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
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/38—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/08—Inorganic dielectrics
  • H01G4/12—Ceramic dielectrics
  • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/30—Stacked capacitors

Definitions

• the present invention relates to a resin used as a binder and the like, and a resin composition comprising the resin.
• Resins such as polyvinyl acetal-based resins, acrylic-based resins, and polyvinyl alcohol-based resins are widely used as organic binders.
• Organic binders are used in interlayer films for laminated glass, inks, paints, baking enamels, lacquers, ceramic green sheets, heat-developable photosensitive materials, ink image-receiving layers, and the like.
• polyvinyl acetal resins are generally acetalized unmodified polyvinyl alcohol, and so-called unmodified polyvinyl acetal resins having acetyl groups, hydroxyl groups, and acetal groups in side chains are widely used.
• modified polyvinyl acetal resins having functional groups (modifying groups) other than acetyl groups, hydroxyl groups, and acetal groups have also been investigated in order to impart various functions.
• Patent Documents 1 to 3 disclose modified polyvinyl acetal resins containing polyoxyalkylene groups in side chains.
• carboxyl groups may be introduced into the binder resin to ensure a certain level of cohesion.
• acrylic resins generally have structural units derived from carboxyl group-containing monomers such as (meth)acrylic acid.
• the organic binder is sometimes used in a slurry solution together with the inorganic powder, and in this case, the inorganic powder solution stability is required to appropriately disperse the inorganic powder without increasing the viscosity.
• a resin composition containing an organic binder is often shaped into a sheet, film, or the like, and is often required to have shape stability so that the shape can be maintained after being made into a predetermined shape.
• organic binders are used in ceramic green sheets and the like, they are decarbonized by firing, but if organic substances remain after decarbonization, defects will occur in the fired product and the yield after firing will decrease. Therefore, it is required to improve the decarbonization property when removing the organic binder.
• an object of the present invention is to provide a resin that can improve stability in inorganic powder solution, shape stability after forming into a predetermined shape, and decarbonization.
• the present invention provides the following [1] to [14].
• [1] A resin having a chlorine atom content and a free acid content of 0.03% by mass or less, and satisfying the requirements of Formula I and Formula II below.
• thermoplastic resin is at least one selected from the group consisting of polyvinyl acetal-based resins and polyvinyl alcohol-based resins.
• thermoplastic resin is at least one selected from the group consisting of polyvinyl acetal-based resins and polyvinyl alcohol-based resins.
• at least one selected from the group consisting of polyvinyl acetal-based resins and polyvinyl alcohol-based resins has a polyalkylene oxide structure.
• polyalkylene oxide structure is represented by the following formula (1).
• a 1 O is an oxyalkylene group having 2 to 6 carbon atoms
• m is the average number of repetitions, and is 10 to 200.
• R 1 is an alkyl group having 1 to 8 carbon atoms or It is a hydrogen atom.
• the oxyalkylene group may be one type alone, or two or more types may be mixed.* indicates the bonding position with another group.
• a resin that can improve stability in inorganic powder solutions, shape stability after forming into a predetermined shape, and decarbonization.
• the resin of the present invention (hereinafter also referred to as carboxyl group content)]
• the resin of the present invention (hereinafter sometimes referred to as resin (X) for convenience) has both a chlorine atomic weight and a free acid content of 0.03% by mass or less.
• the slurry containing the resin (X) and the inorganic powder contains chlorine atoms or free acid It is difficult to increase the stability of the inorganic powder solution because the charge becomes unstable due to the influence of the amount, which causes thickening, phase separation, and the like.
• the chlorine atomic weight is preferably 0.024% by mass or less, more preferably 0.020% by mass or less, and even more preferably 0.016% by mass, from the viewpoint of the stability of the inorganic powder solution. The lower the chlorine atom weight, the better, and it is sufficient if it is 0.0% by mass or more.
• the free acid content is preferably 0.024% by mass or less, more preferably 0.020% by mass or less, and preferably 0.016% by mass or less, from the viewpoint of the stability of the inorganic powder solution.
• the amount of the free acid may be 0.0% by mass or more from the viewpoint of the stability of the inorganic powder solution, but may be contained in a certain amount or more depending on the type of the resin (X). In the resin, it is preferable to contain a certain amount or more in order to increase the cohesive force and improve the adhesiveness.
• the chlorine atom content and the free acid content are defined as 0.0% by mass when they are below the detection limit by the measuring method described later.
• the total amount of chlorine atoms and free acids is preferably 0.05% by mass or less, and 0.03% by mass or less, from the viewpoint of the stability of an inorganic powder solution. is more preferably 0.024% by mass or less, still more preferably 0.016% by mass or less, and 0.0% by mass or more.
• the amount of chlorine atoms and the amount of free acid can be reduced to the above upper limits or less by appropriately adjusting the production method of resin (X) and the components that make up resin (X).
• the chlorine atomic weight can be measured by ion analysis using ion chromatography or the like, and the free acid content can be measured by a titration method.
• the resin (X) of the present invention meets the requirements of Formula I and Formula II below.
• Formula II: (A ⁇ C)/A >0.87 (However, with a TG/DTA (differential thermal/thermogravimetric simultaneous measurement device), in the atmosphere, the temperature is raised from 40 ° C. to 600 ° C. at a rate of 5 ° C./min, and the thermal analysis measurement is performed by holding at 600 ° C. for 10 minutes.
• TG/DTA differential thermal/thermogravimetric simultaneous measurement device
• the weight at 100°C is A
• the weight at 200°C is B
• the weight at 600°C for 10 minutes is C.
• the value of (AB)/A represented by formula I serves as an index representing the content of high-boiling-point, low-molecular-weight components contained in resin (X). Therefore, when (AB)/A is 0.01 or more, the high-boiling low-molecular-weight components in the resin (X) increase, and when stored for a long period of time after molding into a predetermined shape such as a sheet, storage Part of the resin (X) evaporates inside, causing a change in shape and a problem of low shape stability.
• the weight loss during heating of resin (X) from room temperature to 100° C. is mainly due to volatilization of water. Therefore, in the present invention, the temperature when measuring the weight A is set to 100 ° C. instead of room temperature, so that the value of (AB) / A is the ratio of low molecular weight components excluding the influence of moisture. It is an index that accurately indicates the
• the value of (AB)/A is preferably as low as possible from the viewpoint of good shape stability, preferably 0.009 or less, more preferably 0.008 or less, and even more preferably 0.007 or less. Also, the value of (AB)/A is not particularly limited as long as it is 0 or more.
• the value of (AC)/A represented by formula II is an index showing the decomposition rate of the resin (X) when heated at a high temperature.
• the value of (AC)/A is 0.87 or less, the resin (X) is not sufficiently decomposed even by high temperature heating. Therefore, for example, when the decarbonization treatment is carried out by firing, etc., the amount of residual carbon increases, causing defects and the like, making it difficult to obtain a fired product or the like with a high yield.
• (AC)/A is preferably 0.88 or more, more preferably 0.9 or more, and 0.88 or more, more preferably 0.9 or more, from the viewpoint of obtaining a baked product with a high yield by reducing the amount of residual carbon when decarbonizing. 91 or more is more preferable.
• the higher the value of (AC)/A represented by formula II the better, and there is no particular limitation as long as it is 1 or less. Typically it will be less than 1, for example 0.99 or less.
• the value of (AB)/A can be reduced by reducing the low-molecular-weight component of the resin (X). Further, (AC)/A can be increased by appropriately adjusting the type of resin (X) and the components constituting resin (X).
• Resin (X) used in the present invention is preferably a thermoplastic resin.
• a thermoplastic resin By using a thermoplastic resin, it becomes easier to mold the resin composition containing the resin (X) into a predetermined shape such as a sheet.
• thermoplastic resins include polyvinyl acetal resins, acrylic resins, polyvinyl alcohol resins, polyvinyl acetate, ethylene-vinyl acetate copolymers, polyurethane resins, and ionomer resins. These may be used individually by 1 type, and may use 2 or more types together. By using these resins, it becomes easy to increase the value of (AC)/A while reducing (AB)/A. Moreover, both the chlorine atom weight and the free acid radical weight can be reduced by appropriately adjusting the production method of the resin (X) and the monomer components constituting the resin (X).
• thermoplastic resins described above at least one of polyvinyl acetal-based resins and polyvinyl alcohol-based resins is preferable from the viewpoint of excellent shape stability after molding into a predetermined shape and excellent decarbonization properties. .
• polyvinyl acetal-based resins are preferred because they are easy to improve the stability of the inorganic powder solution.
• thermoplastic resins may be used singly or in combination of two or more.
• the weight average molecular weight (Mw) of the resin (X) of the present invention is preferably 15,000 or more and 1,000,000 or less. By making the weight average molecular weight equal to or higher than the above lower limit, it becomes easier to reduce (AB)/A, and by making it equal to or lower than the upper limit, it becomes easy to increase (AC)/A. Further, the weight average molecular weight (Mw) of the resin (X) is more preferably 50,000 or more, more preferably 100,000 or more, from the viewpoint of improving the shape stability after being formed into a predetermined shape such as a sheet shape or a film shape. is more preferred, and 150,000 or more is even more preferred.
• the weight average molecular weight (Mw) is more preferably 600,000 or less, even more preferably 500,000 or less, and even more preferably 400,000 or less.
• the weight average molecular weight (Mw) indicates the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the resin (X) contains a polyvinyl alcohol resin, the measurement is performed after reacetylating all the hydroxyl groups of the polyvinyl alcohol resin.
• the polyvinyl acetal resin As described above, it is more preferable to use a polyvinyl acetal-based resin as the resin (X).
• the polyvinyl acetal resin may be a modified polyvinyl acetal resin or an unmodified polyvinyl acetal resin, but a modified polyvinyl acetal resin is preferred.
• Polyvinyl acetal-based resins may be used singly or in combination of two or more.
• the modified polyvinyl acetal resin may have a structure (modifying group) other than an acetal group, a hydroxyl group, and an acetyl group, and preferably has a modifying group in a side chain, as will be described later.
• the value of (AC)/A can be increased by appropriately selecting the type of modifying group.
• the polyvinyl acetal-based resin can be produced by the production method described later, even if it is a modified polyvinyl acetal resin, so that the low-molecular-weight component can be reduced, so that the value of (AB)/A can be easily reduced.
• the modifying group in the present invention preferably has a polyalkylene oxide structure.
• the polyvinyl acetal resin since the polyvinyl acetal resin has a polyalkylene oxide structure, it is excellent in thermal decomposability, the value of (AC)/A tends to be large, and decarbonization is excellent.
• the polyalkylene oxide structure is as represented by the following formula (1).
• a 1 O is an oxyalkylene group having 2 to 6 carbon atoms
• m is the average number of repetitions, and is 10 to 200.
• R 1 is an alkyl group having 1 to 8 carbon atoms or It is a hydrogen atom.
• the oxyalkylene group may be one type alone, or two or more types may be mixed.* indicates the bonding position with another group.
• the oxyalkylene group for A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 or 3 carbon atoms.
• the alkylene group in the oxyalkylene group may be linear or may have a branched structure.
• the oxyalkylene group includes, for example, an oxyethylene group, an oxypropylene group, or an oxybutylene group, preferably an oxyethylene group or an oxypropylene group.
• One type of oxyalkylene group may be used alone, but two or more types may be used in combination.
• each oxyalkylene group may be added at random or may be added in blocks, but is more preferably added at random.
• the random structure makes it easier to increase the value of (AC)/A compared to the block structure.
• the oxyalkylene group in the polyalkylene oxide structure preferably contains at least one of an oxyethylene group and an oxypropylene group, and also preferably contains both an oxyethylene group and an oxypropylene group.
• both an oxyethylene group and an oxypropylene group may constitute a block structure, but more preferably constitute a random structure as described above.
• the oxyalkylene group in the alkylene oxide structure consists of an oxyethylene group or an oxypropylene group, or has an oxyethylene group and an oxypropylene group, and these have a random structure, )/A can be easily increased.
• the ratio (PO/EO) of the oxypropylene group to the oxyethylene group is, for example, 1/9 or more and 9/1 or less, preferably 2 /8 or more and 8/2 or less, more preferably 3/7 or more and 7/3 or less.
• m in formula (1) that is, the average number of repeating oxyalkylene groups in the polyalkylene oxide structure is, for example, 10-200.
• the average repetition number (that is, m in formula (1)) is preferably 15 to 80 from the viewpoint of increasing the value of (AC)/A and improving the decarbonization property, and more It is preferably 20-78, more preferably 25-75, even more preferably 30-70.
• by increasing the number of repetitions it becomes easier to secure flexibility and the like, and moldability when forming into a sheet or the like tends to be improved.
• the alkyl group for R 1 may be linear or may have a branched structure.
• alkyl groups for R 1 include branched butyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl and t-butyl groups, n-pentyl group, branched pentyl group, n branched heptyl groups such as -hexyl group, branched hexyl group, n-heptyl group, isoheptyl group and 3-heptyl group; branched octyl groups such as n-octyl group, isooctyl group and 2-ethylhexyl group; R 1 may be either an alkyl group or a hydrogen atom.
• the alkyl group may have 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1
• the above polyalkylene oxide structure is preferably linked to the main chain via a linking group.
• a linking group an ether bond (-O-), an ester bond (-COO-), an amide bond (-CONR-: R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or at least any of these bonds
• a hydrocarbon group optionally having
• the number of carbon atoms in the linking group is not particularly limited, but may be, for example, about 10 or less, preferably 4 or less.
• the linking group does not need to have carbon atoms, and therefore the linking group may have 0 or more carbon atoms.
• R in -CONR- is preferably a hydrogen atom.
• the carbon number of the hydrocarbon group in the linking group may be, for example, about 1-10, preferably 1-4.
• the polyalkylene oxide structure is linked to the main chain via either an ether bond or —CH 2 O—.
• the polyalkylene oxide structure is attached to the backbone either through ether linkages or -CH 2 O- to facilitate its manufacture.
• an oxygen atom is preferably bonded to the polyalkylene oxide structure.
• a polyvinyl acetal-based resin typically has an acetal group, a hydroxyl group, and an acetyl group. However, the polyvinyl acetal-based resin does not have to contain a hydroxyl group by being modified with a functional group.
• the acetal group, hydroxyl group, and acetyl group are groups bonded directly to the main chain or via an oxygen atom, as shown in formulas (3-1) to (3-3) described later.
• a hydroxyl group, etc., possessed by the polyalkylene oxide structure is not included.
• the polyvinyl acetal-based resin is preferably modified to have a polyalkylene oxide structure represented by the above formula (1) as described above.
• the modified polyvinyl acetal resin preferably has a modification amount of 0.1 mol % or more and 10 mol % or less with the polyalkylene oxide structure (that is, the functional group represented by formula (1)).
• the amount modified by the polyalkylene oxide structure is preferably 0.2 mol% or more, more preferably 0.3 mol% or more, further preferably 0.4 mol% or more, and preferably 8 mol% or less. , is more preferably 6 mol % or less, and even more preferably 4 mol % or less.
• the amount of modification by a functional group refers to the amount of functional groups with respect to all monomer units (usually all vinyl monomer units) constituting a polyvinyl acetal resin or a polyvinyl alcohol resin described later. represents a percentage.
• the amount of modification can be calculated from the spectrum obtained by subjecting the polyvinyl acetal-based resin or polyvinyl alcohol-based resin to proton NMR measurement.
• the degree of acetalization, the amount of hydroxyl groups, and the degree of acetylation, which will be described later, can be calculated from the spectrum obtained by performing proton NMR measurement.
• the polyvinyl acetal-based resin has a vinyl group-derived structural unit as a main chain, and the functional group represented by formula (1) is bonded to the vinyl group-derived structural unit that constitutes the main chain. good. Therefore, the polyvinyl acetal-based resin preferably has a structural unit represented by the following formula (2). It is more preferable to have
• R 2 is an ether bond (-O-), an ester bond (-COO-), an amide bond (-CONR-: R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a hydrocarbon group that may have at least one of these bonds.
• the carbon number of R 2 in formula (2) is, for example, 0-10, preferably 0-4.
• R 2 is preferably an ether bond (--O--) or a hydrocarbon group having at least an ether bond.
• a 1 O, R 1 , and m in the formulas (2), (2-1), and (2-2) are as described above, so description thereof will be omitted.
• a polyvinyl acetal-based resin typically has an acetal group, a hydroxyl group, and an acetyl group. That is, polyvinyl acetal-based resins typically have structural units represented by the following formulas (3-1), (3-2) and (3-3). Therefore, the modified polyvinyl acetal resin contains structural units represented by the following formulas (3-1), (3-2) and (3-3) and structural units represented by the above formula (2). It is preferable to have However, the polyvinyl acetal-based resin does not have a hydroxyl group and may not have the structural unit represented by formula (3-2). That is, the polyvinyl acetal-based resin has structural units represented by the following formulas (3-1) and (3-3), and optionally has a structural unit represented by the following formula (3-2). You may
• R represents a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms.
• the polyvinyl acetal-based resin does not have to have the polyalkylene oxide structure described above.
• a polyvinyl acetal resin may be a modified polyvinyl acetal resin having a modifying group other than a polyalkylene oxide structure, or an unmodified polyvinyl acetal resin having no modifying group.
• the polyvinyl acetal-based resin may be a modified polyvinyl acetal resin having the above-described polyalkylene oxide structure and a modifying group other than the polyalkylene oxide structure.
• the number of carbon atoms in the acetal group contained in the polyvinyl acetal-based resin is not particularly limited. ⁇ 6 is more preferred, and 2, 3 or 4 is even more preferred. Therefore, the number of carbon atoms in R represented by the formula (3-1) is preferably 1 to 9, more preferably 1 to 5, even more preferably 1 to 3. R is preferably linear, but may be partly alicyclic or aromatic.
• the acetal group is particularly preferably a butyral group, and therefore, the polyvinyl acetal-based resin is preferably a polyvinyl butyral-based resin.
• the degree of acetalization (that is, the amount of acetal) of the polyvinyl acetal-based resin is preferably 40 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and even more preferably 64 mol% or more. Also, the degree of acetalization is preferably 90 mol % or less, more preferably 88 mol % or less, even more preferably 85 mol % or less, still more preferably 79 mol % or less. By setting the degree of acetalization within these ranges, it becomes easier to contain a certain amount of the hydroxyl group and the functional group represented by the formula (1).
• the degree of acetalization means the degree of acetoacetalization when the acetal group of the polyvinyl acetal-based resin is an acetoacetal group, and the degree of butyralization when the acetal group is a butyral group. . Further, the degree of acetalization represents the ratio of acetalized vinyl alcohol units to all monomer units constituting the polyvinyl acetal-based resin.
• the hydroxyl group content of the polyvinyl acetal resin is preferably 50 mol % or less, more preferably 45 mol % or less, even more preferably 40 mol % or less, and even more preferably 35 mol % or less.
• the hydroxyl group content of the polyvinyl acetal resin is preferably 0 mol % or more, but it is preferable to contain a certain amount of hydroxyl groups, preferably 5 mol % or more, more preferably 10 mol % or more, further preferably 15 mol % or more. mol % or more, and more preferably 20 mol % or more.
• the amount of hydroxyl groups represents the ratio of hydroxyl groups to the total monomer units constituting the polyvinyl acetal-based resin.
• the degree of acetylation (acetyl group content) of the polyvinyl acetal resin is, for example, 0.01 mol % or more and 50 mol % or less. Therefore, the degree of acetylation should also be below a certain value. Therefore, the degree of acetylation of the polyvinyl acetal resin is preferably 20 mol % or less, more preferably 15 mol % or less, still more preferably 12 mol % or less, and even more preferably 5 mol % or less.
• the degree of acetylation of the modified polyvinyl acetal resin (A) is, for example, 0.01 mol % or more as described above, preferably 0.1 mol % or more, and more preferably 0.5 mol % or more.
• the polyvinyl acetal-based resin used in the present invention is a modified polyvinyl acetal-based resin
• it is obtained by acetalizing polyvinyl alcohol (also referred to as "raw material polyvinyl alcohol") with aldehyde and then reacting it with a modifier. can be done.
• modified polyvinyl alcohol may be used as the raw material polyvinyl alcohol, but usually unmodified polyvinyl alcohol may be used.
• the modified polyvinyl acetal-based resin can also be obtained by using modified polyvinyl alcohol as raw material polyvinyl alcohol and acetalizing the modified polyvinyl alcohol with aldehyde.
• the raw polyvinyl alcohol polyvinyl alcohol having a degree of saponification of 80 to 99.8 mol % is generally used.
• the aldehyde used in producing the polyvinyl acetal-based resin is not particularly limited, and is, for example, an aldehyde having 1 to 20 carbon atoms, but generally an aldehyde having 2 to 10 carbon atoms is preferably used.
• the aldehyde having 2 to 10 carbon atoms is not particularly limited, and examples thereof include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, and n-octylaldehyde.
• aldehydes having 2 to 6 carbon atoms such as acetaldehyde, n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferable, aldehydes having 2, 3 and 4 carbon atoms are more preferable, and n-butyraldehyde is further preferable. preferable.
• aldehydes may be used alone or in combination of two or more.
• the polyvinyl acetal-based resin is preferably produced by the following production method, for example, when producing a modified polyvinyl acetal resin having a polyalkylene oxide structure.
• polyoxyalkylene-modified polyvinyl alcohol is produced as a raw polyvinyl alcohol. Specifically, it is obtained by polymerizing a vinyl ester and a monomer containing a vinyl monomer having a polyoxyalkylene group to obtain a polymer, and then saponifying the polymer.
• Alkali or acid is generally used for saponification, and alkali is preferably used.
• an alkali or acid containing no chlorine may be used, for example, an inorganic alkali such as sodium hydroxide or potassium hydroxide may be used.
• an inorganic alkali such as sodium hydroxide or potassium hydroxide may be used.
• the saponification can be appropriately performed while reducing the chlorine atom weight in the resin (X).
• the polyoxyalkylene-modified polyvinyl alcohol only one type may be used, or two or more types may be used in combination.
• vinyl esters used in the above production method include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isoformate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, Vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like can be used.
• vinyl acetate is preferred.
• vinyl monomers having a polyoxyalkylene group used in the above production method include compounds represented by the following formula (4).
• a polyoxyalkylene vinyl ether represented by the following formula (4-1) and a polyoxyalkylene allyl ether represented by the following formula (4-2) are preferable.
• vinyl monomers having a polyoxyalkylene group include polyoxyethylene monovinyl ether, polyoxyethylene polyoxypropylene monovinyl ether, polyoxypropylene monovinyl ether, polyoxyethylene monoallyl ether, polyoxyethylene polyoxypropylene mono Allyl ether, polyoxypropylene monoallyl ether, polyoxyethylene alkyl vinyl ether, polyoxyethylene polyoxypropylene alkyl vinyl ether, polyoxypropylene alkyl vinyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether, polyoxy and propylene alkyl allyl ether.
• the modified polyvinyl alcohol obtained above is acetalized with an aldehyde to obtain a modified polyvinyl acetal resin.
• an acid catalyst and an aldehyde are added to a polyvinyl alcohol solution in which modified polyvinyl alcohol is dissolved in water, and the obtained polyvinyl acetal resin is preferably precipitated as particles.
• the acid catalyst is less likely to be incorporated into the particles, and even if hydrochloric acid is used as the acid catalyst, the chlorine atom weight in the resin (X) can be reduced.
• the particles of the polyvinyl butyral resin to be deposited have a certain size or more, it is possible to prevent the solution from becoming an emulsion after the deposition, thereby facilitating the collection of the particles.
• the method of adjusting the particle size is not particularly limited, but a method of adjusting the concentration of the modified polyvinyl alcohol in the polyvinyl alcohol solution, the temperature when the polyvinyl acetal resin is precipitated, and the temperature when the reaction is continued after the precipitation is adjusted. or a method of combining them.
• modified polyvinyl alcohol is added to water and heated to obtain a polyvinyl alcohol solution in which the modified polyvinyl alcohol is dissolved in water.
• concentration of the modified polyvinyl alcohol in the polyvinyl alcohol solution is, for example, 3% by mass or more and 15% by mass or less, preferably 5% by mass or more and 13% by mass or less, and still more preferably 7.5% by mass or more and 11% by mass or less. be.
• concentration is equal to or higher than the lower limit, it is possible to prevent the solution from becoming an emulsion after precipitation, and to appropriately collect the precipitated polyvinyl butyral resin particles.
• the polyvinyl alcohol solution may be heated to a temperature of, for example, 50° C. or higher and 100° C. or lower, preferably 60° C. or higher and 100° C. or lower. It is preferable to set the dissolution temperature in multiple stages according to the modified chain length, modified amount, and degree of saponification. Specifically, it is preferable to raise the temperature to 90° C. or higher after constant temperature at 60° C. for 1 hour and keep the temperature constant for 1 hour.
• the solubility of the modified group portion and the hydroxyl group portion of the polyvinyl alcohol can be improved by dissolving at a constant temperature in multiple steps.
• the polyvinyl alcohol solution is cooled, for example, to ⁇ 5° C. or higher and 60° C. or lower, preferably 10° C. or higher and 55° C. or lower.
• an acid catalyst and an aldehyde are added to the polyvinyl alcohol solution maintained within the above temperature range, and after the addition, the liquid temperature is adjusted to, for example, ⁇ 10° C. or higher and 55° C. or lower, preferably 0° C. or higher and 50° C. or lower. More preferably, the temperature is lowered to 20° C. or higher and 45° C. or lower, and even more preferably 23° C. or higher and 40° C. or lower.
• the acetalization reaction is allowed to proceed in the temperature range, for example, for 30 seconds or more and 60 minutes or less, preferably 1 minute or more and 30 minutes or less, more preferably 25 minutes or less, and even more preferably 20 minutes or less, to obtain a reaction product. should be deposited. Thereafter, for example, the liquid temperature is raised to 35° C. or higher and 80° C. or lower, preferably 40° C. or higher and 75° C. or lower, more preferably 43° C. or higher and 70° C. or lower, still more preferably 45° C. or higher and lower than 65° C., and the temperature range The reaction is allowed to proceed further for, for example, 10 minutes or more and 360 minutes or less, preferably 30 minutes or more and 300 minutes or less.
• the temperature before the reaction is set to a relatively high range to improve the compatibility with the catalyst and aldehyde, and the temperature at which the reaction product is deposited and then the reaction is allowed to proceed further.
• the temperature at the time is set to a relatively low temperature range, the grain size of the precipitated particles can be reduced.
• Various inorganic acids may be used as the acid catalyst used in the acetalization reaction, but it is preferable to use hydrochloric acid or sulfuric acid in order to facilitate the acetalization reaction.
• the amount of the acid catalyst used is, for example, 0.5% by mass or more and 6% by mass or less, preferably 1% by mass or more and 4% by mass or less with respect to 100 parts by mass of modified polyvinyl alcohol as a raw material.
• the precipitated reaction product can be obtained as a modified polyvinyl acetal resin through neutralization, washing with water, and drying in a conventional manner.
• washing with water and dehydration may be performed multiple times in order to reduce the amount of chlorine atoms in the modified polyvinyl butyral resin.
• the polyvinyl alcohol-based resin (PVA) used as the resin (X) is obtained by polymerizing a vinyl ester to obtain a polymer and then saponifying, ie, hydrolyzing the polymer according to a conventionally known method.
• PVA polyvinyl alcohol-based resin
• only 1 type may be used independently and 2 or more types may be used together.
• the vinyl ester used in the production of PVA is as described for the polyvinyl acetal resin, preferably vinyl acetate.
• PVA may be unmodified PVA or modified PVA, but modified PVA is preferred.
• the modified PVA preferably has a polyalkylene oxide structure.
• the polyalkylene oxide structure has the structure of the formula (1) as described in the polyvinyl acetal-based resin, and details such as the amount of modification are as described above.
• unmodified PVA examples include those obtained by saponifying polyvinyl ester.
• Modified PVA includes saponified polymers of vinyl esters and other unsaturated monomers.
• the degree of saponification of polyvinyl alcohol is generally 70-99.9 mol %.
• other unsaturated monomers include unsaturated monomers having modifying groups, preferably unsaturated monomers having a polyalkylene oxide structure.
• the unsaturated monomer having a polyalkylene oxide structure is preferably a vinyl monomer having a polyoxyalkylene group represented by the above formula (4).
• the details of the vinyl monomer having a polyoxyalkylene group are as described above for the polyvinyl acetal resin.
• the polyvinyl alcohol-based resin can be produced in the same manner as the raw material polyvinyl alcohol described above.
• Polyvinyl alcohol-based resins can be produced by, for example, the above-described production method, so that the low-molecular-weight components can be reduced, so that the value of (AB)/A can be easily reduced.
• PVA generally has a structural unit of the above formula (3-2), but in addition to the structural unit of the above formula (3-2), it has a structural unit of the above formula (3-3).
• PVA preferably has a polyalkylene oxide structure, and therefore preferably has a structural unit represented by formula (2), among which the above formulas (2-1) and (2-2) It is more preferable to have any of the structural units represented by The details of formula (2), formula (2-1) and formula (2-2) are as described above.
• the acrylic resin used as resin (X) is an acrylic polymer.
• An acrylic polymer is a homopolymer of an acrylic monomer having a (meth)acryloyl group in its molecule, or a copolymer obtained by copolymerizing a monomer containing an acrylic monomer.
• Acrylic resin may be used individually by 1 type, and may use 2 or more types together.
• (meth)acryloyl group means acryloyl group or methacryloyl group
• (meth)acrylate” means acrylate or methacrylate, and the same applies to other similar terms.
• An acrylic monomer constituting an acrylic polymer is, for example, a monofunctional monomer having one (meth)acryloyloxy group.
• acrylic monomers include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, and aromatic ring-containing (meth)acrylates.
• Monofunctional monomers constituting acrylic polymers include monomers having functional groups such as cyclic ether groups, hydroxyl groups, carboxyl groups, amino groups, amide groups, polyoxyethylene groups, and alkoxy groups (hereinafter referred to as "functional group-containing (also referred to as "monomer").
• functional group-containing monomers include cyclic ether group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, carboxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers, polyoxyethylene group-containing monomers, Examples include alkoxy-containing monomers.
• alkyl (meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 18 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, isomyristyl (meth) Acrylate, stearyl (meth)acrylate, isostearyl (meth) (
• the alicyclic structure-containing (meth)acrylates include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.
• aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate.
• Cyclic ether group-containing (meth)acrylates include those having an epoxy ring.
• Epoxy ring-containing (meth)acrylates include, for example, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, 5- Hydroxypentyl (meth)acrylate glycidyl ether, 6-hydroxyhexyl (meth)acrylate glycidyl ether and the like.
• Carboxyl group-containing monomers include acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone mono(meth)acrylate, ⁇ -carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth) ) acryloyloxyethyl hexahydrophthalic acid and the like.
• the number of repeating units of polycaprolactone in ⁇ -carboxy-polycaprolactone mono(meth)acrylate is about 2-5, preferably 2-3.
• the carboxyl group-containing acrylic monomer is preferably at least one selected from the group consisting of acrylic acid and methacrylic acid.
• hydroxyl group-containing acrylic monomers examples include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like. Among these, 2-hydroxyethyl (meth)acrylate is preferable.
• amino group-containing monomers include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate and the like.
• Amide group-containing monomers include N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-diethyl(meth)acrylamide and N-hydroxyethyl(meth)acrylamide.
• Polyoxyethylene-containing (meth)acrylates include diethylene glycol monoethyl ether (meth)acrylate.
• Alkoxy-containing monomers include 3-methoxybutyl (meth)acrylate.
• the monomers constituting the acrylic polymer preferably contain one or more selected from the group consisting of alkyl (meth)acrylates and alicyclic structure-containing (meth)acrylates.
• the total content of monomers selected from these is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total amount of monomers constituting the acrylic polymer.
• alkyl (meth)acrylates are preferably used as monomers constituting the acrylic polymer.
• the alkyl (meth)acrylate is more preferably used together with one selected from alicyclic structure-containing (meth)acrylates, and more preferably used together with the alicyclic structure-containing (meth)acrylate.
• the acrylic monomer constituting the acrylic polymer preferably contains the functional group-containing monomer in addition to the acrylic monomer selected from the group consisting of alkyl (meth)acrylates and alicyclic structure-containing (meth)acrylates.
• the total content of functional group-containing monomers is preferably 0.05% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 40% by mass or less, and still more preferably based on the total amount of monomers constituting the acrylic polymer. is 1% by mass or more and 30% by mass or less.
• the functional group-containing monomer preferably contains a carboxyl group-containing monomer among those described above.
• the acrylic monomer constituting the acrylic polymer contains a carboxyl group-containing monomer, the cohesive force of the resin is improved, the adhesiveness can be improved, and the resin can be appropriately used as a binder.
• the carboxyl group-containing monomer should be used only in a small amount in order to reduce the amount of carboxyl groups, as described above. Therefore, the content of the carboxyl group-containing monomer is preferably 0.003% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, based on the total amount of monomers constituting the acrylic polymer. It is preferably 0.01% by mass or more and 1% by mass or less.
• Monomers other than the above-described monomers may be used in combination with the monomers that constitute the acrylic polymer.
• polyfunctional monomers may be used as the monomers constituting the acrylic polymer as long as they do not impair the effects of the present invention.
• a known polyfunctional (meth)acrylate may be used as the polyfunctional monomer.
• the acrylic polymer may be polymerized by a solution polymerization method, a suspension polymerization method, or the like, but may be polymerized by irradiating an active energy ray.
• the acrylic polymer should have a low amount of low molecular weight components in order to lower the value of (AB)/A. Therefore, the acrylic polymer is preferably polymerized by irradiation with active energy rays, particularly ultraviolet rays (UV).
• Active energy rays particularly ultraviolet rays (UV).
• Polymerization with active energy rays is preferably carried out in the presence of a polymerization initiator. More preferably, the polymerization is carried out by UV irradiation without containing components (solvent, etc.) other than the monomer and the initiator in the reaction system.
• the resin composition of the present invention is a resin composition containing resin (X).
• the resin composition may contain components other than the resin (X) depending on its use, and may contain, for example, a plasticizer and additives other than the plasticizer as appropriate.
• Additives other than plasticizers include, specifically, ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesion modifiers, pigments, dyes, fluorescent brighteners, crystal nucleating agents, surfactants and dispersants such as agents.
• the resin composition of the present invention may contain resin components other than the resin (X) within a range that does not impair the effects of the present invention.
• the resin composition of the present invention contains a solvent and may be used after being diluted with a solvent.
• the resin composition of the present invention may contain a plasticizer as described above. By containing a plasticizer, the resin composition becomes flexible and can be easily molded into a predetermined shape such as a sheet. However, the resin composition of the present invention preferably does not contain a plasticizer or contains a small amount of plasticizer. By containing only a small amount of the plasticizer or not containing it, it becomes easier to improve the shape stability after molding the resin composition into a predetermined shape such as a sheet. In addition, the resin composition of the present invention can improve the adhesiveness to various materials by using the above-described predetermined resin (X) even if the plasticizer is small or not contained, and can be used as a binder. The physical properties of are sufficiently secured.
• X predetermined resin
• the content of the plasticizer in the resin composition is preferably less than 40 parts by mass with respect to 100 parts by mass of the resin (X) contained in the resin composition. By setting the plasticizer to less than 40 parts by mass, it becomes easier to improve the shape stability after molding the resin composition into a predetermined shape such as a sheet.
• the content of the plasticizer is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.
• the content of the plasticizer may be 0 parts by mass or more, it is also preferable that the resin composition does not contain the plasticizer, that is, the content of the plasticizer is 0 parts by mass.
• plasticizers include organic ester plasticizers, organic phosphorus plasticizers such as organic phosphate ester plasticizers and organic phosphite ester plasticizers, polyalkylene glycol plasticizers, polyoxyalkylene ether plasticizers, and the like. organic ether-based plasticizers, alcohol-based plasticizers, and the like.
• a plasticizer may be used individually by 1 type, and may use 2 or more types together. Among them, organic ester plasticizers and polyalkylene glycol plasticizers are preferred, and organic ester plasticizers are more preferred.
• Preferred organic ester plasticizers include monobasic organic acid esters and polybasic organic acid esters. Also, the type of plasticizer to be used may be appropriately selected depending on the type of resin (X).
• the resin (X) is either a polyvinyl acetal resin or an acrylic resin
• an organic ester plasticizer is preferably used. It is preferable to use a polyalkylene glycol-based plasticizer.
• Monobasic organic acid esters include esters of glycols with monobasic organic acids.
• Glycols include polyalkylene glycols in which each alkylene unit has 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and the number of repeating alkylene units is 2 to 10, preferably 2 to 4.
• the glycol may also be a monoalkylene glycol having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms (that is, 1 repeating unit).
• Specific examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and butylene glycol.
• Examples of monobasic organic acids include organic acids having 3 to 10 carbon atoms, and specific examples include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, and 2-ethylhexylic acid. , n-nonylic acid and decylic acid.
• Specific monobasic organic acids include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, di Propylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol Di-n-heptanoate, triethylene glycol di-2-ethylbutyrate,
• polybasic organic acid esters examples include ester compounds of dibasic organic acids having 4 to 12 carbon atoms such as adipic acid, sebacic acid, azelaic acid and phthalic acid and alcohols having 4 to 10 carbon atoms. is mentioned.
• the alcohol having 4 to 10 carbon atoms may be linear, branched, or cyclic.
• oil-modified alkyd sebacic acid may be used.
• Mixed adipates include adipates prepared from two or more alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms.
• the organic phosphorus plasticizer include phosphoric acid esters such as tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.
• the organic ester plasticizer is not limited to the complete ester of each ester described above, and may be a partial ester.
• it may be a partial ester between a glycol and a monobasic organic acid, or a partial ester between a dibasic organic acid and an alcohol.
• Specific examples include triethylene glycol-mono-2-ethylhexanoate.
• it may be a trihydric or higher alcohol such as glycerin and a partial ester of a monobasic organic acid.
• Monobasic organic acids include monobasic organic acids having 3 to 24 carbon atoms, preferably 6 to 18 carbon atoms.
• partial esters of trihydric or higher alcohols and monobasic organic acids include mono- or diesters of glycerin and stearic acid and mono- or diesters of glycerin and 2-ethylhexyl acid.
• organic ester plasticizers triethylene glycol-di-2-ethylhexanoate (3GO) and dioctyl adipate (DOA) are particularly preferably used.
• Polyalkylene glycol-based plasticizers include polyethylene glycol, polypropylene glycol, poly(ethylene oxide/propylene oxide) block copolymer, poly(ethylene oxide/propylene oxide) random copolymer, polytetramethylene glycol and the like. Among them, polypropylene glycol is preferred.
• a polyoxyalkylene ether-based plasticizer is an ether compound of a monohydric or polyhydric alcohol and polyoxyalkylene.
• Specific polyoxyalkylene ether plasticizers include, for example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene nonyl ether, polyoxyethylene Ethylene decyl ether, polyoxyethylene allyl ether, polyoxypropylene allyl ether, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyalkylene pentaerythritol ether, poly and caprolactone triol.
• the polyoxyalkylene ether plasticizer is preferably an ether compound of polyhydric alcohol and polyoxyalkylene, more preferably an ether compound of glycerin or diglycerin and polyoxyalkylene, still more preferably glycerin or diglycerin. and polyoxypropylene.
• Alcohol plasticizers include alcohols other than polyalkylene glycol plasticizers and polyoxyalkylene ether plasticizers. Specific examples include various polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, pentaerythritol, glycerin and diglycerin. Among these, ethylene glycol is preferred.
• the resin other than the resin (X) that can be used in combination with the resin (X) is preferably a thermoplastic resin.
• thermoplastic resins used for resins other than resin (X) include polyvinyl acetal resins, acrylic resins, polyvinyl alcohol resins, polyvinyl acetates, ethylene-vinyl acetate copolymers, polyurethane resins, and ionomers. resin.
• polyvinyl acetal-based resins, acrylic-based resins, and polyvinyl alcohol-based resins are preferable, and polyvinyl acetal-based resins are more preferable. These may be used individually by 1 type, and may use 2 or more types together.
• the content of the resin other than the resin (X) may be within a range that does not impair the object of the present invention.
• it is less than 100 parts by mass, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 15 parts by mass or less.
• the lower limit thereof is not particularly limited, and may be 0 parts by mass or more.
• the resin (X) and resin composition of the present invention can be used in various applications.
• the resin (X) and the resin composition may be used in interlayer films for laminated glass, inks, paints, baking enamels, lacquers, ceramic green sheets, electrode pastes, heat-developable photosensitive materials, ink image-receiving layers. , lithium ion batteries, solar batteries, pressure-sensitive adhesive sheets, modifiers, etc., as a binder. It may also be used as an additive or dispersant in each of these uses or other than these uses.
• the sheet containing the resin (X) may be used as a protective sheet or the like that is attached to an adherend to protect the adherend in the manufacturing process.
• the protective sheet is preferably attached to a wafer or the like in a semiconductor manufacturing process to protect the wafer or the like. Since the sheet containing the resin (X) of the present invention is excellent in shape stability after sheet molding, it becomes easy to protect various adherends. When used as a protective sheet, the protective sheet may have at least one layer made of the resin composition containing the resin (X).
• the resin (X) and the resin composition are preferably used in combination with an inorganic powder, as described later, and particularly preferably used for firing.
• the resin composition containing the inorganic powder described later is formed into a predetermined shape such as a sheet, and then fired to obtain a fired product. preferably used in a method.
• the resin (X) and the resin composition are preferably used for ceramic green sheets or electrode pastes among the above.
• the resin composition of the present invention preferably contains an inorganic powder in addition to the resin (X). Further, even when the resin composition contains inorganic powder, as described above, the resin composition may appropriately contain a plasticizer or an additive other than the plasticizer.
• the resin composition containing inorganic powder will be referred to as "inorganic powder-containing resin composition”
• the later-described inorganic powder-containing resin composition in the form of slurry will be referred to as "slurry composition”.
• the inorganic powder-containing resin composition generally further contains a solvent and is preferably used in the form of slurry.
• the resin (X) of the present invention has high inorganic powder solution stability, and when used in combination with an inorganic powder in a slurry, improves the dispersibility of the inorganic powder and prevents the viscosity of the slurry from increasing. can be done.
• the content of the resin (X) in the slurry composition is preferably 1% by mass or more and 20% by mass or less with respect to the total amount of the slurry composition.
• the content of the resin (X) in the slurry composition By setting the content of the resin (X) in the slurry composition to 1% by mass or more, the film-forming property and flexibility of the ceramic green sheet can be improved, and the occurrence of cracks and the like after sintering can be prevented. Moreover, by setting the resin (X) content to 20% by mass or less, the viscosity of the slurry composition is prevented from becoming too high, and the dispersibility of the slurry composition is prevented from deteriorating. Moreover, the decarbonization property at the time of firing can be improved.
• the content of the resin (X) in the slurry composition is more preferably 2% by mass or more and 10% by mass or less, and still more preferably 2.5% by mass or more and 5% by mass or less.
• the inorganic powder any suitable type can be used depending on the application, but ceramic powder is preferable.
• ceramic powder the inorganic powder-containing resin composition can be suitably used for ceramic green sheets.
• the ceramic powder is not particularly limited, and examples thereof include alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, magnesia, sialon, spinemullite, crystallized glass, silicon carbide, silicon nitride, and aluminum nitride. and other powders. These ceramic powders may be used alone or in combination of two or more.
• the ceramic powder may be MgO—SiO 2 —CaO, B 2 O 2 —SiO 2 , PbO—B 2 O 2 —SiO 2 , CaO—SiO 2 —MgO—
• a glass frit such as B 2 O 2 or PbO—SiO 2 —B 2 O 2 —CaO may be added.
• the inorganic-containing resin composition can be suitably used for the electrode paste.
• the conductive powder is not particularly limited, and examples thereof include nickel, copper, aluminum, silver, gold, platinum, palladium, solder, tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO ) and the like.
• the content of the inorganic powder with respect to the total amount of the slurry composition is preferably 20% by mass or more and 80% by mass or less.
• the content is 20% by mass or more, the viscosity is prevented from becoming too low, and the handleability when molding a ceramic green sheet or the like is improved.
• the content of the inorganic powder is 80% by mass or less, the viscosity of the slurry composition is prevented from becoming too high. More preferably, the content of the inorganic powder is 30% by mass or more and 70% by mass or less.
• the solvent contained in the slurry composition may be water or an organic solvent, but an organic solvent is preferred.
• the organic solvent is not particularly limited, and examples include ketones such as acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone; alcohols such as methanol, ethanol, isopropanol and butanol; aromatic hydrocarbons such as toluene and xylene; Methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, acetic acid 2 esters such as -ethylhexyl and 2-ethylhexyl ketone
• the content of the solvent with respect to the total amount of the slurry composition is preferably 20% by mass or more and 80% by mass or less.
• the slurry composition is provided with appropriate mixability, and the viscosity is set in an appropriate range, so that the handleability when molding a ceramic green sheet or the like is improved.
• the solvent content is 30% by mass or more and 70% by mass or less.
• the slurry composition is preferably used for ceramic green sheets or electrode pastes. Accordingly, one embodiment of the present invention also provides a ceramic green sheet or electrode paste obtained using the above slurry composition.
• the method for producing the ceramic green sheet is not particularly limited, and the ceramic green sheet can be produced by a conventionally known production method. For example, after defoaming the slurry composition as necessary, it is applied in the form of a film onto a peelable support such as a polyethylene terephthalate film, and the solvent and the like are distilled off by heating or the like. A peeling method and the like can be mentioned.
• the ceramic green sheet is decarbonized by firing as described below to decompose the resin (X) to obtain a fired ceramic body. A fired ceramic body is commonly used as a dielectric layer.
• the electrode paste can be prepared by mixing the resin (X), the conductive powder, and an optional solvent.
• Ceramic green sheets are typically used to manufacture multilayer ceramic capacitors.
• the laminated ceramic capacitor is preferably obtained by using the above ceramic green sheets and electrode paste, and is preferably obtained by laminating ceramic green sheets coated with electrode paste.
• a multilayer ceramic capacitor can be manufactured by a conventionally known manufacturing method.
• the surface of the ceramic green sheet of the present invention is coated with an electrode paste to be an internal electrode by screen printing or the like, and a plurality of sheets are stacked and heat-pressed to obtain a laminate.
• the laminate is heated to thermally decompose and remove the resin (X) and the like contained in the laminate to obtain a sintered body, and an external electrode is attached to the sintered body. can be manufactured.
• the present invention will be described in more detail by way of examples, the present invention is not limited by these examples.
• the measuring method of each physical-property value in this invention, and the evaluation method are as follows.
• ⁇ Weight average molecular weight (Mw)> A polyvinyl acetal-based resin, a polyvinyl alcohol-based resin, or an acrylic resin (resin (X) or resin (x)) was dissolved in tetrahydrofuran to a concentration of 0.05% by weight. Then, after filtering using a syringe filter (Merck, Millex-LH 0.45 ⁇ m), the molecular weight was measured using gel permeation chromatography (GPC, Waters, e2690). Weight average molecular weight (Mw) was calculated using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples. Shodex GPC KF-806L (manufactured by Showa Denko) was used as a column, and tetrahydrofuran was used as an eluent.
• the resin (X) obtained in each example and the resin (x) obtained in the comparative example were set as measurement samples and measured using a thermal analyzer (TG/DTA7300, manufactured by Hitachi High-Tech Science). In the atmosphere, the temperature is raised from 40 ° C. to 600 ° C. at a rate of 5 ° C./min and held at 600 ° C. for 10 minutes. B, the weight at the time of holding at 600° C. for 10 minutes was measured as C. From the measured A, B, and C, the value of (AB)/A and the value of (AC)/A were calculated.
• TG/DTA7300 manufactured by Hitachi High-Tech Science
• ⁇ Inorganic powder solution stability> The slurry compositions obtained in each example and comparative example were subjected to particle size distribution measurement using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., LA-910) to measure the average particle size. In addition, the average particle size after standing at 23° C. for one week was also measured, and the average particle size change rate was evaluated according to the following criteria. In addition, the lower the average particle size change rate, the higher the inorganic powder solution stability. I: less than 40% II: 40% or more and less than 80% III: 80% or more
• Example 1 [Synthesis of propylene oxide-modified polyvinyl alcohol] An allyl ether monomer (1) represented by formula (4-2) was prepared.
• the allyl ether monomer (1) has an oxypropylene group (PO) as A 1 O, an average repetition number of 25, and a hydrogen atom as a terminal group (R 1 ).
• PO oxypropylene group
• R 1 a hydrogen atom as a terminal group
• 723 parts by mass of vinyl acetate, 257 parts by mass of allyl ether monomer (1), and 20 parts by mass of methanol were added to a flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, and the system was purged with nitrogen. After that, the temperature was raised to 60°C.
• resin solution (X') 90 parts by mass of resin (X) and 10 parts by mass of triethylene glycol-di-2-ethylhexanoate (3GO) as a plasticizer were added to 900 parts by mass of an ethanol/toluene mixed solvent (mass ratio of 1:1), A resin solution (X') was prepared by stirring and dissolving.
• slurry composition 1 part by mass of polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd., BL-1) is added to a mixed solvent of 20 parts by mass of ethanol and 20 parts by mass of toluene, dissolved and stirred, and 100 parts by mass of barium titanate powder (Sakai BT01 manufactured by Kagaku Kogyo Co., Ltd.) was added and stirred for 60 minutes with a bead mill. Thereafter, 100 parts by mass of the previously obtained resin solution (X') was added and stirred for 180 minutes in a bead mill (manufactured by Imex, Ready Mill) to prepare an inorganic dispersion (slurry composition). Each evaluation was performed using the obtained slurry composition. Table 1 shows the evaluation results.
• Example 2 Allyl ether monomer (2) was used as the allyl ether monomer.
• a 1 O is a mixture of oxypropylene group (PO) and oxyethylene group (EO), and the average number of repetitions is 34 and 34, respectively.
• rice field Moreover, the terminal group (R 1 ) was a hydrogen atom.
• a modified polyvinyl butyral resin (EO/PO-PVB) was obtained in the same manner as in Example 1, except that 515 parts by mass of vinyl acetate, 152 parts by mass of allyl ether monomer (2), and 333 parts by mass of methanol were used.
• Table 1 shows the structure and physical properties of the resulting modified polyvinyl butyral resin (resin (X)). Further, instead of PO-PVB1, the obtained modified polyvinyl butyral resin (EO/PO-PVB) is used, and the resin (X) and the plasticizer are mixed in the resin solution (X') without using a plasticizer.
• a slurry composition was prepared in the same manner as in Example 1, except that the number of parts (mass parts) was changed as shown in Table 1. Each evaluation was performed using the produced slurry composition. Table 1 shows the evaluation results.
• Example 3 Allyl ether monomer (3) was used as the allyl ether monomer.
• a 1 O of allyl ether monomer (3) was an oxyethylene group (EO), and the average number of repetitions was 33.
• the terminal group (R 1 ) was a hydrogen atom.
• Modified polyvinyl butyral resin (EO-PVB) was prepared in the same manner as in Example 1, except that the allyl ether monomer (3), 834 parts by mass of vinyl acetate, 147 parts by mass of allyl ether monomer (3), and 20 parts by mass of methanol were used. got Table 1 shows the structure and physical properties of the resulting modified polyvinyl butyral resin (resin (X)).
• modified polyvinyl butyral resin (EO-PVB) was used instead of PO-PVB1, and the number of parts (mass parts) of the resin (X) and the plasticizer in the resin solution (X') was shown in Table 1.
• a slurry composition was prepared in the same manner as in Example 1, except for changing as described in . Each evaluation was performed using the produced slurry composition. Table 1 shows the evaluation results.
• Example 4 The propylene oxide-modified polyvinyl alcohol (PO-PVA) produced in Example 1 was used as resin (X).
• Table 1 shows the structure and physical properties of PO-PVA (resin (X)).
• the obtained PO-PVA was measured after reacetylating all the hydroxyl groups by a conventional method.
• a resin solution ( X′) was prepared, and a composition was prepared in the same manner as in Example 1, except that the mixed solvent used for preparing the slurry composition was changed to water. Each evaluation was performed using the produced slurry composition. Table 1 shows the evaluation results.
• Example 5 30 parts by weight of 2-ethylhexyl acrylate (2EHA), 45 parts by weight of isobornyl acrylate (IBOA), 15 parts by weight of dimethylacrylamide, 9.99 parts by weight of 2-hydroxyethyl acrylate (HEA), and 0.2 parts by weight of acrylic acid (Aac). 01 parts by mass and 0.2 parts by mass of a photopolymerization initiator ("IRGACURE 184", manufactured by BASF) were mixed. This was sandwiched between two single-sided release-treated PET sheets and a spacer was arranged so that the thickness was 100 ⁇ m. It was dissolved in THF and reprecipitated with ethanol. Acrylic polymer 1 was obtained by drying at 100° C. for 1 hour.
• 2EHA 2-ethylhexyl acrylate
• IBOA isobornyl acrylate
• HOA 2-hydroxyethyl acrylate
• Aac acrylic acid
• Table 1 shows the physical properties of the obtained acrylic polymer 1 (resin (X)). Except that 97 parts by mass of the obtained acrylic polymer 1 was used instead of PO-PVB1, dioctyl adipate (DOA) was used as a plasticizer, and the amount was changed to 3 parts by mass.
• a resin solution (X') was prepared in the same manner as in Example 1, and a slurry composition was obtained from the resin solution (X'). Each evaluation was performed using the produced slurry composition. Table 1 shows the evaluation results.
• Barium powder (BT01, manufactured by Sakai Chemical Industry Co., Ltd.) was added and dispersed using a bead mill (Ready Mill, manufactured by Imex Corporation). After that, the mixed liquid was transferred to three rolls, 100 parts by mass of nickel powder (manufactured by Sumitomo Metal Mining Co., Ltd., average particle size 0.2 ⁇ m) was added, and kneaded for 180 minutes to prepare an inorganic dispersion (slurry composition). Each evaluation was performed.
• a vinyl monomer represented by formula (4) was prepared.
• a 1 O was an oxyethylene group (EO) and an oxypropylene group (PO), and the average number of repetitions was 8 and 18, respectively.
• EO and PO were each present in blocks, and there were polyoxyethylene and polyoxypropylene blocks.
• the terminal group (R 1 ) was a hydrogen atom.
• the linking group (R 2 ) was an amide bond (-CONH-*). * is the bonding position with A 1 O.
• Polymer powder of modified polyvinyl alcohol resin (EO/PO block-PVA) was prepared in the same manner as in Example 2 except that 65 parts by mass of the vinyl monomer was used and 425 parts by mass of vinyl acetate and 510 parts by mass of methanol were used. got
• PVB-acrylic was obtained by cooling to room temperature.
• Table 1 shows the physical properties of the obtained PVB-acrylic (resin (x)).
• Example 1 except that the obtained PVB-acrylic was used instead of PO-PVB1, dioctyl phthalate (DOP) was used as a plasticizer, and the blending amounts were changed as shown in Table 1.
• a resin solution (x') was prepared in the same manner as above, and a slurry composition was obtained from the resin solution (x'). Each evaluation was performed using the produced slurry composition. Table 1 shows the evaluation results.

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