit. That is, the number average molecular weight is preferably 98,000 to 250,000, and more preferably 98,000 to 160,000.
  • the polyvinyl acetal resin of the present invention has a molecular weight distribution, which is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), with a preferred lower limit of 2.2, a more preferred lower limit of 2.4, a preferred upper limit of 3.5, more preferably 3.0, even more preferably 2.75, particularly preferably 2.73, and most preferably 2.7. That is, the Mw/Mn is preferably 2.2 to 3.5, more preferably 2.4 to 3.0, even more preferably 2.4 to 2.75, particularly preferably 2.4 to 2.73, and most preferably 2.4 to 2.7.
  • the Mw and Mn can be measured, for example, by gel permeation chromatography (GPC) using an appropriate standard (for example, a polystyrene standard). Examples of columns used in measuring the Mw and Mn include TSKgel Super HZM-H.
  • the average polymerization degree has a preferable lower limit of 600, a more preferable lower limit of 800, and a still more preferable lower limit of 1000, and from the viewpoint of solubility in an organic solvent and dissolution viscosity, the average polymerization degree is preferably 4000, a more preferable upper limit of 3000, and a still more preferable upper limit of 2500. That is, the average polymerization degree is preferably 600 to 4000, more preferably 800 to 3000, and further preferably 1000 to 2500.
  • the average degree of polymerization of the polyvinyl acetal resin is the same as that of the raw material polyvinyl alcohol, and can be measured in accordance with JIS K 6726.
  • the half width of a peak observed in a retention time range of 20 to 30 minutes in high performance liquid chromatography (HPLC) measurement is 0.50 or less.
  • HPLC half width is within the above range, the uniformity of the tensile strength of the obtained ceramic green sheet can be improved.
  • the HPLC half-width is preferably 0.30 to 0.50, more preferably 0.31 to 0.45, even more preferably 0.32 to 0.42, and particularly preferably 0.33 to 0.40. That is, the HPLC half-width is preferably 0.30 to 0.50, more preferably 0.31 to 0.45, even more preferably 0.32 to 0.42, and particularly preferably 0.33 to 0.40.
  • the half-width means the peak width at a position that is 1/2 (50%) of the height of the observed peak.
  • HPLC measurement can be carried out, for example, under the following measurement conditions.
  • HPLC device Shimadzu Corporation Prominence Sample concentration: 0.2 mg/mL
  • Detector Shimadzu Corporation Evaporative Light Scattering Detector (hereinafter referred to as ELSD) "ELSD_LTII”
  • the inside of the column of the HPLC system is filled with a mixed solvent of mobile phase A/mobile phase B with a volume ratio of 9/1. In this state, the sample is injected, and the ratio of mobile phase B in the mobile phase is increased at a constant rate (4.5 vol%/min) over 20 minutes from immediately after the sample injection. Only mobile phase B is allowed to flow for 10 minutes from 20 minutes after the injection.
  • Polyvinyl acetal resin has low polarity sites derived from acetal ring monomers and vinyl ester monomers, and high polarity sites derived from vinyl alcohol monomers in the molecule. Therefore, it was found that there is a distribution of low polarity sites and high polarity sites in the molecule of polyvinyl acetal resin, which affects the uniformity of tensile strength.
  • the peak half width W 0.5h by HPLC analysis can determine the distribution of low polarity sites and high polarity sites in the polymer.
  • An increase in W 0.5h indicates that the distribution of low polarity sites and high polarity sites becomes wider, and a decrease in W 0.5h indicates that the distribution becomes narrower.
  • polyvinyl acetal resin can be dissolved uniformly, and a uniform ceramic green sheet can be produced, thereby improving the uniformity of tensile strength.
  • the HPLC half-width (peak half-width W 0.5h ) measured by HPLC can be adjusted by appropriately setting, for example, the degree of saponification and saponification degree distribution of the raw material polyvinyl alcohol resin, the conditions of the acetalization reaction, the amount of acetal groups, the amount of hydroxyl groups, the amount of acetyl groups, the weight-average molecular weight, the number-average molecular weight, the molecular weight distribution, and the like of the polyvinyl acetal resin.
  • the polyvinyl acetal resin of the present invention can usually be produced by acetalizing a polyvinyl alcohol resin.
  • polyvinyl alcohol resin 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 can be used.
  • the polyvinyl alcohol resin may be fully saponified, but does not need to be fully saponified as long as there is at least one unit having two consecutive hydroxyl groups at the meso and racemo positions at at least one location in the main chain, and may be a partially saponified polyvinyl alcohol resin.
  • polyvinyl alcohol resin 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, may also be used.
  • the polyvinyl acetate resin may be, for example, an ethylene-vinyl acetate copolymer.
  • the polyvinyl alcohol resin preferably has a saponification degree of 70 mol % or more and 99.5 mol % or less, and more preferably 95 mol % or more and 99.3 mol % or less. That is, the saponification degree is preferably 70 to 99.5 mol %, and more preferably 95 to 99.3 mol %.
  • the proportion of peak integral value of a triad unit consisting of three chains of structural units having a hydroxyl group in the polyvinyl acetal resin, the viscosity, and the HPLC half width can be set within a predetermined range.
  • the above acetalization is preferably carried out in a water solvent, in a mixed solvent of water and an organic solvent compatible with water, or in an organic solvent.
  • an organic solvent compatible with water for example, an alcohol-based organic solvent can be used.
  • 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.
  • 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 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 solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, and acetophenone.
  • Examples of the lower paraffin solvent include hexane, pentane, octane, cyclohexane, and decane.
  • Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol diethyl ether.
  • Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and acetanilide.
  • amine solvent examples include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline, and pyridine. These solvents may 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.
  • 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 them, hydrochloric acid, nitric acid, and sulfuric acid are preferred, and hydrochloric acid is particularly preferred.
  • the aldehyde used in the acetalization reaction may be an aldehyde having a chain aliphatic group, a cyclic aliphatic group, or an aromatic group having 1 to 10 carbon atoms. Any known aldehyde may be used as the aldehyde.
  • the aldehyde used in the acetalization reaction is not particularly limited, and may be, for example, an aliphatic aldehyde, an aromatic aldehyde, or the like.
  • 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.
  • aromatic aldehyde examples include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, and ⁇ -phenylpropionaldehyde. These aldehydes may be used alone or in combination of two or more.
  • aldehydes are formaldehyde, acetaldehyde, butylaldehyde, 2-ethylhexylaldehyde, and n-nonylaldehyde, which have excellent acetalization reactivity and can bring about a sufficient internal plasticizing effect in the resin produced, thereby imparting good flexibility.
  • formaldehyde, acetaldehyde, and butylaldehyde are more preferred, since they can provide an adhesive composition that is particularly excellent in impact resistance and adhesion to metals.
  • the amount of the aldehyde to be added can be appropriately set according to the amount of acetal groups in the target polyvinyl acetal resin. In particular, it is preferable to add 55 mol% or more and 95 mol% or less, more preferably 60 mol% or more and 90 mol% or less, based on 100 mol% of polyvinyl alcohol, because this allows the acetalization reaction to proceed efficiently and makes it easy to remove unreacted aldehyde. That is, the amount of the aldehyde to be added is preferably 55 to 95 mol%, more preferably 60 to 90 mol%.
  • the temperature at which the aldehyde is added is preferably 0° C. or higher, more preferably 10° C.
  • the aldehyde introduction temperature is preferably 0 to 55° C., more preferably 10 to 50° C., even more preferably 15 to 45° C., and particularly preferably 18 to 40° C.
  • the proportion of the peak integral value of a triad unit consisting of three consecutive chains of structural units having a hydroxyl group in the polyvinyl acetal resin, the viscosity, and the HPLC half-width can be set within a predetermined range.
  • the acetalization reaction it is preferable to carry out a hydrolysis step with hydrochloric acid or a saponification step with sodium hydroxide before the acetalization reaction, and it is particularly preferable to carry out a hydrolysis step with hydrochloric acid.
  • the ratio of peak integral values, viscosity, and HPLC half-width of the triad unit consisting of three chains of structural units having hydroxyl groups in the polyvinyl acetal resin can be set within a predetermined range.
  • the hydrolysis step with hydrochloric acid is a step in which polyvinyl alcohol is dissolved by heating in water, hydrochloric acid is added, and the mixture is heated and stirred for a certain period of time to hydrolyze the acetyl groups contained in the polyvinyl alcohol to hydroxyl groups.
  • the hydrolysis temperature, hydrolysis time, and amount of hydrochloric acid may be appropriately adjusted depending on the saponification degree of the raw material polyvinyl alcohol and the target saponification degree after hydrolysis.
  • the hydrolysis temperature is preferably 50° C. or higher and 90° C. or lower. More preferably, it is 53° C. or higher and 85° C. or lower, even more preferably, it is 55° C. or higher and 80° C.
  • the hydrolysis temperature is preferably 50 to 90° C., more preferably, it is 53 to 85° C., even more preferably, it is 55 to 80° C., and particularly preferably, it is 60 to 75° C.
  • the hydrolysis time is preferably 30 minutes or more and 10 hours or less, more preferably 45 minutes or more and 8 hours or less, even more preferably 1 hour or more and 7 hours or less, and particularly preferably 2 hours or more and 6 hours or less. That is, the hydrolysis time is preferably 30 minutes to 10 hours, more preferably 45 minutes to 8 hours, even more preferably 1 hour to 7 hours, and particularly preferably 2 hours to 6 hours.
  • the amount of hydrochloric acid is preferably 10 parts by weight or more and 250 parts by weight or less relative to 100 parts by weight of polyvinyl alcohol, more preferably 15 parts by weight or more and 200 parts by weight or less, and even more preferably 30 parts by weight or more and 120 parts by weight or less. That is, the amount of hydrochloric acid is preferably 10 to 250 parts by weight, more preferably 15 to 200 parts by weight, and even more preferably 30 to 120 parts by weight, relative to 100 parts by weight of polyvinyl alcohol.
  • the retention time (reaction temperature) in the acetalization reaction is preferably 0.1 hours or more and 7 hours or less, and more preferably 0.5 hours or more and 5 hours or less. That is, the retention time is preferably 0.1 to 7 hours, and more preferably 0.5 to 5 hours.
  • the holding temperature in the acetalization reaction is preferably ⁇ 5° C. or higher and 50° C. or lower, and more preferably 5° C. or higher and 40° C. or lower. That is, the holding temperature is preferably ⁇ 5 to 50° C., and more preferably 5 to 40° C.
  • the proportion of peak integral values of triad units each consisting of three consecutive chains of structural units having a hydroxyl group in the polyvinyl acetal resin, the viscosity, and the HPLC half width can be set within a predetermined range.
  • the temperature difference between the hydrolysis temperature and the holding temperature is preferably 5°C or higher and 50°C or lower, and more preferably 10°C or higher and 40°C or lower.
  • the acetalization reaction may be carried out by adding an aldehyde at a predetermined temperature, raising the temperature at a predetermined rate, and then maintaining the temperature for a certain period of time.
  • the temperature rise time in the acetalization reaction is preferably 30 minutes or more and 500 minutes or less, more preferably 60 minutes or more and 400 minutes or less, and even more preferably 120 minutes or more and 300 minutes or less. That is, the temperature rise time is preferably 30 to 500 minutes, more preferably 60 to 400 minutes, and even more preferably 120 to 300 minutes.
  • the temperature rise rate is preferably 0.1° C./min or more and 2° C./min or less. In other words, the temperature rise rate is preferably 0.1 to 2° C./min.
  • the proportion of peak integral values of triad units each consisting of three consecutive chains of structural units having a hydroxyl group in the polyvinyl acetal resin, the viscosity, and the HPLC half-width can be set within predetermined ranges.
  • a slurry composition for ceramic green sheets can be prepared by mixing the polyvinyl acetal resin of the present invention with an organic solvent and ceramic powder.
  • the organic solvent is not particularly limited, and may be any solvent capable of dissolving the polyvinyl acetal resin, such as ketones, including acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone.
  • ketones including 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.
  • 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.
  • methyl cellosolve examples include methyl cellosolve, ethyl cellosolve, butyl cellosolve, terpineol, dihydroterpineol, butyl cellosolve acetate, butyl carbitol acetate, terpineol acetate, and dihydroterpineol acetate.
  • alcohols, ketones, aromatic hydrocarbons, and mixed solvents thereof are preferred in terms of coating and drying properties.
  • a mixed solvent of ethanol and toluene and a mixed solvent of methyl ethyl ketone and toluene are more preferred.
  • the content of the organic solvent in the ceramic green sheet slurry composition is set according to the type of polyvinyl acetal resin used, and is not particularly limited, but if it is too small, it is difficult to exhibit the solubility required for kneading. Also, if it is too much, the viscosity of the ceramic green sheet slurry composition may become too low, resulting in poor handling when producing ceramic green sheets.
  • the organic solvent content is preferably 20% by weight or more and 80% by weight or less. In other words, the organic solvent content is preferably 20 to 80% by weight.
  • the ceramic powder includes metal or nonmetal oxide or non-oxide powders used in the manufacture of ceramics.
  • the composition of these powders may be a single composition, a compound, or a mixture.
  • the constituent elements of the metal oxide or non-oxide may be a single element or a plurality of elements, both as cations and anions, and may further include additives added to improve the properties of the oxide or non-oxide. Specifically, oxides, carbides, nitrides, borides, sulfides, etc.
  • Those having a spinel structure include MgAl2O4 , ZnAl2O4 , CoAl2O4 , NiAl2O4 , MgFe2O4 , etc.
  • Those having an ilmenite structure include MgTiO3 , MnTiO3 , FeTiO3 , etc.
  • Those having a garnet structure include GdGa5O12 , Y6Fe5O12 , etc.
  • the modified polyvinyl acetal resin of the present invention exhibits excellent properties when mixed with BaTiO3 powder in a ceramic green sheet.
  • the slurry composition for ceramic green sheets may contain a plasticizer.
  • a plasticizer By adding a plasticizer, the mechanical strength and flexibility of the resulting ceramic green sheet can be significantly improved.
  • the plasticizer include phthalic acid 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.
  • phthalic acid diesters such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP)
  • the average particle size of the ceramic powder is not particularly limited, but for example, for producing thin-layer ceramic green sheets (thickness 5 ⁇ m or less), it is preferable that it is 0.5 ⁇ m or less.
  • the content of the above plasticizer is preferably 7 parts by weight, more preferably 8.5 parts by weight, and preferably 40 parts by weight, more preferably 30 parts by weight, relative to 100 parts by weight of polyvinyl acetal resin.
  • the content of the above plasticizer is preferably 7 to 40 parts by weight, and more preferably 8.5 to 30 parts by weight.
  • the above-mentioned slurry composition for ceramic green sheets may contain other resins such as polyvinyl acetal resins other than the polyvinyl acetal resin of the present invention, acrylic resins, ethyl cellulose, etc., within a range that does not impair the effects of the present invention. In such cases, it is preferable that the content of the polyvinyl acetal resin of the present invention relative to the total binder resin is 50% by weight or more.
  • the above-mentioned ceramic green sheet slurry composition may contain, as necessary, dispersants, antioxidants, UV absorbers, surfactants, fillers, release agents, etc., and in some cases, small amounts of other resins such as acrylic resins and urethane resins may be added.
  • the method for producing the above-mentioned slurry composition for ceramic green sheets 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 added as necessary are mixed using various mixers such as a ball mill, a blender mill, and a three-roll mill.
  • the composition is heated and dried to obtain ceramic green sheets.
  • the ceramic green sheets can be used to manufacture ceramic electronic components.
  • the ceramic electronic components can be manufactured by carrying out a step of applying an electrode layer paste to the surface of the ceramic green sheets, and a step of stacking the ceramic green sheets on which the electrode layers have been formed, and heat-pressing the stack to obtain a laminate, followed by degreasing and firing the laminate.
  • the method for applying the above-mentioned slurry composition for ceramic green sheets is not particularly limited, and examples thereof include methods using a roll coater, a die coater, a curtain coater, etc. Note that other specific methods may be used that are conventionally known.
  • the ceramic electronic components are not particularly limited, and examples thereof include multilayer ceramic capacitors, multilayer ceramic inductors, capacitors, piezoelectric actuators, multilayer varistors, multilayer thermistors, EMI filters, aluminum nitride multilayer substrates, and alumina multilayer substrates. Such multilayer ceramic capacitors are also part of the present invention.
  • the method for producing a ceramic electronic component includes a step of applying a paste for electrode layers to the surfaces of the ceramic green sheets.
  • the electrode layer paste can be obtained by dissolving, for example, polyvinyl acetal resin, ethyl cellulose, acrylic resin, etc. as a binder resin in an organic solvent and dispersing conductive powder, etc. These resins may be used alone or in combination of two or more.
  • the electrode layer paste containing polyvinyl acetal resin is preferred because it exhibits excellent adhesion to the ceramic green sheet in the heat-pressure bonding process.
  • the above-mentioned ceramic green sheets having electrode layers formed thereon are produced, and then similarly produced ceramic green sheets having electrode layers formed thereon are stacked and heated and pressed to obtain a laminate, which is then degreased and fired, thereby obtaining a multilayer ceramic electronic component in which problems such as sheet attack and cracks are solved.
  • the above-mentioned heat-pressure bonding step, and the steps of degreasing and firing the laminate are not particularly limited, and conventionally known methods can be used.
  • the present invention provides a polyvinyl acetal resin that, when used as a binder for ceramic green sheets in particular, can produce ceramic green sheets with uniform tensile strength and high breaking stress.
  • Example 11 The polyvinyl acetal resin obtained in Example 11 was subjected to 13 C-NMR measurement, and the measurement data was obtained by measuring the proportion of the peak integral value of a triad unit consisting of three consecutive chains of structural units having a hydroxyl group.
  • FIG. 1 shows measurement data obtained by carrying out HPLC measurement on the polyvinyl acetal resin obtained in Example 5.
  • Example 1 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours. The solution was cooled to 40°C, and 160 g of n-butyl aldehyde was added. The mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed. The mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 2 3000 g of pure water was added to 200 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours.
  • the solution was cooled to 40°C, and 107 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 3 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,500, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours.
  • the solution was cooled to 40°C, and 160 g of n-butyl aldehyde was added thereto.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 4 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 5 hours.
  • the solution was cooled to 40°C, and 160 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 5 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 60°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 5 hours.
  • the solution was cooled to 40°C, and 160 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 6 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 80°C, and 200 g of hydrochloric acid with a concentration of 35% by weight was added and held for 1 hour. The solution was cooled to 40°C, and 160 g of n-butyl aldehyde was added. The mixture was held at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was then completed. The mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.
  • Example 7 150 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%, first PVA) and 150 g of polyvinyl alcohol resin (average polymerization degree 1,500, saponification degree 88.1 mol%, second PVA) were added with 3000 g of pure water and stirred at 90 ° C for about 2 hours to dissolve. The solution was cooled to 70 ° C, and 200 g of hydrochloric acid with a concentration of 35 wt % was added and held for 3 hours.
  • the solution was cooled to 40 ° C, and 160 g of n-butyl aldehyde was added, and the mixture was held at 40 ° C for 3 hours to carry out an acetalization reaction, after which the reaction was completed, and neutralization, washing with water and drying were carried out by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 8 150 g of polyvinyl alcohol resin (average polymerization degree 2,400, saponification degree 88.1 mol%, first PVA) and 150 g of polyvinyl alcohol resin (average polymerization degree 1,500, saponification degree 88.1 mol%, second PVA) were added with 3000 g of pure water and stirred at 90 ° C for about 2 hours to dissolve. The solution was cooled to 70 ° C, and 200 g of hydrochloric acid with a concentration of 35 wt % was added and held for 3 hours.
  • the solution was cooled to 40 ° C, and 160 g of n-butyl aldehyde was added, and the mixture was held at 40 ° C for 3 hours to carry out an acetalization reaction, after which the reaction was completed, and neutralization, washing with water and drying were carried out by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 9 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours.
  • the solution was cooled to 40°C, and 165 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 10 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 250 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours. The solution was cooled to 40°C, and 165 g of n-butyl aldehyde was added. The mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed. The mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 11 3000 g of pure water was added to 200 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 100 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 10 hours.
  • the solution was cooled to 40°C, and 110 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 5 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 12 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and held for 3 hours. The solution was cooled to 10°C, and 165 g of n-butyl aldehyde was added.
  • the temperature was then raised to 40°C in 60 minutes, and the mixture was held at 40°C for 3 hours to carry out an acetalization reaction, after which the reaction was completed, and the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 13 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and held for 3 hours. The solution was cooled to 10°C, and 165 g of n-butyl aldehyde was added.
  • the temperature was then raised to 40°C in 180 minutes, and the mixture was held at 40°C for 3 hours to carry out an acetalization reaction, after which the reaction was completed, and the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 14 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours. The solution was cooled to 20°C, and 165 g of n-butyl aldehyde was added. The mixture was maintained at 20°C for 7 hours to carry out an acetalization reaction, and the reaction was completed. The mixture was neutralized, washed with water, and dried in a conventional manner to obtain a white powder of polyvinyl acetal resin.
  • Example 15 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,000, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours.
  • the solution was cooled to 40°C, and 165 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 16 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 2,500, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours. The solution was cooled to 40°C, and 165 g of n-butyl aldehyde was added. The mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed. The mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • Example 17 3000 g of pure water was added to 300 g of polyvinyl alcohol resin (average polymerization degree 1,800, saponification degree 88.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve.
  • the solution was cooled to 70°C, and 215 g of hydrochloric acid with a concentration of 35% by weight was added and maintained for 3 hours.
  • the solution was cooled to 40°C, and 165 g of n-butyl aldehyde was added.
  • the mixture was maintained at 40°C for 3 hours to carry out an acetalization reaction, and the reaction was completed.
  • the mixture was neutralized, washed with water, and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • 13 C-NMR measurement was carried out at 80°C.
  • the polyvinyl acetal resin obtained in Example 11 was subjected to 13C -NMR measurement to measure the ratio of the peak integral value of the triad unit consisting of three consecutive chains of the structural units having a hydroxyl group.
  • the measurement data obtained are shown in FIG. 1.
  • (1-4) Viscosity Measurement The obtained polyvinyl acetal resin was dissolved in a mixed solution of ethanol and toluene at a weight ratio of 1:1 to give 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 B-type viscometer.
  • the B-type viscometer used was a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.), and the measurements were performed with the following rotation speeds and rotors: Examples 1 to 14, 17, Comparative Examples 1, 4 to 7: Rotational speed 30 rpm, SPINDLE No. M1 Example 16, Comparative Example 2: Rotational speed 30 rpm, SPINDLE No. M2 Example 15, Comparative Example 3: Rotational speed 60 rpm, SPINDLE No. M1
  • the inside of the column of the HPLC system was filled with a mixed solvent of mobile phase A/mobile phase B in a volume ratio of 9/1.
  • the sample was injected, and the ratio of mobile phase B in the mobile phase was increased at a constant rate (4.5 vol%/min) over 20 minutes from immediately after the sample injection. Only mobile phase B was allowed to flow for 10 minutes from 20 minutes after the injection.
  • the column temperature was 45°C, and the liquid delivery flow rate was 0.4 mL/min.
  • the polyvinyl acetal resin obtained in Example 5 was subjected to HPLC measurement, and the measurement data obtained (vertical axis: peak intensity, horizontal axis: retention time [RT]) are shown in FIG.
  • the peak half-width W0.5h is measured by reversed-phase partition gradient high-performance liquid chromatography under the above conditions, and represents the peak width at the 50% height position.
  • the actual data obtained was analyzed using Shimadzu Corporation's Labsolutions LC (ver. 5.7.1 SP1) under the following conditions. Width: 100 seconds Slope: 200 ⁇ m Drift: 0 ⁇ V/min T. DBL: 1000 min Minimum area/height: 10,000 counts The 50% height width of the peak calculated when analyzed under these conditions was calculated as W 0.5h .
  • Viscosity change rate is 400% or less
  • the breaking stress (MPa) of the obtained ceramic green sheets was measured at a tensile speed of 20 mm/min in an environment of 23° C. using a tensile tester (AUTOGRAPH AGS-J, manufactured by Shimadzu Corporation) in accordance with JIS K 7113. Thirty test pieces were prepared, and the measurement was performed 30 times to determine the average value of the breaking stress, which was evaluated according to the following criteria.
  • Breaking stress is more than 32 MPa
  • Standard deviation of stress at break is 0.40 or less
  • a polyvinyl acetal resin which, particularly when used as a binder for ceramic green sheets, can provide ceramic green sheets having uniform tensile strength and high breaking stress.

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