WO2024122521A1 - 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
WO2024122521A1
WO2024122521A1 PCT/JP2023/043382 JP2023043382W WO2024122521A1 WO 2024122521 A1 WO2024122521 A1 WO 2024122521A1 JP 2023043382 W JP2023043382 W JP 2023043382W WO 2024122521 A1 WO2024122521 A1 WO 2024122521A1
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Prior art keywords
polyvinyl acetal
acetal resin
mol
ceramic green
formula
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PCT/JP2023/043382
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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 KR1020247036519A priority Critical patent/KR20250119425A/ko
Priority to JP2024517177A priority patent/JPWO2024122521A1/ja
Priority to CN202380040610.1A priority patent/CN119213039A/zh
Publication of WO2024122521A1 publication Critical patent/WO2024122521A1/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 a reduction rate of a filtration flow rate is less than 10% when a polyvinyl acetal resin solution, which is prepared by dissolving the polyvinyl acetal resin in a 1:1 mixed solvent of methyl ethyl ketone and/or toluene and ethanol to prepare a 5 wt % solution, is filtered through a filter having an aperture of 5 ⁇ m under conditions of a filtration temperature of 25° C. and a filtration pressure of 10 mmHg.
  • Patent Document 2 proposes a polyvinyl acetal resin in which the wave number A (cm ⁇ 1 ) of a peak within the wave number range of 3100 to 3700 cm ⁇ 1 in an 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 it is 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 can provide ceramic green sheets with excellent sheet attack resistance and tensile strength, particularly when used as a binder for ceramic green sheets.
  • a polyvinyl acetal resin that can provide ceramic green sheets with excellent sheet attack resistance and tensile strength, particularly when used as a binder for ceramic green sheets.
  • the present disclosure (1) is a polyvinyl acetal resin having a ratio of the peak integral value of a 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), which is obtained by 13C-NMR (nuclear magnetic resonance) measurement, of 0.22 or more, and having a weight average molecular weight of 230,000 or more.
  • 13C-NMR nuclear magnetic resonance
  • 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 a polyvinyl acetal resin according to the present disclosure ( 1 ), in which the ratio of the peak integral value of the methine C atom shown in (a)' of the 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 above formulas (a), (b) and (c) is 0.23 or more, as obtained by 13C-NMR (nuclear magnetic resonance) measurement:
  • the present disclosure (3) is the polyvinyl acetal resin according to the present disclosure (1) or (2), in which a solution viscosity of a 5% by 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 (4) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (3), in which the amount of hydroxyl groups is 23 mol % or more and 40 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 amount of acetyl groups is 0.1 mol % or more and 5 mol % or less.
  • the present disclosure (6) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (5), in which the molecular weight distribution is 2.75 or less.
  • the present disclosure (7) is the polyvinyl acetal resin according to any one of the present disclosures (1) to (6), which is used for a ceramic green sheet.
  • the present disclosure (8) is a slurry composition for a ceramic green sheet, comprising the polyvinyl acetal resin according to any one of the present disclosures (1) to (7), an organic solvent, and ceramic powder.
  • the present disclosure (9) is a ceramic green sheet obtained by using the slurry composition for a ceramic green sheet according to the present disclosure (8).
  • the present disclosure (10) is a multilayer ceramic capacitor obtained by using the ceramic green sheet according to the present disclosure (9). The present invention will be described in detail below.
  • the ratio of the peak integral value of a triad unit consisting of three consecutive chains of structural units having a hydroxyl group measured by 13C -NMR is 0.22 or more. By setting it in the above range, sheet attack resistance can be improved.
  • the ratio of the peak integral value of a triad unit consisting of three consecutive chains of structural units having a hydroxyl group is preferably 0.23 or more.
  • the ratio of the peak integral value of the triad unit consisting of three consecutive chains of the structural units having the hydroxyl group is preferably 0.24 at the lower limit, more preferably 0.25 at the lower limit, and more preferably 0.32 at the upper limit.
  • the ratio of the peak integral value of the triad unit consisting of three consecutive chains of the structural units having the hydroxyl group is preferably 0.23 to 0.32, more preferably 0.24 to 0.32, and even more preferably 0.25 to 0.30. If it is equal to or more than the lower limit, the hydrogen bonding property by the hydroxyl group is improved, and the ceramic green sheet produced using the polyvinyl acetal resin of the present invention can be made to have low solubility in organic solvents, so that the sheet attack resistance is good, and if it is equal to or less than the upper limit, the solubility of the polyvinyl acetal resin in organic solvents is not too low, and the handling property such as solution preparation is good.
  • 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)
  • 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 triad unit consisting of three chains of structural units having a hydroxyl group can be adjusted, for example, by appropriately setting the degree of saponification of the raw material polyvinyl alcohol resin, the type of aldehyde, the conditions of the acetalization reaction, and the amount of acetal groups, hydroxyl groups, and acetyl groups of the polyvinyl acetal resin.
  • the maturation temperature (holding temperature) of the acetalization reaction is preferably 45° C. or higher, and more preferably 50° C. or higher.
  • the proportion of the peak integral value of the triad unit consisting of three consecutive chains of structural units having hydroxyl groups can be increased, making it easier to satisfy the proportion of the peak integral value of the triad unit consisting of three consecutive chains of structural units having hydroxyl groups specified in the present invention.
  • 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. From the viewpoint of improving the tensile strength, 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 viscosity can be adjusted by appropriately setting, for example, the degree of saponification or 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 maturation temperature (retention temperature) in the acetalization reaction is preferably 45° C. or higher, more preferably 50° C. or higher, and is preferably 75° C. or lower, more preferably 72° C. or lower.
  • the retention temperature is preferably 45 to 75° C., more preferably 50 to 72° C.
  • 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 %, even 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 %, even 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 a ceramic green sheet 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. That is, 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. When the weight average molecular weight is 230000 or more, the tensile strength can be improved.
  • the weight average molecular weight has a preferred lower limit of 270,000, more preferably 290,000, and a preferred upper limit of 700,000, more preferably 450,000. That is, the weight average molecular weight is preferably 270,000 to 700,000, and more preferably 290,000 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), preferably having a lower limit of 2.2, more preferably a lower limit of 2.3, and preferably having an upper limit of 2.75, more preferably an upper limit of 2.73, and even more preferably an upper limit of 2.7. That is, the Mw/Mn is preferably from 2.2 to 2.75, more preferably from 2.3 to 2.73, and even more preferably from 2.3 to 2.7.
  • 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 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 values of triad units each consisting of three chains of structural units having a hydroxyl group in the polyvinyl acetal resin and the viscosity can be set within a predetermined range.
  • the polyvinyl alcohol resin may be of a single type or of multiple types. By using multiple types of polyvinyl alcohol resins, it is easy to set the viscosity within a predetermined range, and a slurry composition for ceramic green sheets having excellent viscosity stability over time can be produced.
  • 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.
  • 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.
  • the aldehyde introduction temperature is preferably 0 to 38° C., and more preferably 10 to 35° C.
  • the retention time 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 45° C. or higher and 75° C. or lower, more preferably 50° C. or higher and 72° C. or lower, and even more preferably 59° C. or higher and 71° C.
  • the holding temperature is preferably 45 to 75° C., more preferably 50 to 72° C., and even more preferably 59 to 71° C.
  • the ratio of peak integral values of triad units consisting of three chains of structural units having hydroxyl groups in the polyvinyl acetal resin and the viscosity can be set within a predetermined range.
  • the total time of the temperature increase time and the holding time in the acetalization reaction is preferably 4 hours or more and 15 hours or less, and more preferably 4.5 hours or more and 12 hours or less. That is, the total time is preferably 4 to 15 hours, and more preferably 4.5 to 12 hours.
  • the average reaction temperature in the acetalization reaction is preferably 41°C or higher and 60°C or lower, and more preferably 45°C or higher and 55°C or lower. In other words, the average reaction temperature is preferably 41 to 60°C, and more preferably 45 to 55°C.
  • the average reaction temperature is calculated by dividing the total value of "temperature x time" calculated in each step of the acetalization reaction by the total time.
  • 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 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 slurry composition for ceramic green sheets is not particularly limited, and examples 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 can be used to obtain ceramic green sheets that have excellent sheet attack resistance and tensile strength, particularly when used as a binder for ceramic green sheets, and that is less susceptible to deterioration in electrical properties and increased defect rates, and can be used to produce highly reliable multilayer ceramic capacitors.
  • the polyvinyl acetal resin obtained in Example 6 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.
  • Example 1 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,750, saponification degree 99.1 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 115 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 2 193 g of polyvinyl alcohol resin (average polymerization degree 1,750, saponification degree 99.1 mol%, first PVA) and 17 g of polyvinyl alcohol resin (average polymerization degree 800, saponification degree 98.4 mol%, second PVA) were added with 3000 g of pure water and dissolved by stirring at 90 ° C. for about 2 hours. The solution was cooled to 20 ° C., and 200 g of hydrochloric acid having a concentration of 35 wt % and 120 g of n-butyl aldehyde were added thereto.
  • Example 3 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and dissolved by stirring at 90° C. for about 2 hours. The solution was cooled to 20° C., and 200 g of hydrochloric acid having a concentration of 35% by weight and 115 g of n-butylaldehyde were added thereto. After 60 minutes had elapsed since the addition of n-butylaldehyde, the temperature was increased at a rate of 0.30° C./min (temperature increase time 150 min), and the mixture was held at 65° C. for 2 hours to carry out an acetalization reaction. The reaction was then completed, and the mixture was neutralized, washed with water and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • polyvinyl alcohol resin average polymerization degree 1,700, saponification degree 99.0 mol%
  • Example 4 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 2,500, saponification degree 96.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 115 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 5 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,000, saponification degree 98.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 120 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 6 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 120 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 7 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 30°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 120 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 8 147 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%, first PVA) and 63 g of polyvinyl alcohol resin (average polymerization degree 800, saponification degree 98.4 mol%, second PVA) were added with 3000 g of pure water and dissolved by stirring at 90 ° C. for about 2 hours. The solution was cooled to 30 ° C., and 200 g of hydrochloric acid having a concentration of 35 wt % and 120 g of n-butyl aldehyde were added thereto.
  • Example 9 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 115 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 10 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 20°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 115 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 11 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and the mixture was stirred at 90°C for about 2 hours to dissolve. The solution was cooled to 10°C, and 200 g of hydrochloric acid with a concentration of 35% by weight and 120 g of n-butyl aldehyde were added thereto to precipitate a polyvinyl acetal resin.
  • Example 12 3000 g of pure water was added to 210 g of polyvinyl alcohol resin (average polymerization degree 1,700, saponification degree 99.0 mol%), and dissolved by stirring at 90° C. for about 2 hours. The solution was cooled to 20° C., and 200 g of hydrochloric acid having a concentration of 35% by weight and 115 g of n-butylaldehyde were added thereto. After 60 minutes had elapsed since the addition of n-butylaldehyde, the temperature was increased at a rate of 0.30° C./min (temperature increase time 150 min), and the mixture was held at 65° C. for 1.5 hours to carry out an acetalization reaction. The reaction was then completed, and the mixture was neutralized, washed with water and dried by a conventional method to obtain a white powder of polyvinyl acetal resin.
  • polyvinyl alcohol resin average polymerization degree 1,700, saponification degree 99.0 mol%
  • 13 C-NMR measurement was carried out at 80°C.
  • the polyvinyl acetal resin obtained in Example 6 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.
  • AA Dissolution rate is less than 2.0%.
  • A Dissolution rate is 2.0% or more and less than 2.5%.
  • B Dissolution rate is 2.5% or more and less than 3.0%.
  • C Dissolution rate is 3.0% or more.
  • 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.
  • the breaking stress obtained was evaluated according to the following criteria.
  • Breaking stress is more than 32 MPa
  • a polyvinyl acetal resin that can obtain a ceramic green sheet having excellent sheet attack resistance and tensile strength, particularly when used as a binder for a ceramic green sheet, and that is unlikely to cause a decrease in electrical characteristics or an increase in the defective rate, and can be used to fabricate a multilayer ceramic capacitor with excellent reliability.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015125690A1 (ja) * 2014-02-18 2015-08-27 株式会社クラレ 合わせガラス用中間膜
WO2015125689A1 (ja) * 2014-02-18 2015-08-27 株式会社クラレ ポリビニルアセタール溶液からなる接着性改良剤
JP2016104697A (ja) * 2014-01-15 2016-06-09 積水化学工業株式会社 合わせガラス用中間膜及び合わせガラス

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3276261B2 (ja) * 1995-03-27 2002-04-22 積水化学工業株式会社 グリーンシート成形用セラミック泥漿物及びグリーンシート
JP2005325342A (ja) 2004-04-12 2005-11-24 Sekisui Chem Co Ltd ポリビニルアセタール樹脂及びポリビニルアセタール樹脂の製造方法
JP4752691B2 (ja) * 2006-09-08 2011-08-17 パナソニック株式会社 セラミックグリーンシートとそれを用いた積層セラミック電子部品及びその製造方法
CN102575080B (zh) * 2009-08-07 2014-11-26 可乐丽股份有限公司 聚乙烯醇缩醛组合物、层叠体及其用途
CN103124766B (zh) * 2010-09-29 2015-09-16 积水化学工业株式会社 浆料组合物的制造方法
TWI557096B (zh) 2011-09-28 2016-11-11 可樂麗股份有限公司 漿料組成物、陶瓷坯片及積層陶瓷電容器
US11008414B2 (en) 2015-10-02 2021-05-18 Cis Pharma Ag Polymer materials for contact lens applications
JP6836001B1 (ja) 2019-09-27 2021-02-24 積水化学工業株式会社 ポリビニルアセタール樹脂

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016104697A (ja) * 2014-01-15 2016-06-09 積水化学工業株式会社 合わせガラス用中間膜及び合わせガラス
WO2015125690A1 (ja) * 2014-02-18 2015-08-27 株式会社クラレ 合わせガラス用中間膜
WO2015125689A1 (ja) * 2014-02-18 2015-08-27 株式会社クラレ ポリビニルアセタール溶液からなる接着性改良剤

Cited By (7)

* Cited by examiner, † Cited by third party
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JP7612929B1 (ja) 2024-05-22 2025-01-14 積水化学工業株式会社 ポリビニルアセタール樹脂
JP7735523B1 (ja) 2024-05-22 2025-09-08 積水化学工業株式会社 ポリビニルアセタール樹脂
WO2025244076A1 (ja) * 2024-05-22 2025-11-27 積水化学工業株式会社 ポリビニルアセタール樹脂
JP2025178083A (ja) * 2024-05-22 2025-12-05 積水化学工業株式会社 ポリビニルアセタール樹脂
JP2025178010A (ja) * 2024-05-22 2025-12-05 積水化学工業株式会社 ポリビニルアセタール樹脂
JP2025179098A (ja) * 2024-05-22 2025-12-09 積水化学工業株式会社 ポリビニルアセタール樹脂
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