JP6162962B2 - Polyoxyalkylene-modified vinyl acetal polymer, production method and composition thereof - Google Patents

Description

  The present invention relates to a polyoxyalkylene-modified vinyl acetal polymer, a method for producing the same, a composition, and a use of the composition.

  A vinyl acetal polymer typified by a vinyl butyral polymer is excellent in toughness, film-forming property, dispersibility of added inorganic or organic powder, adhesion to a coated surface, and the like. Therefore, the vinyl acetal polymer is used for interlayer films of laminated glass, inks, paints, baking enamels, wash primers, lacquers, dispersants, adhesives, ceramic green sheets, photothermographic materials, water-based ink receiving layers. It is used in various applications such as binders. The main reason why the vinyl acetal polymer is used in such various applications is that the vinyl acetal polymer has excellent toughness, but on the other hand, there is also a disadvantage that the flexibility is somewhat poor. . In addition, since the vinyl acetal polymer has a high glass transition temperature, there is also a disadvantage that the fluidity is low even at a high temperature.

  In order to perform thermoplastic processing on the vinyl acetal polymer, for example, phthalate ester of alcohol having 6 to 10 carbon atoms, triethylene glycol di-n-heptanoate, tri (2-ethylhexyl) phosphate, It is necessary to add a plasticizer such as tricresyl phosphate. However, the composition containing the vinyl acetal polymer and the plasticizer, if the plasticizer is not properly selected, is easily phase-separated and the plasticizer is eluted in the solvent, and the properties of the composition are remarkably changed. There are inconveniences. For this reason, films, sheets, and the like obtained from the above composition have insufficient film strength, transparency, storage stability, and the like, and ink may flow out when printing on the surface.

  Accordingly, attempts have been made to internally plasticize the vinyl acetal polymer in order to prevent such deterioration of various physical properties due to the addition of the plasticizer. For example, the side chain of a vinyl alcohol polymer (hereinafter sometimes abbreviated as “PVA”) is modified with a polyoxyalkylene group (hereinafter sometimes abbreviated as “POA group”), and then acetalized. The resulting modified vinyl acetal polymer has been developed. This modified vinyl acetal polymer is said to have an internal plasticizing action by the side chain polyoxyalkylene groups, and the flexibility of the green sheet produced using the modified vinyl acetal polymer is said to be improved. (See JP-A-6-263521). However, the polyoxyalkylene group is composed of a single oxyalkylene unit and is mainly a polyoxyethylene group or a polyoxypropylene group. When such a modified vinyl acetal polymer having a polyoxyalkylene group is processed into a film or sheet, unreacted monomers remaining during polymerization cause yellowing, turbidity, and yellowing in the resulting film or sheet. There is an inconvenience. In addition, when this modified vinyl acetal polymer is used as a ceramic binder, the dispersibility of the ceramic powder in the modified vinyl acetal polymer is insufficient, and the flexibility of the resulting green sheet and the like is poor. There are inconveniences such as sufficient. Furthermore, since this modified vinyl acetal polymer has poor storage stability, there are also disadvantages such as an increase in viscosity over time.

  There has also been proposed a vinyl acetal polymer obtained by acetalizing PVA with oxyethylene aldehydes / oxyalkanals whose ends are etherified (see JP-A-2-300209). This vinyl acetal polymer has a high content of vinyl alcohol units, and can be processed thermoplastically without the addition of a plasticizer, and has good adhesiveness to metals and glass. ing. However, since unreacted oxyethylene aldehydes / oxyalkanals remain in the vinyl acetal polymer obtained by this method, it becomes turbid and yellowed when processed into a film or sheet. There is an inconvenience.

  Further, a polymer obtained by acetalizing PVA containing a 1,2-diol component in the side chain as a vinyl acetal polymer that exhibits improved flexibility, reduced viscosity, and good viscosity stability. Is disclosed (see JP 2006-104309 A). However, when this vinyl acetal polymer is processed into a film, sheet or the like, there is an inconvenience that its film strength is insufficient.

JP-A-6-263521 JP-A-2-300209 JP 2006-104309 A

  The present invention has been made based on the above-mentioned circumstances, has sufficient plasticity, solubility in alcohol solvents, low viscosity and viscosity stability of the solution, and causes phase separation with other components. It is an object of the present invention to provide a polyoxyalkylene-modified vinyl acetal polymer that is difficult to obtain a slurry excellent in particle dispersibility and thixotropy and a sheet excellent in strength, peelability and flexibility.

The invention made to solve the above problems is
A polyoxyalkylene-modified vinyl acetal polymer obtained by acetalizing a polyoxyalkylene-modified vinyl alcohol polymer,
Monomer containing a block represented by the following formula (1) (hereinafter also referred to as “block (1)”) and a block represented by the following formula (2) (hereinafter also referred to as “block (2)”) The monomer unit content is 0.05 mol% or more and 10 mol% or less, the viscosity average polymerization degree is 150 or more and 5,000 or less, and the degree of acetalization is 10 mol% or more and 85 mol%. % Polyoxyalkylene-modified vinyl acetal polymer (hereinafter also referred to as “POA-modified vinyl acetal polymer”).

（式（１）中、Ｒ^１及びＲ^２は、いずれか一方がメチル基であり、他方が水素原子である。ｍは、繰り返し単位数を表し、１０以上４０以下の整数である。複数のＲ^１及びＲ^２は、それぞれ同一でも異なっていてもよい。）

(In Formula (1), ^one of R ¹ and R ² is a methyl group and the other is a hydrogen atom. M represents the number of repeating units and is an integer of 10 to 40.] R ¹ and R ² may be the same or different.)

（式（２）中、ｎは、繰り返し単位数を表し、１以上５０以下の整数である。）

(In formula (2), n represents the number of repeating units and is an integer of 1 to 50.)

  The POA-modified vinyl acetal polymer has a low glass transition point, excellent plasticity, high solubility in an alcohol solvent, a low solution viscosity, and an excellent stability of the solution viscosity over time. In addition, the POA-modified vinyl acetal polymer hardly causes phase separation with other components when formed into a composition, is excellent in dispersibility of inorganic particles such as ceramic powder, and is particularly a composition such as a slurry-like paint. In this case, thixotropy can be imparted. Furthermore, films, sheets, and the like obtained by processing the POA-modified vinyl acetal polymer are excellent in strength, ease of peeling, and flexibility. The details of the mechanism by which the POA-modified vinyl acetal polymer exhibits the above-mentioned effects have not been clarified. For example, the POA-modified vinyl acetal polymer includes the block (1) and the block (2) having the specific structure. It is presumed that the inclusion of the monomer unit increases the hydrophobic interaction between POA groups between the molecules of the vinyl acetal polymer, resulting in excellent internal plasticity. . Further, the viscosity average polymerization degree of the POA-modified vinyl acetal polymer and the content of the monomer unit are within the specific range, so that the solubility in an alcohol solvent, the film obtained by processing, and the sheet are obtained. Etc., such as excellent strength. Furthermore, by setting the degree of acetalization of the POA-modified vinyl acetal polymer within the above specified range, the solubility in an alcohol solvent can be improved and the solution viscosity can be kept low. Can be improved.

  The monomer unit preferably has a block represented by the above formula (1) and a block represented by the above formula (2) in the side chain. It is considered that the above-mentioned hydrophobic interaction is strengthened when the monomer unit has the respective blocks in the side chain, and as a result, the internal plasticity of the POA-modified vinyl acetal polymer is further increased. Can do.

  The block represented by the above formula (1) is preferably located closer to the main chain than the block represented by the above formula (2). Thus, it is considered that the hydrophobic interaction described above is further strengthened by having the respective blocks at the specific positions, and as a result, the internal plasticity of the POA-modified vinyl acetal polymer can be further increased. . Although the details of the mechanism that exerts the above-mentioned effect by locating the block (1) on the main chain side from the block (2) have not been clarified, for example, a polyoxyethylene block (block (2) that is relatively hydrophilic) ) On the terminal side of the POA group, the hydrophobic interaction between POA groups between molecules of the POA-modified vinyl acetal polymer is further promoted.

  It is preferable that the block represented by the formula (1) and the block represented by the formula (2) are directly bonded. When these blocks are located adjacent to each other, the internal plasticity of the POA-modified vinyl acetal polymer can be further enhanced.

  The aldehyde used for acetalization is preferably at least one selected from the group consisting of butyraldehyde and acetaldehyde, and butyraldehyde is particularly preferable. By acetalizing using the specific aldehyde, the POA-modified vinyl acetal polymer can be produced efficiently.

  The composition of the present invention contains the POA-modified vinyl acetal polymer. Since the composition contains the POA-modified vinyl acetal polymer, it is excellent in particle dispersibility, strength, ease of peeling, flexibility, etc. In addition to the binder of the internal electrode of the ceramic green sheet or multilayer ceramic capacitor, For example, it can be widely used as coating materials such as paints, inks, adhesives, powder paints, heat-developable photosensitive materials, pellets, films and the like.

  The composition further contains a ceramic powder and an organic solvent, and is preferably used as a slurry composition for a ceramic green sheet. Since the composition contains the POA-modified vinyl acetal polymer, the ceramic powder, which is an inorganic particle, has excellent dispersibility, and the ceramic powder is uniformly dispersed without agglomeration. It can be suitably used as a product. Moreover, since the said composition has high thixotropic property, it is excellent also in handling property.

  The ceramic green sheet of the present invention is obtained using the above-described composition. Since the ceramic green sheet uses the composition containing the POA-modified vinyl acetal polymer, the ceramic particles are uniformly dispersed in the sheet and are excellent in balance in strength, ease of peeling, and flexibility. .

  The multilayer ceramic capacitor of the present invention is obtained using the ceramic green sheet. The ceramic green sheet exhibits high performance as a ceramic dielectric because the ceramic powder is uniformly dispersed in the sheet. The multilayer ceramic capacitor produced by laminating such ceramic green sheets has an excellent function as a capacitor and high reliability.

  The interlayer film for laminated glass of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the interlayer film for laminated glass is excellent in whitening resistance, penetration resistance, and adhesion to glass when exposed to a long period of time under high humidity.

  The ink of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the ink has a low solution viscosity and has sufficient ink dispersibility.

  The coating agent of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the coating agent has sufficient handleability and viscosity stability, and can obtain a film having high water resistance and water stopping performance.

  The photothermographic material of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the heat developable photosensitive material is excellent in heat developability and image stability after development.

  The conductive paste of the present invention contains the POA-modified vinyl acetal polymer. Accordingly, the conductive paste is excellent in printability such as thixotropy, yarn pulling resistance, bleeding resistance, and sheet attack resistance.

  The pellet of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the pellet has the characteristics that the apparent specific gravity is large, the handleability is good, and the odor is hardly generated at the time of manufacturing and handling.

  The film of the present invention contains the POA-modified vinyl acetal polymer and does not contain a plasticizer. The film is excellent in internal plasticity by containing the POA-modified vinyl acetal polymer, and the film does not become hard even if it does not contain a plasticizer and has sufficient handleability and suppresses the generation of droplets. Can do.

The method for producing the polyoxyalkylene-modified vinyl acetal polymer of the present invention comprises:
By copolymerization of an unsaturated monomer represented by the following formula (3) and a vinyl ester monomer, the viscosity average polymerization degree is 150 to 5,000, and the content of the unsaturated monomer unit is A step of obtaining 0.05 to 10 mol% of a polyoxyalkylene-modified vinyl ester polymer,
A step of obtaining a polyoxyalkylene-modified vinyl alcohol polymer having a saponification degree of 20 mol% or more and 99.99 mol% or less by saponification of the polyoxyalkylene-modified vinyl ester polymer; and A step of obtaining a polyoxyalkylene-modified vinyl acetal polymer having a degree of acetalization of 10 mol% to 85 mol% by acetalization of the polymer;

（式（３）中、Ｒ^３は、水素原子又は炭素数１〜８のアルキル基である。Ｒ^４は、水素原子又はメチル基である。Ｘは−Ｏ−、−ＣＨ_２−Ｏ−、−ＣＯ−、−（ＣＨ_２）_ｋ−、−ＣＯＯ−又は−ＣＯ−ＮＲ^５−である。Ｒ^５は、水素原子又は炭素数１〜４のアルキル基である。ｋは、１〜１５の整数である。Ｙは、下記式（１）で表されるブロック及び下記式（２）で表されるブロックを含む基である。）

(In Formula (3), R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ is a hydrogen atom or a methyl group. X is —O—, —CH ₂ —O—, —CO—, — (CH ₂ ) _k —, —COO—, or —CO—NR ⁵ —, wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k is 1 to 15; Y is a group including a block represented by the following formula (1) and a block represented by the following formula (2).

（式（１）中、Ｒ^１及びＲ^２は、いずれか一方がメチル基であり、他方が水素原子である。ｍは、繰り返し単位数を表し、１０以上４０以下の整数である。複数のＲ^１及びＲ^２は、それぞれ同一でも異なっていてもよい。）

(In Formula (1), ^one of R ¹ and R ² is a methyl group and the other is a hydrogen atom. M represents the number of repeating units and is an integer of 10 to 40.] R ¹ and R ² may be the same or different.)

（式（２）中、ｎは、繰り返し単位数を表し、１以上５０以下の整数である。）

(In formula (2), n represents the number of repeating units and is an integer of 1 to 50.)

  According to the production method of the present invention, it has sufficient plasticity, solubility in alcohol solvents, low viscosity and viscosity stability of the solution, hardly causes phase separation with other components, particle dispersibility and thixotropy. It is possible to easily produce a POA-modified vinyl acetal polymer capable of obtaining a slurry having excellent properties and a sheet having excellent strength, peelability and flexibility.

  The POA-modified vinyl acetal polymer of the present invention has a low glass transition point and excellent plasticity. The POA-modified vinyl acetal polymer has high solubility in an alcohol solvent, its solution viscosity is low, and the stability of the solution viscosity over time is sufficiently satisfied. A composition using the POA-modified vinyl acetal polymer as various binders hardly causes phase separation, and exhibits high dispersibility of particles and thixotropic properties. Furthermore, since the POA-modified vinyl acetal polymer of the present invention is internally plasticized, thermoplastic processing is possible even if the amount of plasticizer used is reduced. Therefore, by using the POA-modified vinyl acetal polymer, problems such as deterioration of physical properties due to the addition of a large amount of plasticizer can be avoided, and films, sheets and the like excellent in strength, ease of peeling and flexibility can be produced. can do.

<POA-modified vinyl acetal polymer>
The POA-modified vinyl acetal polymer of the present invention is obtained by acetalizing POA-modified PVA and is represented by the following formula (1) (hereinafter also referred to as “block (1)”) and the following formula (2). The monomer unit containing a block represented by the formula (hereinafter also referred to as “block (2)”) has a content (hereinafter also referred to as “POA group modification rate”) of 0. A viscosity average polymerization degree is from 150 to 5,000, and an acetalization degree is from 10 to 85 mol%. Below, POA modified PVA which is a raw material of the said POA modified vinyl acetal polymer is demonstrated.

[POA-modified PVA]
As said POA modified PVA, it contains the monomer unit containing block (1) and block (2), the content rate of the said monomer unit is 0.05 mol% or more and 10 mol% or less, and a viscosity average Those having a degree of polymerization of 150 to 5,000 are used. The POA-modified vinyl acetal polymer obtained by the POA-modified PVA containing monomer units containing the block (1) and the block (2) exhibits excellent internal plasticity. Although details of the mechanism at this time have not been clarified, for example, the hydrophobic interaction between POA groups between molecules of the POA-modified vinyl acetal polymer is increased, and as a result, internal plasticity is improved. Can be mentioned.

(Block (1))
In formula (1), ^one of R ¹ and R ² is a methyl group and the other is a hydrogen atom. m represents the number of repeating units and is an integer of 10 or more and 40 or less. A plurality of R ¹ and R ² may be the same or different.

  Examples of the block (1) include a polyoxypropylene block in which the number of repeating units of oxypropylene units is m, a polyoxybutylene block in which the number of repeating units of oxybutylene units is m, and the like.

  The number m of repeating units of the oxyalkylene unit in the block (1) needs to be an integer of 10 or more and 40 or less, preferably 15 or more and 38 or less, and more preferably 20 or more and 35 or less. When m is less than 10, internal plasticity due to the hydrophobic interaction between POA groups between molecules of the POA-modified vinyl acetal polymer may not be sufficiently exhibited.

In the formula (1), it is preferable that R ¹ is a methyl group and R ² is a hydrogen atom because the POA-modified PVA is easy to produce.

(Block (2))
In formula (2), n represents the number of repeating units and is an integer of 1 to 50.

  Block (2) is a (poly) oxyethylene block in which the number of repeating units of oxyethylene units is n.

  n is preferably an integer of 3 to 40 and more preferably an integer of 5 to 10. When n is 0, since the hydrophobic interaction between POA groups is insufficient, the internal plasticizing effect of the POA-modified vinyl acetal polymer, high solubility in an alcohol solvent, and the like may not be sufficiently exhibited. . On the other hand, when n exceeds 50, the solubility of the POA-modified vinyl acetal polymer in an alcohol solvent may decrease.

  The monomer unit may further include a block (a) different from the block (1) or the block (2). Examples of the block (a) include a polyoxypentylene block, a polyoxyhexylene block, a polyoxystyrene block, a polyalkylene block, and a polyoxyethylene block having 51 to 70 repeating units.

  These block (1), block (2) and block (a) may be contained in any of the main chain, side chain and terminal of the POA-modified PVA, respectively, From the viewpoint of ease of synthesis, it is preferably contained in the side chain. Here, the “main chain” refers to the longest chain among the chains formed by bonding a plurality of atoms constituting the POA-modified PVA. “Side chain” refers to a chain other than the main chain in the POA-modified PVA.

  Moreover, it is preferable that the said monomer unit has both a block (1) and a block (2) in a side chain. In this case, in the side chain, the block (1) may be located on either the main chain side or the opposite side of the block (2), but is preferably located on the main chain side. Further, in this case, it is preferable that the block (1) and the block (2) are directly coupled. By setting the positions of such block (1) and block (2), the above-mentioned hydrophobic interaction can be further promoted, and as a result, various performances of the POA-modified vinyl acetal polymer are further improved. Can be made.

The POA-modified PVA is a copolymer including a monomer unit containing a POA group and a vinyl alcohol unit (—CH ₂ —CHOH—), and may further have another monomer unit.

  The saponification degree of the POA-modified PVA is preferably 20 to 99.99 mol%, more preferably 40 to 99.9 mol%, particularly preferably 70 to 99.9 mol%, and 80 to 99.9 mol%. Most preferred. When the saponification degree is less than 20 mol%, the water solubility of the POA-modified PVA decreases, and it is difficult to prepare an aqueous solution of the POA-modified PVA. Therefore, the modified vinyl acetal polymer is produced in the aqueous solution. Becomes difficult. As a result, since the degree of acetalization decreases, various performances of the obtained POA-modified vinyl acetal polymer may decrease. If the degree of saponification exceeds 99.99 mol%, the production of the POA-modified PVA becomes difficult, which is not practical. The saponification degree of the POA-modified PVA is a value that can be measured according to JIS-K6726.

  As the POA-modified PVA, those having a POA group modification rate of 0.05 mol% to 10 mol% are used, preferably 0.1 mol% to 2 mol%, preferably 0.2 mol% to 1 mol%. The following is more preferable. When the POA group modification rate exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of POA-modified PVA increases, the water solubility of this PVA decreases, and the acetalization reaction described below can be carried out in an aqueous solution. It can be difficult. On the other hand, when the POA group modification rate is less than 0.05 mol%, the water solubility of the POA-modified PVA is excellent, but the number of POA groups contained in the PVA is small and the physical properties based on the POA modification are not expressed. There is.

  The POA group modification rate is the ratio (mol%) of the number of moles of monomer units having the block (1) and the block (2) in the number of moles of all monomer units constituting the POA-modified PVA. is there. The POA group modification rate may be determined from POA-modified PVA or may be determined from the precursor POA-modified vinyl ester polymer, both of which can be determined by proton NMR.

When the POA-modified PVA is composed only of a vinyl alcohol unit, a vinyl acetate unit and a polyoxypropylene (poly) oxyethylene monomethacrylamide unit as an unsaturated monomer unit represented by the above formula (3), the following method Thus, the POA group modification rate can be calculated. That is, for example, when obtaining from a precursor POA-modified vinyl ester polymer (POA-modified polyvinyl acetate), specifically, first, a POA-modified vinyl ester polymer using a mixed solvent of n-hexane / acetone. After the reprecipitation purification is sufficiently performed three times or more, drying is performed under reduced pressure at 50 ° C. for 2 days to prepare a sample of POA-modified vinyl ester polymer for analysis. The sample is then dissolved in CDCl ₃ and measured at room temperature using proton NMR. And the area of the peak α (4.7 to 5.2 ppm) derived from the proton of the main chain methine of the vinyl ester monomer and the peak β (0.8 to 0.8 derived from the proton of the terminal methyl group of the oxypropylene unit) From the area of 1.0 ppm), the POA group modification rate can be calculated using the following formula. In the following formula, m represents the number of repeating units of oxypropylene units.

POA group modification rate (mol%) = [(Area of peak β / 3 m) / {Area of peak α + (Area of peak β / 3 m)}] × 100

  Even when the POA-modified PVA has a structure other than the above structure, the POA group modification rate can be easily obtained by appropriately changing the calculation target peak or calculation formula.

The viscosity average polymerization degree of the POA-modified PVA used in the present invention (hereinafter sometimes abbreviated as “polymerization degree”) is measured according to JIS K6726. That is, after re-saponifying and purifying the above PVA, it is obtained from the intrinsic viscosity [η] (unit: deciliter / g) measured in water at 30 ° C. by the following formula. When two or more kinds of PVA are mixed and used as the POA-modified PVA, the apparent viscosity average polymerization degree of the whole PVA after mixing is defined as the viscosity average polymerization degree P in that case.

Degree of polymerization P = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}

  As the polymerization degree P of the POA-modified PVA used as a raw material for the POA-modified vinyl acetal polymer, those having a polymerization degree of 150 to 5,000 are used. When the polymerization degree P exceeds 5,000, the productivity of the POA-modified PVA is lowered, which is not practical. The lower limit of the polymerization degree P of the POA-modified PVA is preferably 200, more preferably 500, particularly preferably 800, and most preferably 1,000. On the other hand, the upper limit of the polymerization degree P of the POA-modified PVA is preferably 4,500, more preferably 3,500.

  The polymerization degree P of the POA-modified vinyl acetal polymer is determined from the polymerization degree of the POA-modified PVA used for producing the POA-modified vinyl acetal polymer. That is, since the polymerization degree does not change by acetalization, the polymerization degree of POA-modified PVA and the polymerization degree of the POA-modified vinyl acetal polymer obtained by acetalizing it are the same.

[POA-modified vinyl acetal polymer]
The POA-modified vinyl acetal polymer can be obtained by acetalizing the above-mentioned POA-modified PVA according to a conventionally known method. In the POA-modified vinyl acetal polymer, the degree of acetalization is from 10 mol% to 85 mol%, preferably from 35 mol% to 85 mol%, more preferably from 50 mol% to 85 mol%. By adjusting the degree of acetalization within the above range, the solubility of the POA-modified vinyl acetal polymer in an alcohol solvent can be further improved, and an alkyl-modified vinyl acetal polymer that is further excellent in toughness is obtained. Can be easily obtained. When the degree of acetalization is less than 10 mol%, it is difficult to obtain industrially, resulting in a decrease in productivity. On the other hand, when the degree of acetalization exceeds 85 mol%, it is not only difficult to obtain industrially from the viewpoint of reactivity, but also the residual hydroxyl group is reduced, and the toughness of the POA-modified vinyl acetal polymer is impaired. In order to adjust the degree of acetalization of the POA-modified vinyl acetal polymer, the amount of aldehyde added to the POA-modified PVA, the reaction time after adding the aldehyde and acid, and the like may be adjusted as appropriate.

Here, the degree of acetalization of the POA-modified vinyl acetal polymer represents the ratio of the acetalized vinyl alcohol unit to the total monomer units constituting the POA-modified vinyl acetal polymer. It can be calculated from the spectrum obtained by performing ¹ H-NMR measurement using a DMSO-d ₆ (dimethyl sulfoxide) solution of an acetal polymer as a sample.

  The viscosity average polymerization degree P of the POA-modified vinyl acetal polymer of the present invention needs to be 150 or more and 5,000 or less. When the polymerization degree P of the POA-modified vinyl acetal polymer is less than 150, the mechanical strength of the obtained sheet or film becomes insufficient when a sheet or film such as a thin film ceramic green sheet is produced. On the other hand, when the polymerization degree P of the POA-modified vinyl acetal polymer exceeds 5,000, the coating property and the dispersibility are deteriorated due to insufficient dissolution in the alcohol solvent or excessively high solution viscosity. There is. The lower limit of the polymerization degree P of the POA-modified vinyl acetal polymer is preferably 200, more preferably 500, particularly preferably 800, and most preferably 1,000. On the other hand, the upper limit of the degree of polymerization P of the modified vinyl acetal polymer is preferably 4,500, more preferably 3,500.

  The viscosity average polymerization degree P of the POA-modified vinyl acetal polymer is determined from the viscosity average polymerization degree of the POA-modified PVA used for the production of the POA-modified vinyl acetal polymer. That is, since the polymerization degree does not change by acetalization, the polymerization degree of POA-modified PVA and the polymerization degree of POA-modified vinyl acetal polymer obtained by acetalizing it are the same.

  The POA group modification rate of the POA-modified vinyl acetal polymer needs to be 0.05 mol% or more and 10 mol% or less. The upper limit of the POA group modification rate in the POA-modified vinyl acetal polymer is preferably 2 mol%, more preferably 1.5 mol%. When the POA group modification rate exceeds 10 mol%, the water solubility of the POA-modified PVA is lowered, and as a result, the degree of acetalization of the obtained POA-modified vinyl acetal polymer is lowered. Various performances of the polymer may decrease. On the other hand, when the POA group modification rate is less than 0.05 mol%, the number of POA groups contained in the POA-modified vinyl acetal polymer is small, and physical properties based on POA modification may not be exhibited. As a minimum of a POA group modification rate, 0.1 mol% is preferred and 0.2 mol% is more preferred.

  The POA group modification rate of the POA-modified vinyl acetal polymer is a single amount having the block (1) and the block (2) in the number of moles of all monomer units constituting the POA-modified vinyl acetal polymer. It is the ratio (mol%) of moles of body units. Even if the POA-modified PVA is acetalized, the ratio of the number of moles of units derived from the unsaturated monomer having the block (1) and the block (2) in the number of moles of all monomer units in the molecule ( Mol%) does not change. Therefore, the POA group modification rate of the POA-modified PVA described above is the same as the POA group modification rate of the POA-modified vinyl acetal polymer obtained by acetalizing it.

  The POA group modification rate of the POA-modified vinyl acetal polymer may be determined from this POA-modified vinyl acetal polymer, or from the precursor POA-modified PVA or POA-modified vinyl ester polymer. Both can be determined by proton NMR. When obtaining the POA group modification rate of the POA modified vinyl acetal polymer from the POA modified vinyl ester polymer, it can be obtained by the method described above as a method for obtaining the POA group modification rate of the POA modified PVA.

  In the POA-modified vinyl acetal polymer of the present invention, the content of the vinyl ester monomer unit is preferably 0.01 mol% or more and 29.9 mol% or less. When the content of the vinyl ester monomer unit is less than 0.01 mol%, intramolecular and intermolecular hydrogen bonds due to hydroxyl groups in the POA-modified vinyl acetal polymer increase. Therefore, when a slurry composition for a ceramic green sheet is used, the viscosity may become too high, or the solubility in an organic solvent may become too high, resulting in a sheet attack phenomenon. On the other hand, if the content of the vinyl ester monomer unit exceeds 29.9 mol%, the glass transition temperature of the POA-modified vinyl acetal polymer is lowered, and it becomes too flexible. Therefore, the handling property, mechanical strength, and dimensional stability during thermocompression bonding of the ceramic green sheet produced using the POA-modified vinyl acetal polymer may be deteriorated. The lower limit of the content of the vinyl ester monomer unit is more preferably 0.5 mol%. On the other hand, the upper limit of the content of the vinyl ester monomer unit is more preferably 23 mol%, further preferably 20 mol%. The modified vinyl acetal polymer having a vinyl ester monomer unit content of 0.01 to 29.9 mol% has a vinyl ester monomer unit content of 0.01 to 29.9. It is obtained by acetalizing POA-modified PVA that is mol%. That is, it is obtained by acetalizing POA-modified PVA having a saponification degree of 70.0 to 99.99 mol%.

  In the POA-modified vinyl acetal polymer of the present invention, the content of the vinyl alcohol monomer unit is preferably 20 mol% or more and 60 mol% or less. When the content of the vinyl alcohol monomer unit is less than 20 mol%, the strength of the ceramic green sheet produced using the POA-modified vinyl acetal polymer is lowered or the solubility in an organic solvent is low. This may cause a sheet attack phenomenon. On the other hand, when the content of the vinyl alcohol monomer unit exceeds 60 mol%, intramolecular and intermolecular hydrogen bonds due to hydroxyl groups in the POA-modified vinyl acetal polymer increase. Therefore, when it is set as the slurry composition for ceramic green sheets, a viscosity may become high too much.

<Method for producing POA-modified vinyl acetal polymer>
The method for producing the POA-modified vinyl acetal polymer of the present invention includes:
By copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer, the viscosity average polymerization degree P is 150 or more and 5,000 or less, the content of the unsaturated monomer unit. Is a step of obtaining a polyoxyalkylene-modified vinyl ester polymer of 0.05 mol% or more and 10 mol% or less (hereinafter also referred to as “step (1)”),
A step of obtaining POA-modified PVA having a saponification degree of 20 mol% or more and 99.99 mol% or less by saponification of the polyoxyalkylene-modified vinyl ester polymer (hereinafter also referred to as “step (2)”), and the POA A step of obtaining a POA-modified vinyl acetal polymer having a degree of acetalization of 10 mol% or more and 85 mol% or less by acetalization of the modified PVA (hereinafter also referred to as “step (3)”)
Have The specific method of each process is explained in full detail below.

[Step (1)]
In this step, the unsaturated monomer represented by the above formula (3) and a vinyl ester monomer are copolymerized so that the viscosity average polymerization degree P is 150 or more and 5,000 or less. This is a step of obtaining a polyoxyalkylene-modified vinyl ester polymer having a unit content of 0.05 mol% or more and 10 mol% or less.

In Formula (3), R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ is a hydrogen atom or a methyl group. X is —O—, —CH ₂ —O—, —CO—, — (CH ₂ ) _k —, —COO— or —CO—NR ⁵ —. R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. k is an integer of 1-15. Y is a group including a block represented by the following formula (1) and a block represented by the following formula (2).

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³ include a methyl group, an ethyl group, a propyl group, and a butyl group. As said R < ³ >, a hydrogen atom, a methyl group, and a butyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

In the above formula (3), when X is asymmetric, that is, —CH ₂ —O—, —COO— or —CO—NR ⁵ —, the direction of X may be any. As the _{X, -O -, - CH 2} -O -, - CO-NR 5 - is preferably, -CO-NR ⁵ - is more preferable, -CO-NH- is more preferred. R ⁵ is preferably a hydrogen atom.

  The direction of the group represented by Y (the arrangement of the block (1), the block (2), etc.) is as described above.

  As the unsaturated monomer represented by the above formula (3), an unsaturated monomer represented by the following formula (3-1) or (3-2) is preferable, and in the following formula (3-1): The unsaturated monomer represented is more preferred.

In formulas (3-1) and (3-2), R ¹ , R ² and m are the same as those in formula (1). n is the same as in the above formula (2). R ³ , R ⁴ and X are the same as in the above formula (3). “B” indicates that both adjacent units are formed by block copolymerization.

When R ^{3 in the} above formula (3) is a hydrogen atom and R ⁴ is a hydrogen atom or a methyl group, the unsaturated monomer represented by the above formula (3) may be polyoxyalkylene mono (meth) acrylamide, poly Examples include oxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, polyoxyalkylene mono (meth) acrylate, and more specifically, polyoxypropylene (poly) oxyethylene monoacrylamide, polyoxypropylene (poly) Oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monoallyl ether, polyoxypropylene (poly) oxyethylene monomethallyl ether, polyoxypropylene (poly) oxyethylene monovinyl ether, polyoxypropylene (poly) oxy Chi Ren monoacrylate, polyoxypropylene (poly) oxyethylene monomethacrylate, and the like.

  Among these, polyoxypropylene (poly) oxyethylene monoacrylamide, polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monovinyl ether, polyoxypropylene (poly) oxyethylene monoallyl ether are preferable.

When R ^{3 in the} formula (3) is an alkyl group having 1 to 8 carbon atoms, examples of the unsaturated monomer represented by the formula (3-1) include R ^{3 in the} formula (3-1). Examples include those in which the hydroxyl group at the terminal of the unsaturated monomer exemplified in the case of a hydrogen atom is substituted with an alkoxy group having 1 to 8 carbon atoms. Among these, polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monoallyl ether, polyoxypropylene (poly) oxyethylene monovinyl ether and the hydroxyl group at the terminal are substituted with methoxy groups. Saturated monomers are preferred.

  The temperature at which the unsaturated monomer represented by the above formula (3) is copolymerized with the vinyl ester monomer is not particularly limited, but is preferably 0 ° C or higher and 200 ° C or lower, and 30 ° C or higher and 140 ° C or lower. Is more preferable. When the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate. Moreover, when the temperature which superposes | polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA group modification rate prescribed | regulated by this invention. As a method for controlling the temperature employed in the copolymerization to 0 ° C. or more and 200 ° C. or less, for example, by controlling the polymerization rate, the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. And a method of controlling by an external jacket using an appropriate heat medium. The latter method is preferable from the viewpoint of safety.

  The polymerization method employed for the copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer is batch polymerization, semi-batch polymerization, continuous polymerization, or semi-continuous polymerization. Either is acceptable. As the polymerization method, an arbitrary method can be adopted from known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or in the presence of an alcohol solvent is preferable. For the purpose of producing a copolymer having a high degree of polymerization, an emulsion polymerization method is employed. As an alcohol solvent used in the bulk polymerization method or the solution polymerization method, for example, methanol, ethanol, n-propanol or the like can be used. Two or more of these solvents may be used in combination.

  As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method. As the azo initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like, and peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, α-cumylperoxyneodecanate, and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc. Is mentioned. Furthermore, the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator. Moreover, as a redox-type initiator, what combined said peroxide and reducing agents, such as sodium hydrogen sulfite, sodium hydrogencarbonate, tartaric acid, L-ascorbic acid, Rongalite, is mentioned.

  Further, when copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer is performed at a high temperature, the coloring of the POA-modified PVA caused by the decomposition of the vinyl ester monomer Etc. may be seen. In that case, an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 ppm to 100 ppm (relative to the mass of the vinyl ester monomer) for the purpose of preventing coloring.

  Vinyl ester monomers used for copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid. Examples thereof include vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is most preferred.

  When the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer are copolymerized, other monomers may be copolymerized as long as the effects of the present invention are not impaired. Examples of the monomer that can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylic acid esters; methacrylic acid and salts thereof; methacrylic acid esters; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt or its quaternary salt, N-methylolacrylamide and its derivative, etc. Methacrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and its salt, methacrylamide propyl dimethylamine and its salt or Methacrylamide derivatives such as quaternary salts, N-methylol methacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl Vinyl ethers such as vinyl ether, stearyl vinyl ether and 2,3-diacetoxy-1-vinyloxypropane; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene chloride and vinylidene fluoride Vinylidene halides such as allyl compounds such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane, allyl chloride, etc .; unsaturated such as maleic acid, itaconic acid, fumaric acid, etc. And dicarboxylic acids and salts or esters thereof; vinylsilyl compounds such as vinyltrimethoxysilane; and isopropenyl acetate.

  Furthermore, you may copolymerize the monomer which gives an alpha olefin unit as another monomer in the range which does not impair the effect of this invention. As content of the said alpha olefin unit, 1 mol% or more and 20 mol% or less are preferable.

  In the copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer, for the purpose of adjusting the degree of polymerization of the resulting POA-modified vinyl ester polymer, etc. Copolymerization may be performed in the presence of a chain transfer agent as long as the effect is not impaired. Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate 1 And phosphinic acid salts such as hydrates. Of these, aldehydes and ketones are preferred. The addition amount of the chain transfer agent may be determined according to the chain transfer constant of the added chain transfer agent and the degree of polymerization of the target POA-modified vinyl ester polymer. Usually, 0.1 mass% or more and 10 mass% or less are preferable with respect to a vinyl ester-type monomer.

[Step (2)]
This step is a step of obtaining a POA-modified PVA having a saponification degree of 20 mol% or more and 99.99 mol% or less by saponification of the POA-modified vinyl ester polymer.

  In the saponification reaction of the obtained POA-modified vinyl ester polymer, alcohol addition using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or acidic catalyst such as p-toluenesulfonic acid. Decomposition reaction or hydrolysis reaction can be applied. Examples of the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.

[Step (3)]
This step is a step of obtaining a POA-modified vinyl acetal polymer having an acetalization degree of 10 mol% or more and 85 mol% or less by acetalization of the POA-modified PVA.

  As the acetalization method in the present invention, there are generally a one-step method and a two-step method, and either may be adopted.

  The two-stage method is a method in which saponification of a POA-modified vinyl ester polymer and acetalization of the generated POA-modified PVA are performed in separate reactors. The two-stage method is further roughly divided into a precipitation method and a dissolution method. As the precipitation method, an aqueous solution of POA-modified PVA is used, and the acetalization reaction of POA-modified PVA is carried out at a low temperature in a solvent mainly composed of water. After the POA-modified vinyl acetal polymer is precipitated, the temperature of the system is raised. And ripening reaction (completion of acetalization reaction and rearrangement of acetalization moiety) is preferable. In the dissolution method, an acetalization reaction of POA-modified PVA is carried out at a high temperature in an alcohol solvent such as isopropanol or in a mixed solution in which water or the like is used together, and then water is added to the system to add the POA-modified vinyl acetal. The system polymer is precipitated. On the other hand, in the above one-step method, saponification of the POA-modified vinyl ester polymer and acetalization of the generated POA-modified PVA are performed in one pot.

  Of the above acetalization methods, the precipitation method will be described more specifically. An aqueous solution of 3% by mass or more and 15% by mass or less of POA-modified PVA is adjusted to a temperature range of 80 ° C. or more and 100 ° C. or less, and then gradually cooled over 10 minutes or more and 60 minutes or less. When the temperature drops to −10 ° C. or more and 40 ° C. or less, an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 10 minutes or more and 300 minutes or less while keeping the temperature constant. The amount of aldehyde used at this time is preferably 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the POA-modified PVA. Thereafter, it is preferable to include a aging step in which the reaction solution is heated to a temperature of 15 ° C. or more and 80 ° C. or less over 30 minutes or more and 200 minutes or less, and the temperature is maintained for 0 minutes or more and 360 minutes or less. Next, the reaction solution is preferably cooled to room temperature, washed with water, then added with a neutralizing agent such as alkali, washed and dried to obtain the target POA-modified vinyl acetal polymer.

  Examples of aldehydes that can be used in the acetalization reaction include formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, valeraldehyde, pivalaldehyde, Aliphatic aldehydes such as amyl aldehyde, hexyl aldehyde, heptyl aldehyde, 2-ethylhexyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde; cyclopentane aldehyde, methyl cyclopentane aldehyde, dimethyl cyclopentane aldehyde, cyclohexane aldehyde, methyl cyclohexane Aldehyde, dimethylcyclohexanealdehyde, cyclohexaneacetate Alicyclic aldehydes such as aldehyde; Cyclic unsaturated aldehydes such as cyclopentene aldehyde and cyclohexene aldehyde; benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, dimethylbenzaldehyde, methoxybenzaldehyde, phenylacetaldehyde, β-phenylpropialdehyde Aromatic or unsaturated bond-containing aldehydes such as onaldehyde, cuminaldehyde, naphthylaldehyde, anthraldehyde, cinnamaldehyde, crotonaldehyde, acroleinaldehyde, 7-octen-1-al; heterocyclic aldehydes such as furfural and methylfurfural Can be mentioned.

  Among these, aldehydes having 2 to 8 carbon atoms are preferable, at least one selected from the group consisting of butyraldehyde and acetaldehyde is more preferable, and butyraldehyde is particularly preferable. These may be used alone or in combination of two or more. By making acetalization using such a specific aldehyde, the POA-modified vinyl acetal polymer can be produced efficiently. In addition, these may be used independently and may use 2 or more types together.

  Moreover, you may use the aldehyde which has a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. as a functional group in the range which does not impair the characteristic of this invention. Examples of such aldehydes include hydroxyl-containing aldehydes such as hydroxyacetaldehyde, hydroxypropionaldehyde, hydroxybutyraldehyde, hydroxypentylaldehyde, salicylaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, dihydroxybenzaldehyde; glyoxylic acid, 2- Formylacetic acid, 3-formylpropionic acid, 5-formylpentanoic acid, 4-formylphenoxyacetic acid, 2-carboxybenzaldehyde, 4-carboxybenzaldehyde, 2,4-dicarboxybenzaldehyde, benzaldehyde 2-sulfonic acid, benzaldehyde-2,4 -Disulfonic acid, 4-formylphenoxysulfonic acid, 3-formyl-1-propanesulfonic acid, 7-formyl- - heptanoic acid, 4-formyl phenoxy phosphonic acid acid-containing aldehydes such as, a metal salt or an ammonium salt, and the like.

  Furthermore, you may use the aldehyde which has an amino group, a cyano group, a nitro group, or a quaternary ammonium salt as a functional group in the range which does not impair the effect of this invention. Examples of such aldehydes include aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, aminopropionaldehyde, dimethylaminopropionaldehyde, aminobutyraldehyde, aminopentylaldehyde, aminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylaminobenzaldehyde, diethylaminobenzaldehyde. Pyrrolidylacetaldehyde, piperidylacetaldehyde, pyridylacetaldehyde, cyanoacetaldehyde, α-cyanopropionaldehyde, nitrobenzaldehyde, trimethyl-p-formylphenylammonium iodyne, triethyl-p-formylphenylammonium iodyne, trimethyl-2-formylethyl Ammonium ions dyne, and the like.

  Furthermore, you may use the aldehyde which has a halogen as a functional group in the range which does not impair the effect of this invention. Examples of such aldehydes include chloroacetaldehyde, bromoacetaldehyde, fluoroacetaldehyde, chloropropionaldehyde, bromopropionaldehyde, fluoropropionaldehyde, chlorobutyraldehyde, bromobutyraldehyde, fluorobutyraldehyde, chloropentylaldehyde, bromopentylaldehyde, Fluoropentylaldehyde, chlorobenzaldehyde, dichlorobenzaldehyde, trichlorobenzaldehyde, bromobenzaldehyde, dibromobenzaldehyde, tribromobenzaldehyde, fluorobenzaldehyde, difluorobenzaldehyde, trifluorobenzaldehyde, trichloromethylbenzaldehyde, tribromomethylbenzaldehyde, trif Oro methylbenzaldehyde and alkyl acetal and the like.

  In the acetalization of the POA-modified PVA, a polyvalent aldehyde such as glyoxal or glutaraldehyde may be used in combination with the above aldehyde. However, when POA-modified PVA is acetalized with a polyvalent aldehyde, the stress relaxation force at the cross-linked site is different from that at the non-cross-linked site. Therefore, the aldehyde used is preferably only monoaldehyde, and even when a polyvalent aldehyde group is used, the amount used is preferably less than 0.005 mol% with respect to the vinyl alcohol unit of the POA-modified PVA. 0.003 mol% or less is more preferable.

  In the acetalization, the alkyl acetals of the aldehydes exemplified above can be used in the same manner.

  It does not specifically limit as an acid used for acetalization, Any of an organic acid and an inorganic acid can be used, For example, an acetic acid, p-toluenesulfonic acid, nitric acid, a sulfuric acid, hydrochloric acid etc. are mentioned. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferable, and hydrochloric acid and nitric acid are more preferable. In addition, these acids may use 2 or more types together.

  The use of the POA-modified vinyl acetal polymer is not particularly limited, but the composition containing the POA-modified vinyl acetal polymer has high strength and flexibility, and is a binder for internal electrodes of ceramic green sheets and multilayer ceramic capacitors. In addition, it can be widely used as, for example, coating materials such as paints, inks, adhesives, powder paints, heat-developable photosensitive materials, pellets, films and the like.

<Composition>
The composition of the present invention contains the POA-modified vinyl acetal polymer, but depending on the use, an antioxidant, an ultraviolet absorber, a plasticizer, an adhesion improver, as long as the effects of the present invention are not impaired. It preferably contains a heat ray absorbent, a colorant, a filler, a fluidity improver, a lubricant, a dispersant, an antistatic agent, a peptizer, a wetting agent, an antifoaming agent, and a solvent such as an organic solvent. . These additives and solvents may be added during the production of the POA-modified vinyl acetal polymer, or may be added after production and before use in various applications. Of the above additives, a plasticizer is preferred.

  The plasticizer is not particularly limited as long as it has excellent compatibility with the vinyl acetal polymer. For example, dioctyl phthalate, benzylbutyl phthalate, dibutyl phthalate, dihexyl phthalate, diphthalate diphthalate (2-ethylhexyl) (hereinafter sometimes abbreviated as “DOP”), phthalic acid plasticizers such as di (2-ethylbutyl) phthalate; dihexyl adipate, di (2-ethylhexyl) adipate (hereinafter referred to as Adipate plasticizers such as ethylene glycol, diethylene glycol and triethylene glycol; triethylene glycol dibutyrate, triethylene glycol di (2-ethylbutyrate) , Triethylene glycol di (2-ethylhexanoate) Call ester plasticizer; tricresyl phosphate, tributyl phosphate, phosphate plasticizers such as triethyl phosphate, and the like. These may be used alone or in combination of two or more.

  The organic solvent is not particularly limited, and examples thereof 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 ethyl hexyl and 2-ethyl hexyl butyrate; glycols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, α-terpineol, butyl cellosolve acetate, butyl carbitol acetate, terpenes System, and the like. These organic solvents may be used independently and may use 2 or more types together.

  As the said composition, the slurry composition for ceramic green sheets containing the said POA modified vinyl acetal polymer, ceramic powder, and an organic solvent is preferable.

<Slurry composition for ceramic green sheet>
The slurry composition for a ceramic green sheet of the present invention contains the POA-modified vinyl acetal polymer, ceramic powder, and an organic solvent. When the POA-modified vinyl acetal polymer is dissolved in a 1: 1 mixed solvent of ethanol and toluene or an alcohol such as ethanol in the production process of a ceramic green sheet, the solution viscosity does not become too high. Therefore, the ceramic powder can be uniformly dispersed in the composition without agglomerating. The composition is also excellent in coatability. In this respect, the slurry composition is particularly useful.

  As content of the said POA modified vinyl acetal polymer in the said composition used as a slurry composition for ceramic green sheets, 3 mass% or more and 30 mass% or less are preferable with respect to the said composition whole quantity. By setting the content of the POA-modified vinyl acetal polymer in the above range, the film forming performance of the obtained ceramic green sheet is further improved. When the content of the POA-modified vinyl acetal polymer is less than 3% by mass, the amount of the POA-modified vinyl acetal polymer dispersed in the entire ceramic powder becomes insufficient, and the resulting ceramic green sheet is formed. Since the performance is inferior or the flexibility of the ceramic green sheet is lowered, cracks or the like may occur after sintering. When the content of the POA-modified vinyl acetal polymer exceeds 30% by mass, the viscosity of the slurry composition for a ceramic green sheet of the present invention becomes too high and the dispersibility is lowered. The carbon component may easily remain after degreasing and firing. The content of the POA-modified vinyl acetal polymer is more preferably 3% by mass or more and 20% by mass or less.

  Further, the composition used as the slurry composition for ceramic green sheets contains an unmodified vinyl acetal polymer, an acrylic polymer, and a cellulose polymer in addition to the POA-modified vinyl acetal polymer as a binder resin. May be. When an acrylic polymer, a cellulose polymer, or the like is contained as a binder resin, the lower limit of the content of the POA-modified vinyl acetal polymer in the entire binder resin is the mechanical strength of the resulting ceramic green sheet, heating 30 mass% is preferable from a viewpoint of press bonding.

The ceramic powder is not particularly limited. For example, alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, magnesia, sialon, spinemulite, crystallized glass, silicon carbide, silicon nitride, aluminum nitride And the like. 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 ₃ —SiO ₂ , PbO—B ₂ O ₃ —SiO ₂ , CaO—SiO ₂ —MgO—B ₂ O ₃ or PbO—SiO _2. Glass frit such as —B ₂ O ₃ —CaO may be added.

  The upper limit of the ceramic powder content relative to the total amount of the composition used as the ceramic green sheet slurry composition is preferably 80 mass%, and the lower limit is preferably 30 mass%. If it is less than 30% by mass, the viscosity may be too low and handling properties may be deteriorated when the ceramic green sheet is formed. If it exceeds 80% by mass, the viscosity of the slurry composition for ceramic green sheet becomes too high. Kneadability tends to decrease.

  As an organic solvent contained in the said composition used as a slurry composition for ceramic green sheets, what was mentioned above as an organic solvent used for the composition of this invention is mentioned. These organic solvents may be used alone or in combination of two or more. Of these, a mixed solvent of toluene and ethanol, or ethanol, α-terpineol, butyl cellosolve acetate or butyl carbitol acetate is preferable because of good handling properties.

  The upper limit of the organic solvent content relative to the total amount of the composition used as the ceramic green sheet slurry composition is preferably 80% by mass, and the lower limit is preferably 20% by mass. By setting the content of the organic solvent in the above range, an appropriate kneadability can be imparted to the ceramic green sheet slurry composition of the present invention.

  As a plasticizer added to the composition used as the slurry composition for a ceramic green sheet of the present invention, DOP, DOA, triethylene glycol-2-ethylhexyl is used because of low volatility and easy maintenance of the sheet flexibility. preferable. These may be used alone or in combination of two or more. The amount of the plasticizer used is not particularly limited, but is preferably 0.1% by mass or more and 10% by mass or less, and preferably 1% by mass or more and 8% by mass with respect to the total amount of the composition used as the slurry composition for ceramic green sheets. The following is more preferable.

<Method for preparing composition>
The composition can be prepared by dissolving or dispersing the additive such as the POA-modified vinyl acetal polymer and plasticizer in a solvent such as an organic solvent. Specifically, for example, as a method for preparing the composition used as a slurry composition for a ceramic green sheet, a binder resin containing at least the POA-modified vinyl acetal polymer, a ceramic powder, an organic solvent and, if necessary, added The method of mixing various additives using a mixer etc. is mentioned. As said mixer, various mixers, such as a ball mill, a blender mill, and a 3 roll, are mentioned.

<Ceramic green sheet>
The ceramic green sheet of this invention is obtained from the said composition used as said slurry composition for ceramic green sheets. Since the composition used as the above-mentioned slurry composition for a ceramic green sheet has the above-described performance, a thin-film ceramic green sheet having sufficient mechanical strength, ease of peeling and flexibility can be produced. . A ceramic green sheet obtained using the composition of the present invention is one of the preferred embodiments of the present invention.

  It does not specifically limit as a manufacturing method of the said ceramic green sheet, It can manufacture with a conventionally well-known manufacturing method. For example, the composition used as a slurry composition for a ceramic green sheet is subjected to a defoaming treatment as necessary, and then applied to a peelable support such as a polyethylene terephthalate film in a coating form, and a solvent or the like by heating or the like. The method of peeling from a support body after distilling off is mentioned.

<Multilayer ceramic capacitor>
A multilayer ceramic capacitor obtained using the ceramic green sheet of the present invention is also one of the preferred embodiments of the present invention. The multilayer ceramic capacitor is preferably obtained using the ceramic green sheet and a conductive paste, and more preferably a laminate of a ceramic green sheet obtained by applying a conductive paste.

  The production method of the multilayer ceramic capacitor is not particularly limited, and can be produced by a conventionally known production method. For example, multiple layers of conductive ceramic paste applied to the surface of the ceramic green sheet by screen printing, etc. are stacked and heat-pressed to obtain a laminate, and the binder components contained in this laminate are pyrolyzed For example, a method of sintering an external electrode on the end face of a fired ceramic product obtained by firing (degreasing treatment) and the like.

<Interlayer film for laminated glass>
The interlayer film for laminated glass of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the interlayer film for laminated glass is excellent in whitening resistance, penetration resistance, and adhesion to glass when exposed to a long period of time under high humidity.

<Ink>
The ink of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the ink has a low solution viscosity and sufficient ink dispersibility. That is, the ink used for printing has a large pigment content at a desired viscosity, and has excellent features such as high color strength even when the thickness of the coating film formed by printing is thin, It can be suitably used for a printing machine that operates at high speed.

<Coating agent>
The coating agent of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the coating agent has sufficient handleability and viscosity stability, and can obtain a film having high water resistance and water stopping performance.

<Heat-developable photosensitive material>
The photothermographic material of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the heat-developable photosensitive material is excellent in heat developability and image stability after development, and the coating solution prepared in the production of the heat-developable photosensitive material is excellent in storage stability.

<Conductive paste>
The conductive paste of the present invention contains the POA-modified vinyl acetal polymer. Accordingly, the conductive paste is excellent in printability such as thixotropy, yarn pulling resistance, bleeding resistance, and sheet attack resistance.

<Pellets>
The pellet of the present invention contains the POA-modified vinyl acetal polymer. Therefore, the pellet has the characteristics that the apparent specific gravity is large, the handleability is good, and the odor is hardly generated at the time of manufacturing and handling.

<Film>
The film of the present invention contains the POA-modified vinyl acetal polymer and does not contain a plasticizer. By containing the POA-modified vinyl acetal polymer, the film does not become hard even if it does not contain a plasticizer and has sufficient handleability and can suppress the generation of droplets.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, unless otherwise specified, parts and% represent parts by mass and% by mass, respectively.

<Method for producing PVA>
[Production Example 1] (Production of PVA1)
A 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer dropping port and an initiator addition port was added to 900 g of vinyl acetate, 100 g of methanol, and a single monomer that is an unsaturated monomer having a POA group. Monomer A (monomer A is represented by the above formula (3), and R ^{1 to} R ⁴ , X, m, and n are as shown in Table 2. The arrangement of oxypropylene units and oxyethylene units is in a block form The block of the oxypropylene unit is located on the X side with respect to the block of the oxyethylene unit.) 3.7 g was charged, and the inside of the system was purged with nitrogen for 30 minutes while carrying out nitrogen bubbling. Moreover, the solution which made the density | concentration 20% by melt | dissolving the monomer A in methanol as a delay solution was prepared, and nitrogen substitution was carried out by bubbling of nitrogen gas. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours, and then the polymerization was stopped by cooling. The total amount of monomers used until the polymerization was stopped was 17 g. Further, the solid content concentration when the polymerization was stopped was 26.2%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution (concentration 35%) of POA-modified vinyl ester polymer (POA-modified PVAc). Furthermore, 14.0 g of alkaline solution (10% methanol solution of sodium hydroxide) was added to 386 g of POA-modified PVAc methanol solution prepared by adding methanol to this solution (100.0 g of POA-modified PVAc in the solution). (POA modified PVAc concentration in saponified solution 25%, molar ratio of sodium hydroxide to vinyl acetate units in POA modified PVAc 0.03). After adding the alkaline solution, a gel-like material was formed in about 1 minute. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed, and then 500 g of methyl acetate was added to remain. The alkali was neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and a washing operation was carried out for 3 hours at room temperature. After this washing operation was repeated three times, the white solid obtained by centrifugal drainage was left to dry in a dryer at 65 ° C. for 2 days to obtain POA-modified PVA (PVA1). PVA1 had a viscosity average polymerization degree of 3,000, a saponification degree of 98.5 mol%, and a POA group modification rate of 0.2 mol%. Table 1 shows the production conditions, and Table 3 shows the measurement results of the degree of polymerization, the degree of saponification, and the POA group modification rate.

[Production Examples 2 to 13, 16 to 22, 24 and 25]
(Production of PVA 2-13, 16-22, 24 and 25)
Charge amount of vinyl acetate and methanol (before the start of polymerization), type of unsaturated monomer having POA group used during polymerization (Table 2), use amount and polymerization rate, concentration of POA-modified PVAc during saponification, acetic acid Each POA-modified PVA (PVA 2-13, 16-22, 24 and 25) was produced in the same manner as in Production Example 1 except that the molar ratio of sodium hydroxide to vinyl units was changed as shown in Table 1. . Table 1 shows the production conditions, and Table 3 shows the degree of polymerization, the degree of saponification, and the POA group modification rate.

[Production Example 14] (Production of PVA14)
Monomer I which is an unsaturated monomer having 850 g of vinyl acetate, 150 g of methanol and POA group was added to a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and an initiator addition port. The body I is represented by the above formula (3), and R ^{1 to} R ⁴ , X, m, and n are as shown in Table 2. The arrangement of the oxypropylene unit and the oxyethylene unit is block-like, and the oxypropylene unit Was placed on the X side with respect to the block of the oxyethylene unit.) 42 g was charged, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and the polymerization was started at 60 ° C. for 3 hours. After the polymerization, the polymerization was stopped by cooling. The solid content concentration when the polymerization was stopped was 25.5%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution (concentration 30%) of POA-modified vinyl ester polymer (POA-modified PVAc). Furthermore, 16.7 g of an alkali solution (10% methanol solution of sodium hydroxide) was added to 463.2 g of a methanol solution of POA-modified PVAc prepared by adding methanol thereto (120.0 g of POA-modified PVAc in the solution). Saponification was carried out (POA modified PVAc concentration in saponified solution 25%, molar ratio of sodium hydroxide to vinyl acetate units in POA modified PVAc 0.03). After adding the alkaline solution, a gel-like material was formed in about 1 minute. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed, and then 500 g of methyl acetate was added to remain. The alkali was neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and a washing operation was carried out for 3 hours at room temperature. This washing operation was repeated three times, and then the white solid obtained by centrifugal drainage was left to dry in a dryer at 65 ° C. for 2 days to obtain POA-modified PVA (PVA14). PVA14 had a viscosity average polymerization degree of 2,400, a saponification degree of 98.5 mol%, and a POA group modification rate of 0.2 mol%. The production conditions are shown in Table 1, and the measurement results of the polymerization degree P, the saponification degree, and the POA group modification rate are shown in Table 3, respectively.

[Production Examples 15 and 23]
(Production of PVA 15 and 23)
Each POA-modified PVA (PVA15) was prepared in the same manner as in Production Example 14 except that the type of unsaturated monomer having a POA group used during polymerization (Table 2) and the amount used were changed as shown in Table 1. And 23) were produced. Table 3 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.

[Production Examples 26 and 27]
(Production of PVA 26 and 27)
As an unsaturated monomer having a POA group used at the time of polymerization, an unsaturated monomer (compound (III)) represented by the following formula (III) and an unsaturated monomer represented by the following formula (IV): (Compound Compound (IV)) was used, and the same amounts as in Production Example 1 were used except that the amounts used and the amounts of vinyl acetate and methanol (before the start of polymerization) were changed as shown in Table 1. POA modified PVA (PVA 26 and 27) was produced. Table 3 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.

  In the compound (III), the oxypropylene unit and the oxyethylene unit are each arranged in a block shape, and the positions of the polyoxyethylene block and the polyoxypropylene block are as described in the above formula.

  In the compound (IV), oxypropylene units and oxyethylene units are randomly arranged.

[Production Example 28]
(Manufacture of PVA28)
750 g of vinyl acetate and 250 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and the polymerization was started at 60 ° C. for 3 hours. After the polymerization, the polymerization was stopped by cooling. The solid content concentration when the polymerization was stopped was 31.0% by mass. Subsequently, unreacted vinyl acetate monomer was removed while sometimes adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 35% by mass) of unmodified polyvinyl acetate (unmodified PVAc). Further, 777.9 g of methanol solution of unmodified PVAc prepared by adding methanol thereto (200.0 g of unmodified PVAc in the solution) was added 27.9 g of an alkaline solution (10 mass% methanol solution of sodium hydroxide). Then, saponification was carried out (the concentration of unmodified PVAc in the saponified solution was 25% by mass, the molar ratio of sodium hydroxide to the vinyl acetate unit in the unmodified PVAc was 0.03). A gel-like material was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification, and then 500 g of methyl acetate was added to remove the remaining alkali. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours. After the above washing operation was repeated three times, the white solid obtained by centrifugal drainage was left to dry in a dryer at 65 ° C. for 2 days to obtain unmodified PVA (PVA28). The polymerization degree of PVA28 was 1,700, and the saponification degree was 98.5 mol%.
The production conditions for the unmodified PVA are shown in Table 1, and the degree of polymerization, the degree of saponification, and the POA group modification rate are shown in Table 3, respectively.

<Synthesis of POA-modified vinyl acetal polymer>
[Example 1]
As shown in Table 1 and Table 3, as POA-modified PVA, the polymerization degree is 3,000, the saponification degree is 98.5 mol%, the POA group modification rate is 0.2 mol% (in the above formula (3), R ^{1 to} R ⁴ , X, m and n are as shown in Table 2. The arrangement of the oxypropylene unit and the oxyethylene unit is a block, and the block of the oxypropylene unit is located on the X side with respect to the block of the oxyethylene unit. PVA1 was prepared. In a glass container having an internal volume of 5 liters equipped with a reflux condenser, a thermometer, and a squid type stirring blade, 205 g of POA-modified PVA (PVA1) and 2,795 g of water are added, and stirred at 90 ° C. or more for about 2 hours. It was completely dissolved. The POA-modified PVA solution was cooled to 38 ° C. with stirring, and 150 mL of hydrochloric acid having a concentration of 20% by mass and 109 g of n-butyraldehyde were added thereto as an acetalization catalyst. The acetalization of was started. This temperature was maintained for 15 minutes to precipitate a POA-modified vinyl butyral polymer. Thereafter, the temperature was raised to 65 ° C., held at 65 ° C. for 3 hours, and then cooled to room temperature. After filtering the precipitated resin, it was washed 10 times with 100 times the amount of ion-exchanged water, added with 0.3 mass% sodium hydroxide solution for neutralization, and held at 70 ° C. for 5 hours. Further, re-washing with 10 times the amount of ion-exchanged water was repeated 10 times, followed by dehydration, followed by drying at 40 ° C. under reduced pressure for 18 hours to obtain a POA-modified vinyl butyral polymer. In the obtained POA-modified vinyl butyral polymer, the degree of butyral (acetal) conversion was 70.1 mol%, the amount of vinyl acetate units relative to the number of moles of all monomer units was 1.0 mol%, The amount of vinyl alcohol unit relative to the number of moles was 28.7 mol%. The obtained POA-modified vinyl butyral polymer was measured by the following method, and the glass transition point, haze, solution viscosity and viscosity stability were evaluated by the following methods. Table 4 shows the composition, physical property values, and evaluation results of the POA-modified vinyl butyral polymer. Note that the POA-modified vinyl butyral polymer and the plasticizer used for preparing the test piece for haze measurement were well dissolved in the mixed solvent.

[Examples 2 to 21 and Comparative Examples 1 to 10]
Each POA-modified vinyl butyral polymer was synthesized in the same manner as in Example 1 except that the POA-modified PVA shown in Tables 1 to 3 was used instead of PVA1 and the acetalization conditions were changed. The physical property values were measured and evaluated. The results are shown in Table 4. In each example, the vinyl butyral polymer and the plasticizer used for preparing the test piece for haze measurement were well dissolved in the mixed solvent.

[Comparative Example 11]
A vinyl butyral polymer was synthesized in the same manner as in Example 1 except that unmodified PVA was used instead of PVA1, and the following physical property values were measured and evaluated. The results are shown in Table 4.

[Comparative Example 12]
Instead of POA-modified PVA, PVA29 having a side chain represented by the following formula (V) described in Patent Document 1 (Japanese Patent Laid-Open No. 06-263521) (composition is described in Table 3) was used. The modified vinyl butyral polymer was synthesized in the same manner as in Example 1 except that the following physical property values were measured and evaluated. The results are shown in Table 4.

[Comparative Example 13]
Instead of POA-modified PVA, modified PVA30 having a monomer unit represented by the following formula (VI) described in Patent Document 3 (Japanese Patent Laid-Open No. 2006-104309) (composition is described in Table 3) A modified vinyl butyral polymer was synthesized in the same manner as in Example 1 except that the following physical property values were measured and evaluated. The results are shown in Table 4.

<Measurement and evaluation of physical properties of vinyl acetal polymer>
The following physical property values were measured and evaluated for each of the prepared vinyl acetal polymers. Table 4 shows the composition, physical property values, and evaluation results of each vinyl acetal polymer.

(Vinyl acetate unit amount, vinyl alcohol unit amount and degree of acetalization)
The vinyl acetate unit amount, vinyl alcohol unit amount and degree of acetalization of each vinyl acetal polymer were calculated from ¹ H-NMR spectrum.

(Glass transition point (Tg))
For measurement of the glass transition point of each vinyl acetal polymer, “EXTAR6000 (RD220)” manufactured by Seiko Instruments Inc. was used. Specifically, in nitrogen, each vinyl acetal polymer is heated from 30 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min, cooled to 30 ° C., and again heated to 150 ° C. at a temperature rising rate of 10 The temperature was raised at ° C / min. The measured value at the time of reheating was adopted as the glass transition point (° C.).

(Haze)
10 parts by mass of each vinyl acetal polymer and 2 parts by mass of dibutyl phthalate as a plasticizer were added to a mixed solvent composed of 10 parts by mass of toluene and 10 parts by mass of ethanol, and dissolved by stirring and mixing. The above solution was cast on a transparent polyester film (“Ester A-4140” manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm so that the thickness after drying was 200 μm, and the temperature was 60 ° C. to 80 ° C. using a hot air dryer. Dry for 4 hours. After leaving still at 20 degreeC for 1 day, it cut into 25 mm x 50 mm, and obtained the test piece. Using this test piece, haze (%) was measured according to JIS K7105.

(Solution viscosity and viscosity stability)
After each vinyl acetal polymer was dissolved in ethanol so as to be 5% by mass and confirmed to be completely dissolved, the solution viscosity at 20 ° C. of each solution was measured using a Brookfield type rotational viscometer. It was measured. Furthermore, each solution was sealed and stored for 1 month in a thermostatic chamber adjusted to 20 ° C., and the viscosity of each solution thereafter was measured under the same conditions. The initial viscosity was η ₁ , the viscosity after storage was η ₂ , the viscosity ratio η ₂ / η ₁ was determined, and this was evaluated as viscosity stability.

<Preparation of slurry composition for ceramic green sheet>
10 parts by mass of each vinyl acetal polymer (vinyl butyral polymer) was added to a mixed solvent composed of 10 parts by mass of toluene and 10 parts by mass of ethanol, and dissolved by stirring and mixing. To this solution, 2 parts by mass of dibutyl phthalate was added as a plasticizer and mixed with stirring. 100 parts by mass of alumina powder (average particle diameter 1 μm) as ceramic powder was added to the obtained solution, and mixed for 48 hours with a ball mill to obtain a slurry composition for ceramic green sheets in which the alumina powder was dispersed. The following evaluation was performed about each obtained slurry composition. The evaluation results are shown in Table 5.

[Evaluation]
(Average particle size)
A few drops were taken from each of the prepared slurry compositions, and then diluted 80-fold with a 1: 1 mixed solvent of ethanol and toluene to prepare a measurement sample. About the obtained measurement sample, the particle size distribution measurement was performed using the laser diffraction type particle size distribution analyzer ("LA-910" by Horiba, Ltd.), and the average particle diameter (micrometer) was measured. In addition, when the average particle diameter was 1 μm or less, it was evaluated as good when the average particle diameter exceeded 1 μm because the particles were aggregated.

(Thixotropic properties)
For each of the prepared slurry compositions, using a rheometer (manufactured by Rheologica Instruments: using a parallel plate with a diameter of 10 mm), pre ^- shearing was performed at a shear rate of 500 S ⁻¹ for 1 minute, and then the viscosity was measured at a shear rate of 100 S ^−1. Then, the viscosity (η ′ ₁ ) one minute after the start of measurement was measured. Thereafter, the viscosity was immediately measured at a shear rate of 0.1 S ⁻¹ to obtain a viscosity (η ′ ₂ ) 1 minute after the start of the measurement. The measurement temperature was 20 ° C. The ratio (η ′ ₂ / η ′ ₁ ) between η ′ ₁ and η ′ ₂ measured in this way was determined, and the value was defined as the thixotropic value. In addition, the case where the value of this thixotropic property was 5.0 or more was evaluated as favorable, and the case where it was less than 5.0 was evaluated as poor.

<Production of ceramic green sheet>
Each of the prepared slurry compositions for ceramic green sheets is applied to a release-treated polyester film with a thickness of about 50 μm, air-dried at room temperature for 30 minutes, and further 60 to 80 ° C. in a hot air dryer. And the organic solvent was evaporated to obtain a ceramic green sheet having a thickness of 30 μm. Each ceramic green sheet obtained was evaluated as follows. The evaluation results are shown in Table 5.

[Evaluation]
(Dispersibility of ceramic green sheet)
The dispersibility of the ceramic particles in the ceramic green sheet was measured using a grindometer (manufactured by Taiho Kogyo Co., Ltd., groove depth 0 to 25 μm), and evaluated in the following three stages.
A: No ceramic agglomerates B: No ceramic agglomerates with a particle size of 5 μm or more C: No ceramic agglomerates with a particle size of 5 μm or more

(Strength of ceramic green sheet)
Using a No. 3 type dumbbell-shaped test piece conforming to JIS K6251 and using a tensile tester (manufactured by Shimadzu Corporation, “Autograph”) under the measurement conditions of a measurement temperature of 20 ° C. and a tensile speed of 10 mm / min. The breaking strength (g / cm ² ) of the sheet was measured.

(Peelability of ceramic green sheet)
The ceramic green sheets obtained in Examples 1 to 21 and Comparative Examples 1 to 13 were cut into 10 cm squares, 10 sheets were stacked on a PET film, and the heat and pressure conditions were 70 ° C., pressure 1,500 N / cm ² , 10 minutes. After the lamination, the peeled state when the ceramic green sheet was peeled from the PET film was visually judged and evaluated in the following three stages.
A: There is no ceramic green sheet adhering to the PET film, and there are no cuts or cracks in the ceramic green sheet. B: Some ceramic green sheets adhering to the PET film are recognized, or the ceramic green sheets are cut or cracked. C: Some ceramic green sheets attached to the PET film are recognized, or many ceramic green sheets are cut or cracked.

(Flexibility of ceramic green sheets)
The state of cracks and cracks when the ceramic green sheet was wound around a 5 mmφ rod was visually judged and evaluated in the following four stages.
A: No cracks and cracks B: Some cracks C: Some cracks D: Some cracks

<Manufacture of multilayer ceramic capacitors>
100 parts by mass of nickel powder (“Mitsui Mining & Mining“ 2020SS ”) as conductive powder, 5 parts by mass of ethylcellulose (“ STD-100 ”manufactured by Dow Chemical Company), 60 mass of terpineol-C (manufactured by Nippon Terpene) as a solvent After mixing the parts, a conductive paste was obtained by kneading with three rolls. The conductive paste was applied to one side of each ceramic green sheet by a screen printing method and dried to form a conductive layer having a thickness of about 1.0 μm. The ceramic green sheets having this conductive layer were cut into 5 cm squares, stacked 100, and heated and pressed for 10 minutes at a temperature of 70 ° C. and a pressure of 150 kg / cm ² to obtain a laminate. The obtained laminate was heated to 400 ° C. at a heating rate of 3 ° C./min in a nitrogen atmosphere, held for 5 hours, and further heated to 1,350 ° C. at a heating rate of 5 ° C./min. A multilayer ceramic capacitor was obtained by holding for 10 hours.

  By using the ceramic green sheet prepared using the POA-modified vinyl acetal polymer of the example, a multilayer ceramic capacitor can be produced without any problem, and the obtained multilayer ceramic capacitor operated without any problem as a multilayer ceramic capacitor. .

As shown in Tables 4 and 5, the POA-modified vinyl acetal polymers of the examples had small haze, excellent transparency, sufficiently low solution viscosity, and excellent viscosity stability. Moreover, the slurry composition for ceramic green sheets prepared using the POA-modified vinyl acetal polymer of the example was superior in the dispersibility and thixotropy of the ceramic particles as compared with the comparative example. Furthermore, the ceramic green sheet obtained using the POA-modified vinyl acetal polymer of the example was superior in dispersibility, strength, peelability and flexibility of the ceramic particles as compared with the comparative example. The slurry compositions for ceramic green sheets prepared using the POA-modified vinyl acetal polymers of Examples 1 to 3, Example 5, Example 7, Examples 10 and 11, and Examples 13 to 17 are ceramics. The particles were particularly excellent in dispersibility and thixotropy (average particle diameter (dispersibility of ceramic particles) was less than 0.70 μm and thixotropy was 6.0 or more). Furthermore, the ceramic green sheets obtained using the POA-modified vinyl acetal polymers of Examples 1 to 3, Example 5, Example 7, Examples 10 and 11, and Examples 13 to 17 are dispersed ceramic particles. Property, strength, releasability and flexibility (dispersibility, releasability and flexibility were all evaluated as A, and the strength at break was 25 g / cm ² or more).

  The POA-modified vinyl acetal polymer of the present invention has a low glass transition point and excellent plasticity. The POA-modified vinyl acetal polymer has high solubility in an alcohol solvent, its solution viscosity is low, and the stability of the solution viscosity over time is sufficiently satisfied. A composition using the POA-modified vinyl acetal polymer as various binders hardly causes phase separation, and exhibits high dispersibility of particles and thixotropic properties. Furthermore, since the POA-modified vinyl acetal polymer of the present invention is internally plasticized, thermoplastic processing is possible even if the amount of plasticizer used is reduced. Therefore, by using the POA-modified vinyl acetal polymer, problems such as deterioration of physical properties due to the addition of a large amount of plasticizer can be avoided, and films, sheets and the like excellent in strength, ease of peeling and flexibility can be produced. can do.

Claims (18)

A polyoxyalkylene-modified vinyl acetal polymer obtained by acetalizing a polyoxyalkylene-modified vinyl alcohol polymer,
It contains a monomer unit derived from an unsaturated monomer represented by the following formula (3), the monomer unit content is 0.05 mol% or more and 10 mol% or less, and the viscosity average polymerization A polyoxyalkylene-modified vinyl acetal polymer having a degree of 150 to 5,000 and an acetalization degree of 10 mol% to 85 mol%.

(In Formula (3), R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ is a hydrogen atom or a methyl group. X is —O—, —CH ₂ —O—, —CO—, — (CH ₂ ) _k —, —COO—, or —CO—NR ⁵ — , wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k is 1 to 15; Y is a group including a block represented by the following formula (1) and a block represented by the following formula (2).

(In Formula (1), ^one of R ¹ and R ² is a methyl group and the other is a hydrogen atom. M represents the number of repeating units and is an integer of 10 to 40.] R ¹ and R ² may be the same or different.)

(In formula (2), n represents the number of repeating units and is an integer of 1 to 50.) The polyoxyalkylene-modified vinyl acetal polymer according to claim 1, wherein the block represented by the formula (1) is located on the main chain side from the block represented by the formula (2). The polyoxyalkylene-modified vinyl acetal polymer according to claim 1 or 2, wherein the block represented by the formula (1) and the block represented by the formula (2) are directly bonded. The polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 3 , wherein the aldehyde used for acetalization is at least one selected from the group consisting of butyraldehyde and acetaldehyde. The polyoxyalkylene-modified vinyl acetal polymer according to claim 4 , wherein the aldehyde used for acetalization is butyraldehyde. The composition containing the polyoxyalkylene modified vinyl acetal polymer of any one of Claims 1-5 . The composition according to claim 6 , further comprising a ceramic powder and an organic solvent, and used as a slurry composition for a ceramic green sheet. A ceramic green sheet obtained using the composition according to claim 7 . A multilayer ceramic capacitor obtained by using the ceramic green sheet according to claim 8 . An interlayer film for laminated glass containing the polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 5 . An ink containing the polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 5 . The coating agent containing the polyoxyalkylene modified vinyl acetal polymer of any one of Claims 1-5 . A photothermographic material containing the polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 5 . The electrically conductive paste containing the polyoxyalkylene modified vinyl acetal polymer of any one of Claims 1-5 . The powder coating material containing the polyoxyalkylene modified vinyl acetal polymer of any one of Claims 1-5 . A pellet containing the polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 5 . A film containing the polyoxyalkylene-modified vinyl acetal polymer according to any one of claims 1 to 5 and containing no plasticizer. By copolymerization of an unsaturated monomer represented by the following formula (3) and a vinyl ester monomer, the viscosity average polymerization degree is 150 to 5,000, and the content of the unsaturated monomer unit is A step of obtaining 0.05 to 10 mol% of a polyoxyalkylene-modified vinyl ester polymer,
A step of obtaining a polyoxyalkylene-modified vinyl alcohol polymer having a saponification degree of 20 mol% or more and 99.99 mol% or less by saponification of the polyoxyalkylene-modified vinyl ester polymer; and A method for producing a polyoxyalkylene-modified vinyl acetal polymer comprising a step of obtaining a polyoxyalkylene-modified vinyl acetal polymer having a degree of acetalization of 10 mol% or more and 85 mol% or less by acetalization of the polymer.

(In Formula (3), R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ is a hydrogen atom or a methyl group. X is —O—, —CH ₂ —O—, —CO—, — (CH ₂ ) _k —, —COO—, or —CO—NR ⁵ —, wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, k is 1 to 15; Y is a group including a block represented by the following formula (1) and a block represented by the following formula (2).

(In Formula (1), ^one of R ¹ and R ² is a methyl group and the other is a hydrogen atom. M represents the number of repeating units and is an integer of 10 to 40.] R ¹ and R ² may be the same or different.)

(In formula (2), n represents the number of repeating units and is an integer of 1 to 50.)