WO2019189402A1 - Résine de poly(d'acétal) de vinyle modifiée, et résine de poly(d'acétal) de vinyle - Google Patents

Résine de poly(d'acétal) de vinyle modifiée, et résine de poly(d'acétal) de vinyle Download PDF

Info

Publication number
WO2019189402A1
WO2019189402A1 PCT/JP2019/013262 JP2019013262W WO2019189402A1 WO 2019189402 A1 WO2019189402 A1 WO 2019189402A1 JP 2019013262 W JP2019013262 W JP 2019013262W WO 2019189402 A1 WO2019189402 A1 WO 2019189402A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acetal resin
modified
alkyl
polyvinyl acetal
Prior art date
Application number
PCT/JP2019/013262
Other languages
English (en)
Japanese (ja)
Inventor
陽介 千葉
啓祐 竹中
貴之 前田
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2019519012A priority Critical patent/JP7406373B2/ja
Publication of WO2019189402A1 publication Critical patent/WO2019189402A1/fr

Links

Classifications

    • 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
    • C08F216/00—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
    • C08F216/38—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
    • 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
    • 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

Definitions

  • the present invention relates to a modified polyvinyl acetal resin, a polyvinyl acetal resin, and a modified polyvinyl acetal resin that exhibit a characteristic rheological property and have a high particle dispersibility while realizing an excellent thickening effect and coating property.
  • the present invention relates to a polyvinyl acetal resin composition using a polyvinyl acetal resin.
  • polyvinyl acetal resins have been used in various applications because they are excellent in toughness, film-forming properties, dispersibility of inorganic powders such as pigments and organic powders, and adhesion to coated surfaces.
  • binders such as ink and capacitors are known, and among them, they are often used as materials for multilayer electronic components such as multilayer ceramic capacitors.
  • Such a multilayer electronic component is generally manufactured through the following steps. First, after adding an organic binder resin such as a polyvinyl acetal resin and a poly (meth) acrylic ester resin to a solution in which an organic solvent is dissolved, a plasticizer, a dispersant, and the like are added, and then the ceramic raw material powder is added and mixed uniformly. A ceramic slurry composition having a constant viscosity after defoaming is obtained. This slurry composition is cast on a support surface such as a PET film or a SUS plate which has been subjected to a release treatment. After the volatile matter such as a solvent is distilled off by heating or the like, it is peeled off from the support to obtain a ceramic green sheet.
  • an organic binder resin such as a polyvinyl acetal resin and a poly (meth) acrylic ester resin
  • a plasticizer, a dispersant, and the like are added, and then the ceramic raw material powder is added and mixed uniformly.
  • An electrode layer paste containing a conductive material such as palladium, silver, or nickel is printed in a predetermined pattern on the obtained ceramic green sheet.
  • a plurality of the printed ceramic green sheets obtained are stacked and laminated, and a ceramic green chip is obtained through a press cutting process.
  • the process of forming an external electrode on the end face etc. of the ceramic fired product obtained by performing the process of thermally decomposing and removing the binder component contained in the obtained ceramic green chip, so-called degreasing process, etc.
  • Patent Document 1 describes a modified polyvinyl acetal resin excellent in compatibility with an acrylic resin.
  • Patent Document 2 discloses an inorganic fine particle dispersion containing at least one selected from the group consisting of ethyl cellulose, a (meth) acrylic resin, and a polyvinyl acetal resin, a specific organic compound, inorganic fine particles, and an organic solvent.
  • a paste is described, and it is described that a sintered layer excellent in surface smoothness can be formed.
  • the inorganic fine particle-dispersed paste is required to have viscosity and thixotropy suitable for screen printing. Further, in the inorganic fine particle dispersed paste, it is necessary to consider the dispersibility of the inorganic fine particles in addition to the viscosity characteristics. However, at present, a binder resin satisfying all of these has not been put into practical use.
  • the present invention relates to a modified polyvinyl acetal resin, a polyvinyl acetal resin, and a modified polyvinyl acetal resin that exhibit a characteristic rheological property and have a high particle dispersibility while realizing an excellent thickening effect and coating property.
  • An object of the present invention is to provide a polyvinyl acetal resin composition using a polyvinyl acetal resin.
  • the present invention is a modified polyvinyl acetal resin comprising a structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain.
  • the present invention is described in detail below.
  • the present inventors have found that a modified polyvinyl acetal resin containing a structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain exhibits a characteristic rheological property, and has an excellent thickening effect and coating property.
  • the present inventors have found that it has high particle dispersibility while realizing workability and the like, and has completed the present invention.
  • the side chain refers to a molecular chain branched from the main chain. Therefore, the case where an alkyl-modified group is incorporated in the main chain itself is not included in the present invention.
  • the modified polyvinyl acetal resin of the present invention includes a structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain.
  • a characteristic rheological property can be expressed and an excellent thickening effect can be obtained.
  • remarkable viscosity increase and thixotropy can be provided because carbon number is 4 or more.
  • the alkyl-modifying group may be composed of one kind of alkyl-modifying group or may be composed of two or more kinds of alkyl-modifying groups.
  • the structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain is preferably a structural unit represented by the following formula (1) (hereinafter, such a structural unit is a long-chain alkyl-modified binding unit. Also called).
  • a structural unit represented by the following formula (1) there is an advantage that a characteristic rheological property is expressed and an excellent thickening effect is obtained.
  • the shear rate is low, the viscosity can be high.
  • variety of the viscosity at the time of raising a shear rate can be made small (viscosity ratio is low).
  • R 1 represents an alkyl group having 4 to 25 carbon atoms
  • R 2 represents a single bond, O, COO, or CONH.
  • R 1 is an alkyl group having 4 to 25 carbon atoms.
  • the carbon number of R 1 is preferably 8-20.
  • R 1 may be a combination of two or more alkyl groups having different carbon numbers. Note that R 1 corresponds to an alkyl-modified group.
  • alkyl group having 4 to 25 carbon atoms examples include a butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, and nonyl group. And decyl group. *
  • the alkyl group having 4 to 25 carbon atoms may be linear or branched.
  • Examples of the linear alkyl group include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and an n-undecyl group.
  • Examples of the branched alkyl group include isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylhexyl group, 1-methylheptyl group, 1-methyloctyl group, 1 -Methylnonyl group, 1-methyldecyl group, 1-methylundecyl group, 1-methyldodecyl group and the like.
  • 1-methyltridecyl group, 1-methyltetradecyl group, 1-methylheptadecyl group, 1-methylhexadecyl group, 1-methylpentadecyl group, 1-methyloctadecyl group, 1-methyleicosyl group, etc. Is mentioned.
  • an alkyl group in which an alkyl group having 2 or more carbon atoms is substituted at the 1-position carbon atom for example, 1-ethyldecyl group, 1-propylnonyl group, 1-butyloctyl group, 1-pentylheptyl group, 1-octyldecyl group) and the like.
  • alkyl group in which an alkyl group having 2 or more carbon atoms is substituted with a carbon atom having 2 or more positions include, for example, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethyl Examples include an undecyl group, a 2-ethyloctadecyl group, a 2-propylundecyl group, a 2-butylundecyl group, and a 2-octylundecyl group. Further examples include a 3-ethylundecyl group, a 4-ethyloctadecyl group, a 4-butyloctadecyl group, a neodecyl group, and the like.
  • the alkyl-modified group (R 1 ) is preferably a branched alkyl group.
  • the alkyl-modifying group may be composed of two or more alkyl groups including a branched alkyl group, or may be composed only of a branched alkyl group.
  • the ratio of the branched-chain alkyl group is 40 to 100% with respect to the total modified group amount. It is preferable.
  • the alkyl-modified group is composed of a linear alkyl group and a branched alkyl group
  • the ratio between the two (linear alkyl group: branched alkyl group) is 50 : 50 to 20:80 is preferable.
  • the structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain preferably has a structure in which an alkyl-modified group having 4 or more carbon atoms is bonded via an acetal bond (hereinafter, such a structure).
  • the structural unit is also referred to as a long-chain alkyl-modified acetal unit).
  • a characteristic rheological characteristic is expressed and the outstanding thickening effect can be acquired.
  • the shear rate when the shear rate is low, the viscosity can be relatively low.
  • the shear rate is increased, the width of decrease in the viscosity can be increased (the viscosity ratio is high).
  • the structural unit having an alkyl-modified group having 4 or more carbon atoms in the side chain is preferably a structural unit represented by the following formula (2).
  • R 3 represents an alkyl group having 4 to 25 carbon atoms.
  • the alkyl group having 4 to 25 carbon atoms the same ones as described above can be used.
  • the number of carbon atoms is preferably 6-20, and in particular, n-hexyl group, n-nonyl group, n-undecyl group, n-pentadecyl group, 1-methyloctyl group, 1-methyldecyl group, 2 -Ethylhexyl group, 2-ethylheptyl group, 1-butyloctyl group, neodecyl group and the like are preferable.
  • the preferable lower limit of the content of the structural unit having an alkyl-modified group in the side chain is 0.1 mol%, and the preferable upper limit is 5 mol%.
  • the alkyl-modified unit amount is 0.1 mol% or more, an excellent thickening effect, coating property, and particle dispersibility can be obtained.
  • the amount of the alkyl-modified unit is 5 mol% or less, the properties can be stabilized when an aqueous solution is prepared.
  • the minimum with said more preferable content is 0.5 mol%, and a more preferable upper limit is 3 mol%.
  • the modified polyvinyl acetal resin of the present invention includes a structure (long-chain alkyl-modified acetal unit) in which an alkyl-modified group having 4 or more carbon atoms is bonded via an acetal bond
  • the content of the long-chain alkyl-modified acetal unit is A more preferred lower limit is 0.5 mol%, and a more preferred upper limit is 4.5 mol%.
  • a more preferred upper limit is 4 mol%, and a more preferred upper limit is 3.5 mol%.
  • the content is preferably 0.5 to 5 mol%, and 0 when the long-chain alkyl-modified acetal unit having 7 to 10 carbon atoms is included. 0.1 to 4.5 mol% is preferable, and when the long chain alkyl-modified acetal unit having 11 to 18 carbon atoms is included, the content is preferably 0.1 to 4 mol%. Further, when the long-chain alkyl-modified acetal unit having 19 to 25 carbon atoms is included, the content is preferably 0.1 to 3.5 mol%.
  • the modified polyvinyl acetal resin of the present invention contains a long-chain alkyl-modified acetal unit
  • the square of the carbon number (X) of the alkyl group in the long-chain alkyl-modified acetal unit and the content of the long-chain alkyl-modified acetal unit is preferably 15 to 650. Further, it is more preferably 50 to 500, and further preferably 100 to 400. Further, when the modified polyvinyl acetal resin of the present invention does not contain a long-chain alkyl-modified bond unit but contains a long-chain alkyl-modified acetal unit, the above X 2 ⁇ Y is preferably 50 to 650.
  • the modified polyvinyl acetal resin of the present invention contains both a long-chain alkyl-modified bond unit and a long-chain alkyl-modified acetal unit
  • the above X 2 ⁇ Y is preferably 15 to 600. Further, it is more preferably 50 to 450, and further preferably 100 to 400.
  • the modified polyvinyl acetal resin of the present invention has a structural unit having a hydroxyl group, a structural unit having an acetyl group, and a structural unit having an acetal group.
  • the modified polyvinyl acetal resin of this invention has the structural unit which has the said hydroxyl group.
  • the preferred lower limit of the content of hydroxyl group-containing structural units (hydroxyl group amount) is 40 mol%, and the preferred upper limit is 99 mol%.
  • the modified polyvinyl acetal resin of this invention has the structural unit which has the said acetyl group.
  • the minimum with preferable content (acetyl group amount) of the structural unit which has the said acetyl group in the modified polyvinyl acetal resin of this invention is 0.1 mol%, and a preferable upper limit is 20 mol%.
  • Storage stability can be maintained by setting the amount of acetyl groups to 0.1 mol% or more, and storage stability can be maintained by setting the amount of acetyl groups to 20 mol% or less.
  • the more preferable lower limit of the acetyl group amount is 0.3 mol%, and the more preferable upper limit is 10 mol%.
  • the polyvinyl acetal resin has a structural unit having the acetal group.
  • the content (acetalization degree) of the structural unit having the acetal group in the polyvinyl acetal resin is preferably 0.1 mol% or more and 40 mol% or less. Storage stability and a softness
  • flexibility can be improved because the said acetalization degree shall be 0.1 mol% or more.
  • water solubility can be maintained. More preferably, it is 2 to 20 mol%.
  • the degree of acetalization is the number of hydroxyl groups acetalized with an aldehyde (butyraldehyde, acetaldehyde, etc.) having 3 or less carbon atoms in the portion excluding the aldehyde group out of the number of hydroxyl groups of polyvinyl alcohol. It is a ratio. Therefore, the content of the above-mentioned “structure in which an alkyl-modified group having 4 or more carbon atoms is bonded via an acetal bond” is not included in the degree of acetalization.
  • the degree of acetalization since the acetal group of the polyvinyl acetal resin is formed by acetalizing from two hydroxyl groups, a method of counting the two acetalized hydroxyl groups is employed to obtain the acetal. The mol% of the degree of conversion is calculated.
  • the content of acetoacetal groups acetalized with acetaldehyde in the modified polyvinyl acetal resin of the present invention is preferably 0.1 mol% or more and less than 40 mol%. By being within the above range, water solubility can be maintained and excellent viscosity characteristics can be obtained. Moreover, it is preferable that content of the butyl acetal group acetalized with the butyraldehyde in the modified polyvinyl acetal resin of this invention is 0.1 mol% or more and less than 25 mol%. By being within the above range, water solubility can be maintained and excellent viscosity characteristics can be obtained.
  • the modified polyvinyl acetal resin of the present invention includes both a structural unit having an acetal group (3 or less carbon atoms) and a long-chain alkyl-modified acetal unit
  • the ratio [amount of structural unit having an acetal group / amount of long-chain alkyl-modified acetal unit] is preferably 200 or less.
  • the ratio is more preferably 70 or less, and further preferably 25 or less.
  • 0.01 is preferable.
  • the total amount of the acetalization degree and the alkyl modification unit amount [degree of acetalization + alkyl modification unit amount] is preferably 0.2 to 50. By setting it within the above range, it is possible to maintain water solubility and obtain excellent viscosity characteristics.
  • the degree of acetalization + alkyl modified unit amount is more preferably 1.5 to 25.
  • the ratio of the degree of acetalization to the amount of the alkyl-modified unit in the modified polyvinyl acetal resin of the present invention is preferably 1 to 100. By setting it within the above range, it is possible to maintain water solubility and obtain excellent viscosity characteristics.
  • the acetalization degree / alkyl modified unit amount is more preferably 2.5-20.
  • the preferable lower limit of the degree of polymerization of the modified polyvinyl acetal resin of the present invention is 500, and the preferable upper limit is 4500. Industrial production becomes easy because the said polymerization degree is 500 or more. When the polymerization degree is 4500 or less, the solution viscosity becomes moderate, and it can be industrially produced.
  • the more preferable lower limit of the degree of polymerization is 1000, and the more preferable upper limit is 2500.
  • the modified polyvinyl acetal resin of the present invention may contain both a long-chain alkyl-modified bond unit and a long-chain alkyl-modified acetal unit.
  • the content ratio of the long-chain alkyl-modified bond unit to the long-chain alkyl-modified acetal unit is preferably 0.1 to 10.
  • a polyvinyl alcohol containing a structural unit having an alkyl-modified group in the side chain is prepared, and then acetalized, and a structural unit having an alkyl-modified group in the side chain is included.
  • a method of adding an alkyl-modified group after acetalizing a non-polyvinyl alcohol More specifically, a method of preparing polyvinyl alcohol having the structural unit represented by the above formula (1) in advance and then acetalizing the polyvinyl alcohol having no structural unit represented by the above formula (1) is acetal. For example, a method of adding a portion corresponding to R 1 or R 2 of the structural unit represented by the above formula (1) may be used.
  • polyvinyl alcohol containing a structural unit having an alkyl-modified group in the side chain for example, after copolymerizing vinyl alkyl ether such as vinyl dodecyl ether and vinyl acetate, alcohol of the obtained copolymer
  • examples thereof include a method of adding an acid or alkali to the solution to saponify.
  • the method for adding the alkyl-modifying group include graft polymerization.
  • Examples of a method for producing polyvinyl alcohol containing a structural unit having an alkyl-modified group in the side chain by the method of adding the alkyl-modified group include the following methods. For example, the method etc. which obtain polyvinyl alcohol (graft copolymer) containing the structural unit which has an alkyl modification group by adding polyvinyl alcohol and acrylic acrylates, such as dodecyl acrylate, to ethyl acetate, and carrying out graft polymerization are mentioned.
  • Examples of the method for producing a modified polyvinyl acetal resin containing a long-chain alkyl-modified acetal unit having 4 or more carbon atoms include a method of acetalizing unmodified polyvinyl alcohol with an aldehyde having 5 or more carbon atoms.
  • Polyvinyl alcohol not containing a structural unit having an alkyl-modified group in the side chain can be obtained, for example, by saponifying a copolymer of vinyl ester and ethylene.
  • the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and the like. Of these, vinyl acetate is preferred from the viewpoint of economy.
  • the modified polyvinyl acetal resin of the present invention may be one obtained by copolymerizing an ethylenically unsaturated monomer as long as the effects of the present invention are not impaired. It does not specifically limit as said ethylenically unsaturated monomer, For example, acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid etc. are mentioned. Further, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropane sulfonic acid and its sodium salt can be mentioned.
  • Further examples include ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, and sodium allyl sulfonate.
  • terminal-modified polyvinyl alcohol obtained by copolymerizing vinyl ester monomer such as vinyl acetate with ethylene in the presence of thiol compounds such as thiol acetic acid and mercaptopropionic acid, and saponifying it. Can do.
  • the polyvinyl acetal resin of the present invention which is another embodiment, has a ratio of the maximum value and the minimum value of the viscosity in a shear rate region of 25 ° C. and 1 to 100 [1 / s] in an aqueous solution with a solid content concentration of 5% by weight. .5 to 150. By setting it as such a range, sufficient rheology and a viscosity improvement effect can be acquired.
  • a preferred lower limit is 3, a preferred upper limit is 100, a more preferred lower limit is 10, and a more preferred upper limit is 120.
  • the polyvinyl acetal resin preferably has a maximum value in a shear rate range of 25 ° C. and 1 to 100 [1 / s].
  • the composition similar to the modified polyvinyl acetal resin of this invention can be used as a composition of the polyvinyl acetal resin of another aspect.
  • the polyvinyl acetal resin composition containing the modified polyvinyl acetal resin of the present invention or the polyvinyl acetal resin of another embodiment is also one aspect of the present invention.
  • the content of the modified polyvinyl acetal resin of the present invention in the polyvinyl acetal resin composition of the present invention or the polyvinyl acetal resin of another embodiment is not particularly limited, but the preferred lower limit is 0.5% by weight, and the preferred upper limit is 20%. %.
  • the content of the polyvinyl acetal resin is 0.5% by weight or more, the thickening effect due to the interaction between the resins becomes sufficient, and when it is 20% by weight or less, a resin having good handling properties is obtained. be able to. More preferably, it is 1 to 15% by weight.
  • the polyvinyl acetal resin composition of the present invention contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve the polyvinyl acetal resin, and examples thereof include isopropyl alcohol, methanol, ethanol and the like in addition to water.
  • the said solvent may be used independently and may use 2 or more types together.
  • the content of the solvent in the polyvinyl acetal resin composition of the present invention is not particularly limited, but a preferred lower limit is 1% by weight and a preferred upper limit is 99.5% by weight.
  • the polyvinyl acetal resin composition of the present invention if necessary, such as a flame retardant aid, a thickener, an antifoaming agent, a leveling agent, and an adhesion imparting agent. Additives may be added.
  • the use of the polyvinyl acetal resin composition of the present invention is not particularly limited, for example, a ceramic slurry containing water as a medium containing additives such as ceramic powders and inorganic additives such as ceramic powder, A ceramic green sheet having excellent mechanical strength and flexibility can be obtained by coating on a peelable support and drying. It can also be used as a raw material for binders, adhesives, paints, films, etc. of ink products such as gel inks.
  • water can be used as a solvent instead of an organic solvent, which is preferable from the viewpoint of environmental pollution, toxicity, risk of explosion accidents, and the like.
  • a modified polyvinyl acetal resin, a polyvinyl acetal resin having a high particle dispersibility while expressing a characteristic rheological property and realizing an excellent thickening effect, coating, coating properties and the like, and A polyvinyl acetal resin composition using the modified polyvinyl acetal resin or polyvinyl acetal resin can be provided.
  • the modified polyvinyl acetal resin of the present invention has an appropriate viscosity range even when an external force such as shear is applied, when a long time elapses, when the temperature changes, or when the solution properties such as pH are changed. Can be maintained.
  • it since it has excellent thread breakage, it can be suitably used for coating liquids and the like.
  • the solid content concentration in the system was 53% by weight, and the polymerization yield based on all monomers was 65% by weight.
  • a 45 wt% methanol solution of the copolymer was obtained.
  • the obtained copolymer was confirmed to contain 98.6 mol% of vinyl acetate units, 0.4 mol% of vinyldodecyl ether units, and 1.0 mol% of 1-ethyldecyl vinyl ether units from the determination of unreacted monomers. It was done.
  • polyvinyl alcohol (a) had a saponification degree of 99.5 mol%, an alkyl-modified unit amount of 1.4 mol%, and a polymerization degree of 1500.
  • Example 1 80 g of polyvinyl alcohol (a) was added to 1400 g of pure water, and the mixture was stirred and dissolved at a temperature of 90 ° C. for about 2 hours. The solution was cooled to 40 ° C., 20 g of hydrochloric acid having a concentration of 35% by weight and 5 g of n-butyraldehyde were added thereto, and the liquid temperature was kept at 40 ° C. to carry out an acetalization reaction. Thereafter, the liquid temperature was maintained at 40 ° C.
  • the hydroxyl group amount was 92.7 mol%
  • the acetyl group amount was 0.8 mol%
  • the total acetalization degree (butyralization degree) was 5.1 mol%
  • the alkyl modification unit amount (modification group content) was 1. It was 4 mol%.
  • R 1 was composed of linear alkyl (n-dodecyl group) and branched alkyl (1-ethyldecyl group), and the ratio of linear alkyl to branched alkyl was 3: 7. .
  • Example 2 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 3 g of acetaldehyde was added instead of n-butyraldehyde.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit (modified group content) was measured. The results are shown in Table 1.
  • Example 3 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 6.1 g of acetaldehyde was added instead of n-butyraldehyde. The obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 4 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 3 g of n-butyraldehyde was added. The obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 5 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 10 g of acetaldehyde was added instead of n-butyraldehyde.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 6 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 12 g of acetaldehyde was added instead of n-butyraldehyde. The obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 7 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 1 except that 22 g of acetaldehyde was added instead of n-butyraldehyde. The obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 8 instead of polyvinyl alcohol (a), alkyl-modified polyvinyl was obtained in the same manner as in Example 3, except that PVA having a saponification degree of 87.4 mol%, an alkyl-modified unit amount of 1.4 mol%, and a polymerization degree of 1500 was used. An acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 9 In place of polyvinyl alcohol (a), alkyl modification was performed in the same manner as in Example 3 except that PVA having a saponification degree of 99.5 mol%, an alkyl modification unit amount of 1.4 mol%, and a polymerization degree of 500 was used. A polyvinyl acetal resin solution (resin content: 5% by weight) was obtained. The obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 10 Instead of polyvinyl alcohol (a), alkyl-modified polyvinyl was obtained in the same manner as in Example 3, except that PVA having a saponification degree of 99.5 mol%, an alkyl-modified unit amount of 1.4 mol%, and a polymerization degree of 3000 was used. An acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 11 instead of polyvinyl alcohol (a), alkyl-modified polyvinyl was obtained in the same manner as in Example 3 except that PVA having a saponification degree of 99.5 mol%, an alkyl-modified unit amount of 0.1 mol%, and a polymerization degree of 1500 was used. An acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • Example 12 instead of polyvinyl alcohol (a), alkyl-modified polyvinyl was obtained in the same manner as in Example 3 except that PVA having a saponification degree of 99.5 mol%, an alkyl-modified unit amount of 4.8 mol%, and a polymerization degree of 1500 was used. An acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured.
  • R 1 was composed of linear alkyl (n-octyl group) and branched alkyl (1-ethyldecyl group), and the ratio of linear alkyl to branched alkyl was 25:75. .
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured.
  • R 1 was composed of linear alkyl (n-dodecyl group) and branched alkyl (t-butyl group), and the ratio of linear alkyl to branched alkyl was 29:71. .
  • DMSO-d 6 dimethyl sulfoxide
  • R 1 is composed of linear alkyl (n-dodecyl group) and branched alkyl (1-octyldecyl group), and the ratio of linear alkyl to branched alkyl is 28:72. It was.
  • DMSO-d 6 dimethyl sulfoxide
  • R 1 is composed of linear alkyl (C 24 H 49 group) and branched alkyl (1-ethyldecyl group), and the ratio of linear alkyl to branched alkyl is 30:70. It was.
  • An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured.
  • R 1 is composed of linear alkyl (C 24 H 49 group) and branched alkyl (1-ethyldecyl group), and the ratio of linear alkyl to branched alkyl is 30:70. It was.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of alkyl-modified unit was measured.
  • the results are shown in Table 1.
  • R 1 was composed of linear alkyl (n-octyl group) and branched alkyl (1-ethylhexyl group), and the ratio of linear alkyl to branched alkyl was 30:70. .
  • Example 24 Instead of 5 g of n-butyraldehyde, 2 g of n-butyraldehyde and 1.5 g of decylaldehyde were added, and acetalization was carried out by maintaining the liquid temperature at 60 ° C. for 6 hours to carry out acetalization. By the method, an alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of decylation, and the alkyl content.
  • the modified unit amount total alkyl-modified group content was measured. The results are shown in Table 1.
  • Example 25 An alkyl-modified polyvinyl acetal resin solution (resin) was prepared in the same manner as in Example 24, except that 2.2 g of n-butyraldehyde and 0.7 g of decylaldehyde were added instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde. Content: 5% by weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of decylation, and the alkyl content.
  • the modified unit amount total alkyl-modified group content was measured. The results are shown in Table 1.
  • Example 26 An alkyl-modified polyvinyl acetal resin solution (resin) was prepared in the same manner as in Example 24, except that 2.2 g of n-butyraldehyde and 0.5 g of heptylaldehyde were added instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde. Content: 5% by weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of heptialization, and the alkyl content.
  • the modified unit amount total alkyl-modified group content was measured. The results are shown in Table 1.
  • Example 27 An alkyl-modified polyvinyl acetal resin solution (resin content: 5) was prepared in the same manner as in Example 24 except that 2 g of n-butyraldehyde and 1 g of heptylaldehyde were added instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde. % By weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of heptialization, and the alkyl content.
  • the modified unit amount total alkyl-modified group content was measured. The results are shown in Table 1.
  • Example 28 Instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde, an alkyl-modified polyvinyl acetal resin solution (resin content) was obtained in the same manner as in Example 24 except that 1.6 g of n-butyraldehyde and 2 g of decylaldehyde were added. : 5% by weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of decylation, and the alkyl content.
  • the modified unit amount total alkyl-modified group content was measured. The results are shown in Table 1.
  • Example 29 An alkyl-modified polyvinyl acetal resin solution (resin content: 5% by weight) was prepared in the same manner as in Example 24 except that 1.3 g of decylaldehyde was added instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde. Obtained.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and 1 H-NMR (nuclear magnetic resonance spectrum) was used to determine the amount of hydroxyl group, the amount of acetyl group, the degree of butyralization, the degree of decylation, and the alkyl content.
  • the modified unit amount (total alkyl-modified group content) was measured. The results are shown in Table 1.
  • Example 30 Instead of polyvinyl alcohol (a), unmodified PVA (saponification degree 99.1 mol%, polymerization degree 1500) was used, and instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde, 3 g of decylaldehyde was added. Except for the above, a polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 24.
  • the resulting polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethylsulfoxide), 1 H-NMR hydroxyl group content by using the (nuclear magnetic resonance spectrum), acetyl group amount, Deshiraru degree, and, alkyl-modified unit amount ( Total alkyl-modified group content) was measured. The results are shown in Table 1.
  • Example 31 Instead of polyvinyl alcohol (a), unmodified PVA (saponification degree 99.1 mol%, polymerization degree 1500) was used, and instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde, 6 g of decylaldehyde was added. Except for the above, a polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 24.
  • the resulting polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethylsulfoxide), 1 H-NMR hydroxyl group content by using the (nuclear magnetic resonance spectrum), acetyl group amount, Deshiraru degree, and, alkyl-modified unit amount ( Total alkyl-modified group content) was measured. The results are shown in Table 1.
  • Example 32 Instead of polyvinyl alcohol (a), unmodified PVA (saponification degree 99.1 mol%, polymerization degree 1500) was used, and instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde, 7 g of decylaldehyde was added. Except for the above, a polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 24.
  • the resulting polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethylsulfoxide), 1 H-NMR hydroxyl group content by using the (nuclear magnetic resonance spectrum), acetyl group amount, Deshiraru degree, and, alkyl-modified unit amount ( Total alkyl-modified group content) was measured. The results are shown in Table 1.
  • Example 33 Instead of polyvinyl alcohol (a), unmodified PVA (saponification degree 99.1 mol%, polymerization degree 1500) was used, and instead of 2 g of n-butyraldehyde and 1.5 g of decylaldehyde, 1. A polyvinyl acetal resin solution (resin content: 5% by weight) was obtained in the same manner as in Example 24 except that 2 g and 6 g of decylaldehyde were added.
  • the resulting polyvinyl acetal resin is dissolved in DMSO-d 6 (dimethylsulfoxide), 1 H-NMR hydroxyl group content by using the (nuclear magnetic resonance spectrum), acetyl group amount, Deshiraru degree, and, alkyl-modified unit amount ( Total alkyl-modified group content) was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The modified unit amount (modified group content) was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • Example 4 A polyvinyl acetal resin solution (resin content: 5) was obtained in the same manner as in Example 1 except that unmodified PVA (saponification degree 99.2 mol%, polymerization degree 1500) was used instead of polyvinyl alcohol (a). % By weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • Example 5 A polyvinyl acetal resin solution (resin content: 5) was obtained in the same manner as in Example 6 except that unmodified PVA (saponification degree 99.2 mol%, polymerization degree 1500) was used instead of polyvinyl alcohol (a). % By weight).
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • the obtained polyvinyl acetal resin was dissolved in DMSO-d 6 (dimethyl sulfoxide), and using 1 H-NMR (nuclear magnetic resonance spectrum), the amount of hydroxyl group, the amount of acetyl group, the degree of acetoacetalization, the degree of butyralization, and The amount of denaturing unit was measured. The results are shown in Table 1.
  • Viscosity ratio (temperature 25 ° C, ratio of maximum and minimum viscosity in the shear rate range of 1 to 100 [1 / s])
  • a rotary rheometer Thermo Fisher Scientific; HAAKE Rheo Stress 3000
  • the viscosity at the time of changing was measured, and the maximum / minimum value was determined.
  • Rotating disc Flat plate Rotating disc diameter: 35mm Gap: 0.5mm Speed of changing the shear rate: 0.83 [1 / s 2 ]
  • Viscosity stability over time The change in viscosity after storage of the polyvinyl acetal resin solutions obtained in Examples and Comparative Examples at a temperature of 20 ⁇ 5 ° C. and a humidity of 45 to 55% for 30 days is relative to the viscosity before storage. The case where it was less than 10% was marked as ⁇ and the case where it was 10% or more was marked as x.
  • a modified polyvinyl acetal resin, a polyvinyl acetal resin, and a modified polyvinyl acetal resin that exhibit characteristic rheological properties and have a high particle dispersibility while realizing an excellent thickening effect, coating property, and the like.
  • a polyvinyl acetal resin composition using an acetal resin or a polyvinyl acetal resin can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

Le but de la présente invention est de fournir : une résine de poly(acétal de vinyle) modifiée et une résine de poly(acétal de vinyle) ayant une dispersibilité de particules élevée tout en manifestant des propriétés rhéologiques caractéristiques et réalisant un effet épaississant exceptionnel, des propriétés de revêtement, etc.; et une composition de résine de poly(acétal de vinyle) dans laquelle la résine de poly(acétal de vinyle) modifiée et la résine de poly(acétal de vinyle) sont utilisées. La présente invention concerne une résine de poly (acétal de vinyle) modifiée qui comprend une unité structurale ayant un groupe modifié par alkyle en C4 ou plus dans une chaîne latérale.
PCT/JP2019/013262 2018-03-30 2019-03-27 Résine de poly(d'acétal) de vinyle modifiée, et résine de poly(d'acétal) de vinyle WO2019189402A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019519012A JP7406373B2 (ja) 2018-03-30 2019-03-27 セラミックグリーンシート用変性ポリビニルアセタール樹脂

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018069119 2018-03-30
JP2018-069119 2018-03-30
JP2018185637 2018-09-28
JP2018-185637 2018-09-28

Publications (1)

Publication Number Publication Date
WO2019189402A1 true WO2019189402A1 (fr) 2019-10-03

Family

ID=68061998

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/013262 WO2019189402A1 (fr) 2018-03-30 2019-03-27 Résine de poly(d'acétal) de vinyle modifiée, et résine de poly(d'acétal) de vinyle

Country Status (3)

Country Link
JP (1) JP7406373B2 (fr)
TW (1) TW201942152A (fr)
WO (1) WO2019189402A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05279414A (ja) * 1992-04-01 1993-10-26 Sekisui Chem Co Ltd 星型ポリビニルアセタールおよびその製造方法
JP2011225432A (ja) * 2010-03-29 2011-11-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
WO2012023517A1 (fr) * 2010-08-19 2012-02-23 株式会社クラレ Résine d'acétal de polyvinyle, composition de la suspension préparée à partir de celle-ci, feuille de céramique verte, et condensateur céramique multicouches
WO2012133351A1 (fr) * 2011-03-28 2012-10-04 株式会社クラレ Polymère d'acétal de vinyle modifié par un alkyle et composition associée
JP2017125134A (ja) * 2016-01-14 2017-07-20 積水化学工業株式会社 粘着シート

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05279414A (ja) * 1992-04-01 1993-10-26 Sekisui Chem Co Ltd 星型ポリビニルアセタールおよびその製造方法
JP2011225432A (ja) * 2010-03-29 2011-11-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
WO2012023517A1 (fr) * 2010-08-19 2012-02-23 株式会社クラレ Résine d'acétal de polyvinyle, composition de la suspension préparée à partir de celle-ci, feuille de céramique verte, et condensateur céramique multicouches
WO2012133351A1 (fr) * 2011-03-28 2012-10-04 株式会社クラレ Polymère d'acétal de vinyle modifié par un alkyle et composition associée
JP2017125134A (ja) * 2016-01-14 2017-07-20 積水化学工業株式会社 粘着シート

Also Published As

Publication number Publication date
TW201942152A (zh) 2019-11-01
JPWO2019189402A1 (ja) 2021-02-12
JP7406373B2 (ja) 2023-12-27

Similar Documents

Publication Publication Date Title
JP4977274B2 (ja) スラリー組成物の製造方法
JP5179308B2 (ja) ポリビニルアセタール
JP5038935B2 (ja) 積層セラミックコンデンサ内部電極用導電ペースト
JP6178093B2 (ja) 変性ポリビニルアセタール樹脂
WO2012133351A1 (fr) Polymère d'acétal de vinyle modifié par un alkyle et composition associée
JP2014072103A (ja) 無機ペースト及び積層セラミックコンデンサ
JP2019065166A (ja) 水系ポリビニルアセタール樹脂組成物
KR20210119449A (ko) 중합체, 도전성 페이스트 조성물, 세라믹스용 바인더 수지, 세라믹스 슬러리 조성물 및 도전 페이스트용 바인더 수지
JP2004244631A (ja) ビニルアセタール系重合体およびその用途
JP7406373B2 (ja) セラミックグリーンシート用変性ポリビニルアセタール樹脂
JP2012216488A (ja) 導電ペースト
JP7457487B2 (ja) 導電ペースト
JP5638903B2 (ja) スラリー組成物の製造方法
JP4746526B2 (ja) 導電ペースト
TWI774774B (zh) 聚合物、包含聚合物而成的膏組合物、導電膏用黏結劑樹脂、導電膏組合物、陶瓷用黏結劑樹脂、陶瓷組合物及陶瓷成型體
JP6251001B2 (ja) 樹脂組成物
JP4145263B2 (ja) 導電ペースト
JP5824388B2 (ja) 導電ペースト
JP2013251208A (ja) 導電ペースト
TW201331956A (zh) 導電糊及積層陶瓷電容器
JP4568513B2 (ja) 導電ペースト
JP2021103776A (ja) 導電ペースト
JP2006332621A (ja) ポリビニルアセタール樹脂組成物
JP2012092002A (ja) スラリー組成物の製造方法
JP2013073689A (ja) 導電ペースト

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019519012

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19775715

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19775715

Country of ref document: EP

Kind code of ref document: A1