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
  • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
• • 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
  • 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
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on 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; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • 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
  • C08F216/02—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 alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • 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
  • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • 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
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0856—Iron
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2265—Oxides; Hydroxides of metals of iron
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2265—Oxides; Hydroxides of metals of iron
  • C08K2003/2272—Ferric oxide (Fe2O3)
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols

Definitions

• the present invention relates to a polyvinyl acetal resin capable of producing a molded product having excellent dispersibility and high mechanical strength.
• Polyvinyl acetal resin is excellent in toughness, film-forming property, inorganic powder such as pigment, dispersibility of organic powder, adhesiveness to coated surface, etc. Therefore, for example, ceramic green constituting a laminated ceramic capacitor. It is used in sheets, conductive pastes, inks, paints, baking enamel, wash primers, etc.
• the monolithic ceramic capacitor is generally manufactured through the following steps. First, a ceramic raw material powder is added to a binder resin such as polyvinyl butyral resin and mixed uniformly to obtain a slurry composition. The obtained slurry composition is applied to the release-treated support surface. By heating this to remove volatile components such as a solvent, it is peeled off from the support to obtain a ceramic green sheet. Next, a plurality of pieces of the obtained ceramic green sheet coated with a conductive paste containing polyvinyl butyral resin or the like as a binder resin by screen printing or the like are alternately stacked and heat-pressed to prepare a laminated body. Further, after performing a degreasing treatment, a laminated ceramic capacitor is obtained through a step of sintering an external electrode on the end face of the ceramic fired product obtained by firing.
• a binder resin such as polyvinyl butyral resin
• Patent Document 1 acetic acid is generated from sodium acetate remaining in polyvinyl alcohol, and the obtained acetic acid is used as a catalyst to use a polyvinyl acetal resin obtained by acetalizing the polyvinyl alcohol. It is disclosed that metal corrosion of peripheral equipment can be prevented. Further, Patent Document 2 discloses that the flexibility and heat-sealing property of the obtained sheet can be enhanced by using a polyvinyl acetal resin obtained by acetalizing a specific modified polyvinyl alcohol with acetaldehyde and butyraldehyde. There is.
• magnetic powders such as ferrites are inferior in dispersibility
• the polyvinyl acetal resin described in Patent Documents 1 and 2 is used as a binder resin
• the magnetic powder is not sufficiently dispersed in the slurry composition.
• dispersibility and dispersion stability such as sedimentation over time.
• the mechanical strength of the obtained sheet is low, and problems may occur when processing the molded sheet.
• An object of the present invention is to provide a polyvinyl acetal resin capable of producing a molded product having excellent dispersibility and high mechanical strength.
• the present invention is a polyvinyl acetal resin having a water absorption per unit area of 2 mg / cm 2 or more and 50 mg / cm 2 or less when molded into a film having a thickness of 10 ⁇ m.
• the present invention will be described in detail below.
• the present inventor can improve the dispersibility of difficult-to-dispersible substances such as magnetic powder by adjusting the amount of water absorption per unit area under predetermined conditions, and has high mechanical strength. It has been found that a film having the above can be produced, and the present invention has been completed. In the present invention, high substrate adhesion can be exhibited.
• the polyvinyl acetal resin of the present invention has a water absorption amount of 2 mg / cm 2 or more and 50 mg / cm 2 or less per unit area when molded into a film having a thickness of 10 ⁇ m.
• the preferable lower limit of the amount of water absorption per unit area is 3 mg / cm 2
• the preferable upper limit is 40 mg / cm 2
• the more preferable upper limit is 30 mg / cm 2 .
• the amount of water absorption per unit area can be calculated by the method described later. Specifically, the polyvinyl acetal resin of the present invention is formed into a film having a thickness of 10 ⁇ m, dried at 70 ° C. for 3 hours, and then left in an environment of a temperature of 20 ° C. and a humidity of 55% for 1 hour or more to reduce the weight A of the film. taking measurement. Next, the main surface of the molded and dried film is exposed to steam in warm water having a temperature of 50 ° C. Then, when water droplets are seen on the surface of the film, the exposure to water vapor is stopped and the weight B of the molded film is measured. The amount of water absorption is calculated by subtracting the weight A from the weight B. The amount of water absorption per unit area is calculated by dividing the amount of water absorption by the exposed area. In the present specification, the state in which water droplets are seen on the surface of the film is defined as the saturated water vapor content.
• the polyvinyl acetal resin of the present invention preferably has a water absorption rate of 0.2 mg / min or more and 4.2 mg / min or less under the above-mentioned measurement conditions for the amount of water absorption per unit area.
• the more preferable lower limit of the water absorption rate is 0.3 mg / min, and the more preferable upper limit is 4.0 mg / min.
• the water absorption rate can be measured by the same method as the water absorption amount per unit area. Specifically, the time from the start of water vapor exposure to the time when water vapor exposure is stopped is measured, and the value obtained by dividing the film weight per unit area by the exposure time is defined as the water absorption rate.
• the polyvinyl acetal resin of the present invention is represented by at least a structural unit having a hydroxyl group represented by the following formula (1), a structural unit having an acetal group represented by the following formula (2), and the following formula (3). It is preferable to have a structural unit having an acetyl group.
• R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• the alkyl group may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or iso.
• Pentadecyl group, octadecyl group and the like Of these, a methyl group and an n-propyl group are preferable.
• the preferable lower limit of the content of the structural unit having a hydroxyl group represented by the above formula (1) (hereinafter, also referred to as “hydroxyl amount”) is 35 mol%, and the preferable upper limit is 85 mol%. be.
• the amount of hydroxyl groups is at least the above lower limit, it becomes easy to adjust the amount of water absorption per unit area within a predetermined range.
• the slurry composition obtained by using the polyvinyl acetal resin of the present invention has excellent dispersibility and dispersion stability.
• the mechanical strength and substrate adhesion of the obtained molded product are improved.
• the amount of hydroxyl groups can be measured by, for example, 13 C-NMR.
• the preferable lower limit of the half width of the hydroxyl group quantified by IR measurement is 280 cm -1
• the more preferable lower limit is 290 cm -1
• the preferable upper limit is 420 cm -1
• the more preferable upper limit is 400 cm -1 .
• the polyvinyl acetal resin preferably has a hydroxyl group quantified by NMR measurement and IR measurement with a half-value width in terms of mol% of 0.01 mol% / cm -1 or more and 0.30 mol% / cm -1 or less.
• a half-value width of the hydroxyl group in terms of mol% is 0.05 mol% / cm -1 or more and 0.290 mol% / cm -1 or less.
• the IR measurement is an absorption spectrum measurement by infrared absorption spectroscopy, and can be measured by, for example, an IR measuring meter.
• the half-value width of the hydroxyl group is measured from the peak width at 1/2 of the peak height appearing near 3500 cm -1 by IR measurement, and then the amount of hydroxyl group is measured by NMR measurement.
• the preferable lower limit of the content of the structural unit having an acetal group represented by the above formula (2) (hereinafter, also referred to as “acetal group amount”) is 1 mol%, and the preferable upper limit is 50 mol. %.
• the amount of the acetal group is in the above range, the toughness of the resin can be enhanced.
• the more preferable lower limit of the acetal group amount is 2 mol%, and the more preferable upper limit is 45 mol%.
• the method for calculating the acetal group amount since the acetal group of the polyvinyl acetal resin is obtained by acetalizing two hydroxyl groups, the two acetalized hydroxyl groups are counted.
• the method is used to calculate the amount of acetal groups.
• the acetal group amount can be measured by, for example, NMR.
• R 1 of the above formula (2) is preferably a methyl group or a propyl group.
• the acetal group amount (acetacetal group amount) is preferably 1 mol% or more and 50 mol% or less.
• the acetal group amount (butyral group amount) is preferably 1 mol% or more and 10 mol% or less.
• the preferable lower limit of the content of the structural unit having an acetyl group represented by the above formula (3) (hereinafter, also referred to as “acetyl group amount”) is 1 mol%, and the preferable upper limit is 20 mol. %.
• the amount of the acetyl group is in the above range, the toughness of the resin can be enhanced.
• the more preferable lower limit of the amount of acetyl group is 2 mol%, and the more preferable upper limit is 15 mol%.
• the amount of the acetyl group can be measured by, for example, NMR.
• the polyvinyl acetal resin of the present invention may have a structural unit having an acid-modifying group.
• the acid-modifying group include a carboxyl group, a sulfonic acid group, a maleic acid group, a sulfenic acid group, a sulfenic acid group, a phosphoric acid group, a phosphonic acid group, an amino group, and salts thereof.
• a carboxyl group is preferable. Since the modified polyvinyl acetal resin has a structural unit having the acid-modifying group, the compatibility with the epoxy resin can be improved and high mechanical strength can be realized.
• the structural unit having the acid-modified group may have a structure in which an acid-modified group as a side chain is directly bonded to the carbon constituting the main chain, and the acid-modified group may be directly bonded to the carbon constituting the main chain via an alkylene group. May be a combined structure.
• the structural unit having the acid-modifying group may have a three-dimensional structure in which two acid-modifying groups are bonded to the same carbon constituting the main chain, and one acid-modifying group is bonded to the carbon constituting the main chain. It may have a three-dimensional structure. Further, it may have a three-dimensional structure in which one acid-modifying group is bonded to adjacent carbons constituting the main chain, and an acid-modifying group is bonded to only one of the adjacent carbons constituting the main chain. May be. Among them, it is preferable to have a three-dimensional structure in which two acid-modifying groups are bonded to the same carbon constituting the main chain, or a three-dimensional structure in which one acid-modifying group is bonded to adjacent carbons constituting the main chain. ..
• the steric hindrance can be increased and the network structure of the cured product obtained by the combination with the epoxy resin can be widened, and as a result, the flexibility of the obtained cured product can be improved. It is preferable to have a steric structure in which two acid-modifying groups are bonded to the same constituent carbon.
• the structural unit having the acid-modified group may have a three-dimensional structure having an isotactical arrangement in which the acid-modified group is bonded in the same direction to the carbon constituting the main chain, and the carbon constituting the main chain may be used. It may have a three-dimensional structure having a syndiotactic arrangement in which acid-modifying groups are alternately bonded to the opposite side. Further, it may have a three-dimensional structure having an atactical arrangement in which the acid-modifying group is randomly bonded.
• the alkylene group is an alkylene group having 1 to 10 carbon atoms. Is more preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable.
• Examples of the alkylene group having 1 to 10 carbon atoms include a linear alkylene group, a branched chain alkylene group, and a cyclic alkylene group.
• Examples of the linear alkylene group include a methylene group, a vinylene group, an n-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group and the like.
• Examples of the branched alkylene group include a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group and the like.
• cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclohexylene group and the like. Of these, a linear alkylene group is preferable, a methylene group, a vinylene group, and an n-propylene group are more preferable, and a methylene group and a vinylene group are even more preferable.
• the preferable lower limit of the average degree of polymerization of the polyvinyl acetal resin of the present invention is 200, and the preferable upper limit is 5000.
• the average degree of polymerization is within the above range, the mechanical strength of the obtained coating film can be sufficiently increased.
• the more preferable lower limit of the average degree of polymerization is 300, and the more preferable upper limit is 4000.
• the polyvinyl acetal resin of the present invention for example, a polyvinyl alcohol resin obtained by polymerizing a monomer such as vinyl acetate and saponified by adding an acid or an alkali is converted into acetal. How to do it, etc.
• the amount of water absorption per unit area when formed into a film having a thickness of 10 ⁇ m is predetermined by acetalizing using polyvinyl alcohol having a degree of saponification, an average degree of polymerization, and a half-value width of a hydroxyl group within a predetermined range. Polyvinyl acetal resin within the range of can be produced.
• the half width of the hydroxyl group of the polyvinyl alcohol resin is preferably 340 cm -1 or more and 380 cm -1 or less.
• the average degree of polymerization of the polyvinyl alcohol resin is preferably 200 or more and 5000 or less, and the saponification degree is preferably 70 mol% or more and 99.9 mol% or less.
• the polyvinyl acetal resin of the present invention is preferably an acetal product of a polyvinyl alcohol resin having a saponification degree of 75 mol% or more.
• the specific polyvinyl alcohol as described above is, for example, a method of measuring and selecting the physical properties of a plurality of types of polyvinyl alcohol, a method of selecting by referring to the physical properties presented in commercially available polyvinyl alcohol, and a physical property value in a predetermined step.
• the acetalization can be carried out by a known method, and 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, amine-based solvents and the like.
• the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
• Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, methyl benzoate and the like.
• Examples of the aliphatic ester solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, ethyl acetoacetate and the like.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, acetophenone and the like.
• Examples of the lower paraffin solvent include hexane, pentane, octane, cyclohexane, decane and the like.
• Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether and the like.
• Examples of the amide-based solvent include N, N-dimethylformamide, N, N-dimethyltesetoamide, N-methylpyrrolidone, acetanilide and the like.
• amine-based solvent examples include ammonia, trimethylamine, triethylamine, n-butylamine, din-butylamine, trin-butylamine, aniline, N-methylaniline, N, N-dimethylaniline, and pyridine. These can be used alone or in combination of two or more kinds of solvents. Among these, ethanol, n-propanol, isopropanol, and tetrahydrofuran are particularly preferable from the viewpoint of solubility in the resin and simplicity at the time of purification.
• the acetalization is preferably carried out in the presence of an acid catalyst.
• the above acid catalyst is not particularly limited, and mineral acids such as sulfuric acid, hydrochloric acid, nitrate and phosphoric acid, carboxylic acids such as formic acid, acetic acid and propionic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and paratoluenesulfone are not particularly limited. Examples thereof include sulfonic acids such as acids.
• These acid catalysts may be used alone or in combination of two or more compounds. Of these, hydrochloric acid, nitric acid, and sulfuric acid are preferable, and hydrochloric acid is particularly preferable.
• aldehyde used for the acetalization examples include aldehydes having a chain aliphatic group having 1 to 10 carbon atoms, a cyclic aliphatic group or an aromatic group. As these aldehydes, conventionally known aldehydes can be used.
• the aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include aliphatic aldehydes and aromatic aldehydes.
• Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, n-barrel aldehyde, n-hexyl aldehyde, 2-ethyl butyl aldehyde, 2-ethyl hexyl aldehyde, n-heptyl aldehyde, and n-.
• Octylaldehyde Examples thereof include octylaldehyde, n-nonylaldehyde, n-decylaldehyde, and amylaldehyde.
• aromatic aldehyde examples include aromatic aldehydes such as benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, and ⁇ -phenylpropionaldehyde. And so on. Further, a cyclic multimer such as paraldehyde and metaldehyde can be used. These aldehydes may be used alone or in combination of two or more.
• formaldehyde, acetaldehyde, butyraldehyde, 2-ethylhexyl aldehyde which have excellent acetalization reactivity, can bring about a sufficient internal plasticizing effect on the produced resin, and as a result can impart good flexibility.
• n-Nonylaldehyde and paraldehyde are preferable.
• formaldehyde, acetaldehyde, butyraldehyde, and paraldehyde are more preferable because an adhesive composition having particularly excellent impact resistance and adhesiveness to a metal can be obtained.
• the amount of the aldehyde added can be appropriately set according to the amount of acetal groups of the target polyvinyl acetal resin. In particular, when it is 60 to 95 mol%, preferably 65 to 90 mol% with respect to 100 mol% of polyvinyl alcohol, the acetalization reaction is efficiently carried out and unreacted aldehydes can be easily removed, which is preferable.
• a slurry composition can be prepared by mixing a magnetic powder, a solvent, or the like with the polyvinyl acetal resin of the present invention.
• a slurry composition containing the polyvinyl acetal resin of the present invention, a magnetic powder, and a solvent is also one of the present inventions.
• the content of the polyvinyl acetal resin of the present invention in the slurry composition of the present invention has a preferable lower limit of 20% by weight, a more preferable lower limit of 25% by weight, a preferable upper limit of 65% by weight, and a more preferable upper limit of 60% by weight.
• the slurry composition of the present invention contains a magnetic powder.
• the magnetic powder include metal particles, metal oxide particles, metal nitride particles and the like.
• Examples of the metal particles used as the magnetic powder include iron, cobalt, nickel, and alloys containing these.
• Examples of the alloy include Fe-Ni, Fe-Co, Fe-Cr, Fe-Si, Fe-Al, Fe-Cr-Si, Fe-Cr-Al, Fe-Al-Si, Fe-Pt and the like. Can be mentioned.
• ferrite is preferable, and specifically, for example, MnFe 2 O 4 , CoFe 2 O 4 , NiFe 2 O 4 , CuFe 2 O 4 , ZnFe 2 O 4 , MgFe 2 O 4 , Fe 3 O. 4 , MnFe 2 O 4 , Cu—Zn ferrite, Ni—Zn ferrite, Mn—Zn-ferrite, Ba ferrite, Ni—Cu—Zn ferrite and the like can be used.
• metal nitride examples include Fe 2 N, Fe 3 N, Fe 4 N, Fe 16 N 2 , Sm 2 Fe 17 N 3 , and the like.
• Examples of the shape of the magnetic powder include a spherical shape, an ellipsoidal body, a disk shape, a needle shape, a rod shape, a flat shape, a tetrapod shape, a porous shape, and a porous shape.
• a spherical shape is preferable from the viewpoint of dispersibility and the like.
• the magnetic powder may be surface-treated with a silane coupling agent.
• a silane coupling agent By surface-treating the magnetic powder with a silane coupling agent, aggregation of the magnetic powders can be suppressed even when a large amount of the magnetic powder is blended.
• silane coupling agent examples include N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrietoshishisilane, and 3- (2-aminoethyl) aminopropyltrimethoxy.
• Aminosilane such as silane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, vinylsilane such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, etc.
• 3-Methacryloxypropyltrimethoxysilane methacrylsilane such as 3-methacryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethosisilane, 3-mercaptopropylethoxysilane and the like.
• 3-Glucidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and other epoxysilanes, 3-ureidopropyl Ureidosilane such as triethoxysilane, isocyanatesilane such as 3-isocyandiapropyltrimethoxysilane, 3-isocyandiapropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, n-propyltri Examples thereof include alkylsilanes such as methoxysilane, isopropyldimethoxysilane, isobutyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and phenyl
• a method of surface-treating the magnetic material powder with a silane coupling agent for example, a wet method of treating the magnetic material powder in a solution in which the magnetic material powder is dispersed, or a dry method of directly treating the magnetic material powder as a powder.
• a wet method of treating the magnetic material powder in a solution in which the magnetic material powder is dispersed or a dry method of directly treating the magnetic material powder as a powder.
• examples thereof include an integral blending method in which the magnetic powder is treated in a resin composition in which the magnetic powder is dispersed in the resin.
• the wet method is preferable from the viewpoint of suppressing the aggregation of the magnetic powder.
• the preferable lower limit of the average particle size of the magnetic powder is 0.1 ⁇ m, and the preferable upper limit is 100 ⁇ m.
• the more preferable lower limit of the average particle size of the magnetic powder is 0.5 ⁇ m, and the more preferable upper limit is 70 ⁇ m.
• the average particle size can be measured by, for example, a laser diffraction type particle size distribution measuring device or the like.
• the content of the magnetic powder in the slurry composition of the present invention has a preferable lower limit of 5% by weight, a more preferable lower limit of 10% by weight, a preferable upper limit of 40% by weight, and a more preferable upper limit of 35% by weight.
• water and an organic solvent compatible with water can be used as described above.
• the organic solvent compatible with water include alcohols.
• the slurry composition of the present invention may contain a resin other than the polyvinyl acetal resin such as an acrylic resin and ethyl cellulose as long as the effects of the present invention are not impaired. Further, the slurry composition of the present invention may be added with a plasticizer, a lubricant, an antistatic agent and the like as long as the effects of the present invention are not impaired.
• Example 1 Preparation of polyvinyl acetal resin
• 500 g of polyvinyl alcohol resin (ketenization degree 88 mol%, average polymerization degree 600, half width at half maximum of hydroxyl group 350 cm -1 ) was added to 2500 g of pure water, and the mixture was stirred and dissolved at a temperature of 90 ° C. for about 2 hours.
• This solution was cooled to 40 ° C., 10 g of hydrochloric acid having a concentration of 35% by weight was added thereto, the liquid temperature was lowered to 5 ° C., 75 g of acetaldehyde was added, and the acetalization reaction was carried out while maintaining this temperature. Then, the liquid temperature was maintained at 65 ° C.
• the amount of the hydroxyl group measured by the above 13 C-NMR measurement was divided by the half-value width of the hydroxyl group to calculate the half-value width in terms of mol% of the hydroxyl group.
• Example 2 A polyvinyl acetal resin was obtained in the same manner as in Example 1 except that a polyvinyl alcohol resin (saponification degree 88 mol%, average polymerization degree 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used.
• a polyvinyl alcohol resin (saponification degree 88 mol%, average polymerization degree 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used.
• the acetal group amount acetacetal group amount, butyral group amount
• hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 3 Polyvinyl alcohol resin (consolidation degree 88 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used, and the amount of acetaldehyde added was changed to 7.0 g. Acetal resin was obtained.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half price width, and hydroxyl group mol% equivalent half price width are as shown in Table 1. there were.
• Example 4 The same as in Example 1 except that a polyvinyl alcohol resin (maintenance degree 88 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 380 cm -1 ) was used, and butyraldehyde was changed to 15.0 g instead of acetaldehyde. A polyvinyl acetal resin was obtained.
• the acetal group amount acetacetal group amount, butyral group amount
• hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 5 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (ketenization degree 88 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 370 cm -1 ) was used and the amount of acetaldehyde added was changed to 110 g.
• the acetal group amount acetacetal group amount, butyral group amount
• hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 6 Polyvinyl alcohol resin (sakenization degree 90 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 335 cm -1 ) was used, and the amount of acetaldehyde added was changed to 7.0 g. Acetal resin was obtained.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 7 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (sakenization degree 90 mol%, average degree of polymerization 4500, half width at half maximum of hydroxyl group 345 cm -1 ) was used and the amount of acetaldehyde added was changed to 75 g.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 8 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (ketenization degree 88 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used and the amount of acetaldehyde added was changed to 115 g.
• the acetal group amount acetacetal group amount, butyral group amount
• hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 9 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (sakenization degree 95 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used and the amount of acetaldehyde added was changed to 110 g.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 10 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (sakenization degree 82 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 345 cm -1 ) was used and the amount of acetaldehyde added was changed to 60 g.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 1 A polyvinyl acetal resin was obtained in the same manner as in Example 1 except that a polyvinyl alcohol resin (sakenization degree 88 mol%, average polymerization degree 600, half width at half maximum of hydroxyl group 335 cm -1 ) was used.
• a polyvinyl alcohol resin (sakenization degree 88 mol%, average polymerization degree 600, half width at half maximum of hydroxyl group 335 cm -1 ) was used.
• the acetal group amount acetacetal group amount, butyral group amount
• hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• Example 2 Polyvinyl acetal resin in the same manner as in Example 1 except that a polyvinyl alcohol resin (ketenization degree 88 mol%, average degree of polymerization 600, half width at half maximum of hydroxyl group 335 cm -1 ) was used and the amount of acetaldehyde added was changed to 140 g.
• the acetal group amount (acetacetal group amount, butyral group amount), hydroxyl group amount, acetyl group amount, hydroxyl group half-price range, and hydroxyl group mol% equivalent half-price range are as shown in Table 1. there were.
• the water absorption amount per unit area was calculated by dividing the water absorption amount by the exposed area.
• the exposed area was set to 40 cm 2 . Further, the time (exposure time) from the start of water vapor exposure to the time when water vapor exposure was stopped was measured, and the value obtained by dividing the film weight per unit area by the exposure time was calculated as the water absorption rate.
• a resin sheet is prepared by applying the obtained polyvinyl acetal resin onto a PET film that has been mold-released using a coater so that the thickness after drying is 15 ⁇ m, and then heating and drying at 70 ° C. for 120 minutes. bottom.
• the resin sheets obtained on various substrates were coated so that the film thickness after drying was 20 ⁇ m, and dried to prepare a sample for adhesiveness measurement.
• the obtained measurement sample was evaluated for adhesiveness using a grid test of JIS K 5400.

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