JP2022072708A - Modified polyvinyl acetal resin compound, resin composition and resin film - Google Patents

Abstract

To provide a modified polyvinyl acetal resin compound that can be dissolved in organic solvent to give a low-viscosity acetal solution.SOLUTION: A modified polyvinyl acetal resin compound contains a vinyl alcohol unit of formula (1) 0 mol%-20 mol%, a vinyl acetal unit of formula (2) 30 mol%-90 mol%, a vinyl acetate unit of formula (3) 0 mol%-25 mol%, and an ether modified unit of formula (4) 10 mol%-35 mol%.SELECTED DRAWING: None

Description

The present invention relates to modified polyvinyl acetal resin compounds, resin compositions and resin films.

The polyvinyl butyral resin, which is a polyvinyl acetal resin, is excellent in strength and flexibility. For this reason, polyvinyl butyral resin is used for interlayer films for laminated glass, paints, inks, binders and the like.

The polyvinyl acetal resin is produced by a method of condensing polyvinyl alcohol (PVA) and an aldehyde to acetalize PVA. In the reaction of PVA with aldehyde, PVA is not completely acetalized. Therefore, more than 20 mol% of vinyl alcohol units remain in the structural units of the polyvinyl acetal resin obtained after the reaction. The hydroxyl group of the vinyl alcohol unit has a great influence on the properties of the polyvinyl acetal resin. For example, the viscosity of an acetal solution obtained by dissolving a polyvinyl acetal resin in an organic solvent increases as the number of vinyl alcohol units increases (in other words, the amount of hydroxyl groups increases).

Conventionally, in a polyvinyl acetal resin, a method of reducing the vinyl alcohol unit contained in the polyvinyl acetal resin has been proposed.
For example, Reference 1 describes a method for producing a modified polyvinyl acetal resin in which the residual hydroxyl group of the polyvinyl acetal resin is adjusted to 20 mol% or less in vinyl alcohol units by reacting the residual hydroxyl group of the polyvinyl acetal resin with an isocyanate compound. Have been described.

Further, Reference Document 2 describes a modified polyvinyl acetal containing a vinyl acetal unit, a vinyl alcohol unit, and a vinyl acetate unit. In Reference 2, a modified polyvinyl acetal is obtained by saponifying a 1-alkyl vinyl acetate-vinyl acetate copolymer and then acetalizing a saponified product containing vinyl alcohol and 1-alkyl vinyl alcohol units. It is stated that it will be done.

Japanese Patent No. 3406019 Japanese Patent No. 3315128

However, a conventional acetal solution in which a modified polyvinyl acetal resin compound is dissolved in an organic solvent is required to have a lower viscosity.
As a method for lowering the viscosity of the acetal solution, a modified polyvinyl acetal resin compound having a low degree of polymerization can be used, or the content of the organic solvent in the acetal solution can be increased to reduce the concentration of the modified polyvinyl acetal resin compound. Conceivable. However, if the viscosity of the acetal solution is lowered by these methods, the necessary physical properties required for the acetal solution may not be obtained.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a modified polyvinyl acetal resin compound capable of obtaining an acetal solution having a low viscosity by dissolving it in an organic solvent.
Another object of the present invention is to provide a resin composition and a resin film containing the modified polyvinyl acetal resin compound of the present invention.

[1] The vinyl alcohol unit represented by the following formula (1) is 0 mol% to 20 mol%,
The vinyl acetal unit represented by the following formula (2) is 30 mol% to 90 mol%,
The vinyl acetate unit represented by the following formula (3) is 0 mol% to 25 mol%,
A modified polyvinyl acetal resin compound containing 10 mol% to 35 mol% of an ether modification unit represented by the following formula (4).

（式（２）中において、Ｒ_１は水素原子または炭化水素基である。式（４）中において、Ｒ_２はエーテル結合を含む基である。）

(In formula (2), R ₁ is a hydrogen atom or a hydrocarbon group. In formula (4), R ₂ is a group containing an ether bond.)

[2] The modified polyvinyl acetal resin compound according to [1], wherein the vinyl alcohol unit represented by the formula (1) is 15 mol% or less.
[3] R ₂ in the formula (4) is any one selected from a methoxymethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a methoxyethyl group, and a methoxypropyl group [1] or [2]. The modified polyvinyl acetal resin compound described.

[4] A resin composition containing the modified polyvinyl acetal resin compound according to any one of [1] to [3].
[5] A resin film containing the modified polyvinyl acetal resin compound according to any one of [1] to [3].

The modified polyvinyl acetal resin compound of the present invention contains structural units represented by the formulas (1) to (4), and the content of the vinyl alcohol unit represented by the formula (1) is 0 mol% to 20 mol. It has a small amount of vinyl alcohol unit, which is%. Moreover, the modified polyvinyl acetal resin compound of the present invention contains 10 mol of the ether-modified unit represented by the formula (4) in which the hydrogen atom of the hydroxyl group of the vinyl alcohol unit is modified to a group containing an ether bond represented by _R2 . Contains% to 35 mol%. Therefore, the modified polyvinyl acetal resin compound of the present invention is a non-modified polyvinyl acetal resin compound containing a vinyl alcohol unit represented by the formula (1) instead of the ether modification unit represented by the formula (4). In comparison, it has excellent solubility in organic solvents. Therefore, the modified polyvinyl acetal resin compound of the present invention can be dissolved in an organic solvent to obtain an acetal solution having a low viscosity.

Since the resin composition of the present invention contains the modified polyvinyl acetal resin compound of the present invention, it has good dispersibility, low viscosity, and is easy to handle.
Since the resin film of the present invention contains the modified polyvinyl acetal resin compound of the present invention, it can be produced by using a resin composition containing the modified polyvinyl acetal resin compound of the present invention, which has good dispersibility and low viscosity. Therefore, the resin film of the present invention has good moldability and is excellent in productivity.

Hereinafter, the modified polyvinyl acetal resin compound, the resin composition, and the resin film of the present invention will be described in detail.
[Modified polyvinyl acetal resin compound]
The modified polyvinyl acetal resin compound of the present embodiment contains structural units represented by the following formulas (1) to (4). In the modified polyvinyl acetal resin compound of the present embodiment, the arrangement order of the structural units represented by the formulas (1) to (4) is not particularly limited.

（式（２）中において、Ｒ_１は水素原子または炭化水素基である。式（４）中において、Ｒ_２はエーテル結合を含む基である。）

(In formula (2), R ₁ is a hydrogen atom or a hydrocarbon group. In formula (4), R ₂ is a group containing an ether bond.)

The modified polyvinyl acetal resin compound of the present embodiment contains 0 mol% to 20 mol% of the vinyl alcohol unit represented by the formula (1) and 30 mol% to 90 mol% of the vinyl acetal unit represented by the formula (2). , The vinyl acetate unit represented by the formula (3) is contained in an amount of 0 mol% to 25 mol%, and the ether modification unit represented by the formula (4) is contained in an amount of 10 mol% to 35 mol%.

Since the modified polyvinyl acetal resin compound of the present embodiment has a vinyl alcohol unit content of 20 mol% or less represented by the formula (1), a low-viscosity acetal solution can be obtained by dissolving it in an organic solvent. .. The content of the vinyl alcohol unit is preferably 15 mol% or less. The content of the vinyl alcohol unit may be 0 mol%. The content of the vinyl alcohol unit may be 5 mol% or more because it is a modified polyvinyl acetal resin compound having good productivity and excellent adhesiveness.
In the present embodiment, the "acetal solution" means a solution in which a modified polyvinyl acetal resin compound is dissolved in an organic solvent.

Since the modified polyvinyl acetal resin compound of the present embodiment contains 30 mol% or more of the vinyl acetal unit represented by the formula (2), it is excellent in adhesiveness, strength and flexibility. The content of the vinyl acetal unit is preferably 50 mol% or more. Further, since the content of the vinyl acetal unit is 90 mol% or less, the modified polyvinyl acetal resin compound sufficiently contains the ether modification unit represented by the formula (4). The content of vinyl acetal units is preferably 80 mol% or less.

The acetal group contained in the modified polyvinyl acetal resin compound of the present embodiment is obtained by acetalizing two hydroxyl groups of polyvinyl alcohol (PVA). Therefore, in the present embodiment, the content (degree of acetalization) of the vinyl acetal unit represented by the formula (2) counts the structure in which two hydroxyl groups are acetalized as one vinyl acetal unit. Calculated using the method.

In the formula (2), R ₁ is a hydrogen atom or a hydrocarbon group, and is appropriately determined depending on the use of the modified polyvinyl acetal resin compound. The hydrocarbon group is preferably any one selected from an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group and a benzyl group. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group and a 2-ethylhexyl group. Among the above, R ₁ is preferably an n-propyl group because it has a high glass transition temperature and high solubility in an organic solvent.
Among the plurality of vinyl acetal units represented by the formula (2) contained in the modified polyvinyl acetal resin compound of the present embodiment, the vinyl acetal unit may have only _one type of R1 or 2 It may be more than a seed.

The modified polyvinyl acetal resin compound of the present embodiment contains 0 mol% to 25 mol% of the vinyl acetate unit represented by the formula (3). Since the modified polyvinyl acetal resin compound of the present embodiment has a vinyl acetate unit content of 25 mol% or less, it has excellent solubility in an organic solvent. The content of the vinyl acetate unit is preferably 10 mol% or less. The content of the vinyl acetate unit may be 0 mol%.

In the modified polyvinyl acetal resin compound of the present embodiment, the ether modification unit represented by the formula (4) is a hydrogen atom having a hydroxyl group of the vinyl alcohol unit represented by the formula (1), and an ether bond represented by _R2 . It is a structural unit modified to a group containing.
Since the modified polyvinyl acetal resin compound of the present embodiment has an ether modification unit content of 10 mol% or more, a low-viscosity acetal solution can be obtained by dissolving it in an organic solvent. The content of the ether modification unit is preferably 15 mol% or more. Further, since the content of the ether modification unit is 35 mol% or less, the physical properties peculiar to the polyvinyl acetal resin compound are not impaired by having too many ether modification units. The content of the ether modification unit is preferably 25 mol% or less.

In formula (4), R ₂ is a group containing an ether bond. Among the plurality of ether-modified units represented by the formula (4) contained in the modified polyvinyl acetal resin compound of the present embodiment, only one type of R ₂ may be contained in the ether-modified unit, or 2 It may be more than a seed.
_R2 may be a group containing an ether bond, and is appropriately determined depending on the use of the modified polyvinyl acetal resin compound. Since R ₂ is a modified polyvinyl acetal resin compound having further excellent solubility in an organic solvent, it is preferably a group that does not contain a hydroxyl group and has a small polarity.

Specifically, R ₂ includes a methoxymethyl group (MOM (-CH ₂ OCH ₃ )), a 2-methoxyethoxymethyl group (MEM (-CH ₂ OCH ₂ CH ₂ OCH ₃ )), and a benzyloxymethyl group (BOM (-CH 2 OCH 3)). -CH ₂ OCH ₂ -C ₅ H ₆ )), methoxyethyl group (MOE (-CH ₂ CH ₃ OCH ₃ )), methoxypropyl group (MOP (-CH ₂ CH ₂ CH ₂ OCH ₃ )), ethoxymethyl group (-CH ₂ OCH ₂ CH ₃ ) and the like can be mentioned, and any one selected from a methoxymethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a methoxyethyl group and a methoxypropyl group is preferable.

When R ₂ is any one selected from a methoxymethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a methoxyethyl group, and a methoxypropyl group, the hydroxyl group of the vinyl alcohol unit contained in the polyvinyl acetal resin compound and these. By reacting with a compound having a group of, an ether modification unit is obtained. Therefore, the modified polyvinyl acetal resin compound in which R ₂ is a group thereof can be easily produced. Further, when R ₂ is these groups, the length of the side chain bonded to the main chain of the polyvinyl acetal resin by an ether bond does not become too long. Therefore, the ether modification unit having R ₂ does not interfere with the physical properties peculiar to the polyvinyl acetal resin compound obtained by having the vinyl acetal unit and the vinyl acetate unit, which is preferable.

The modified polyvinyl acetal resin compound of the present embodiment preferably has a degree of polymerization of 100 to 5000, more preferably 300 to 3000. When the degree of polymerization is 100 or more, the modified polyvinyl acetal resin compound has good adhesiveness and strength. When the degree of polymerization is 5000 or less, an acetal solution having a lower viscosity can be obtained by dissolving it in an organic solvent.

"Production method"
The modified polyvinyl acetal resin compound of the present embodiment can be produced, for example, by the method shown below.
Polyvinyl alcohol (PVA) and aldehyde are condensed and reacted to acetalize PVA to produce a polyvinyl acetal resin. As a method for producing the polyvinyl acetal resin, a known method can be used.

The polyvinyl acetal resin produced by a known method usually contains more than 20 mol% and 50 mol% or less of the vinyl alcohol unit represented by the formula (1) and 30 vinyl acetal units represented by the formula (2). It contains 0 mol% to 25 mol% of vinyl acetate unit represented by the formula (3), which is mol% to 90 mol%. That is, more than 20 mol% of vinyl alcohol units remain in the polyvinyl acetal resin produced by a known method.

As the aldehyde used as a raw material for the polyvinyl acetal resin, for example, one or more selected from aldehydes having a hydrocarbon group such as acetaldehyde, propionaldehyde and butyraldehyde, and formaldehyde can be used. As the aldehyde, in the modified polyvinyl acetal resin compound of the present embodiment, an aldehyde having a hydrocarbon group or a hydrogen atom corresponding to _R1 having a vinyl acetal unit represented by the formula (2) is used. Specifically, for example, when a polyvinyl butyral resin is produced as a polyvinyl acetal resin, butyraldehyde is used as the aldehyde.

As the polyvinyl acetal resin, a commercially available one may be used. Examples of the commercially available polyvinyl acetal resin include polyvinyl butyral (trade name; BM-S, average degree of polymerization 860, vinyl alcohol unit of about 23 mol%, and vinyl acetal unit (acetalization degree) of about 72 mol%. It contains about 4 to 6 mol% of vinyl acetate unit. Polyvinyl butyral (trade name; BH-3, average degree of polymerization 1700, vinyl alcohol unit is about 34 mol%), manufactured by Sekisui Chemical Industry Co., Ltd. A vinyl acetal unit (degree of acetalization) of about 65 mol% and a vinyl acetate unit of 3 mol% or less can be used (manufactured by Sekisui Chemical Industry Co., Ltd.).

As the commercially available polyvinyl acetal resin, polyvinyl butyral manufactured by Sekisui Chemical Co., Ltd. shown below may be used. Trade name; BH-6 (contains an average degree of polymerization of 1300, a vinyl alcohol unit of about 30 mol%, a vinyl acetal unit (degree of acetalization) of about 69 mol%, and a vinyl acetate unit of 3 mol% or less). , Trade name; BH-A (contains an average degree of polymerization of 1700, about 27 mol% of vinyl alcohol unit, and about 60 mol% of vinyl acetal unit (degree of acetalization)), trade name: BX-1 (average). Contains 1700 degree of polymerization, 33 ± 3 mol of vinyl alcohol unit and%, vinyl acetal unit (degree of acetalization) of about 72 mol%), trade name; BX-5 (average degree of polymerization 2400, vinyl alcohol unit). Contains 33 ± 3 mol% and vinyl acetal unit (degree of acetalization) of about 72 mol%), trade name; BM-1 (average degree of polymerization: 650, vinyl alcohol unit of about 34 mol%, vinyl acetal. Unit (degree of acetalization) is about 65 mol%), trade name; BM-2 (average degree of polymerization 800, vinyl alcohol unit is about 31 mol%, vinyl acetal unit (degree of acetalization) is about 69. (Contains mol%), trade name; BM-5 (contains an average degree of polymerization of 850, a vinyl alcohol unit of about 34 mol%, and a vinyl acetal unit (degree of acetalization) of about 65 mol%). Product name: BL-1 (average polymerization degree 300, containing about 36 mol% of vinyl alcohol unit), product name: BL-2 (average polymerization degree 450, containing about 36 mol% of vinyl alcohol unit), product name. BL-2H (containing about 29 mol% of vinyl alcohol unit), trade name; BL-10 (containing about 28 mol% of vinyl alcohol unit) and the like may be used.

As the commercially available polyvinyl acetal resin, polyvinyl butyral manufactured by Kuraray Co., Ltd. shown below may be used. Product name: Mobital B20H (average degree of polymerization 250 to 500, containing 26 to 31 mol% of vinyl alcohol unit), trade name: 30T (average degree of polymerization 400 to 650, containing 33 to 38 mol% of vinyl alcohol unit) , Trade name; 30H (average degree of polymerization 400 to 650, containing 26 to 31 mol% of vinyl alcohol unit), trade name; 30HH (average degree of polymerization 400 to 650, containing 30 to 34 mol% of vinyl alcohol unit). , Trade name: 45H (average degree of polymerization 600 to 850, containing 26 to 31 mol% of vinyl alcohol unit), trade name; 60T (average degree of polymerization 750 to 1000, containing 34 to 38 mol% of vinyl alcohol unit). , Trade name: 60H (average degree of polymerization 750 to 1000, containing 26 to 31 mol% of vinyl alcohol unit), trade name; 75H (average degree of polymerization 1500 to 1750, containing 26 to 31 mol% of vinyl alcohol unit). Etc. can be used.

Next, the hydroxyl group of the vinyl alcohol unit of the polyvinyl acetal resin is reacted with sodium hydride to produce a sodium salt of the polyvinyl acetal resin. Next, the sodium salt of the polyvinyl acetal resin is reacted with the halogenated compound having the group corresponding to R ₂ in the formula (4). As a result, the modified polyvinyl acetal resin compound of the present embodiment in which the hydrogen atom contained in the hydroxyl group of the vinyl alcohol unit is modified to a group containing an ether bond represented by R ₂ can be obtained.

Examples of the halogenated compound having a group corresponding to R ₂ in the formula (4) include chloromethyl ether, benzyl chloromethyl ether, 2-methoxyethyl bromide, chloromethyl methyl sulfide, 2-methoxyethoxymethyl chloride, 3-. One or more selected from bromopropylmethyl ethers can be used. As the halogenated compound, a halogenated compound having a group containing an ether bond corresponding to R ₂ in the formula (4) of the modified polyvinyl acetal resin compound is used.

The ratio of the structural units represented by the formulas (1) to (4) contained in the modified polyvinyl acetal resin compound of the present embodiment is the ratio of the formulas (1) to (3) contained in the polyvinyl acetal resin before the modification. ), The amount of sodium hydride and the halogenated compound to be reacted with the polyvinyl acetal resin before modification, and the reaction conditions can be adjusted. The ratio of the structural units represented by the formulas (1) to (3) contained in the polyvinyl acetal resin before the modification adjusts the amount of polyvinyl alcohol (PVA) and aldehyde used as raw materials and the reaction conditions. It can be controlled by doing.
The degree of polymerization of the modified polyvinyl acetal resin compound is determined by the degree of polymerization of the polyvinyl acetal resin before modification. The degree of polymerization of the polyvinyl acetal resin before modification can be controlled by adjusting the degree of polymerization of PVA used as a raw material.

The modified polyvinyl acetal resin compound of the present embodiment contains structural units represented by the formulas (1) to (4), and the content of the vinyl alcohol unit represented by the formula (1) is 0 mol% to 20. It is low in vinyl alcohol units, which is mol%. Moreover, the modified polyvinyl acetal resin compound of the present embodiment contains 10 ether-modified units represented by the formula (4) in which the hydrogen atom of the hydroxyl group of the vinyl alcohol unit is modified to a group containing an ether bond represented by _R2 . Contains mol% to 35 mol%. Therefore, the modified polyvinyl acetal resin compound of the present embodiment is an unmodified polyvinyl acetal resin compound containing a vinyl alcohol unit represented by the formula (1) instead of the ether modification unit represented by the formula (4). It has excellent solubility in organic solvents. Therefore, the modified polyvinyl acetal resin compound of the present embodiment can be dissolved in an organic solvent to obtain an acetal solution having a low viscosity.

On the other hand, for example, in the modified polyvinyl acetal resin compound having a group bonded by a urethane bond instead of the group containing an ether bond represented by R ₂ in the structural unit represented by the formula (4), R ₂ is used. Since the polarity and dielectric constant of the group bonded by the urethane bond are higher than those of the group containing the ether bond shown in (1), the effect of improving the solubility in an organic solvent cannot be sufficiently obtained.

[Resin composition]
Next, the resin composition of the present embodiment will be described in detail.
The resin composition of the present embodiment contains the modified polyvinyl acetal resin compound of the present embodiment and a solvent. The resin composition of the present embodiment may contain, if necessary, other components in addition to the modified polyvinyl acetal resin compound of the present embodiment and the solvent.

The modified polyvinyl acetal resin compound contained in the resin composition of the present embodiment functions as, for example, a binder, a dispersant, an adhesive, a sealing resin, or the like, depending on the use of the resin composition.
The use of the resin composition of the present embodiment is not particularly limited, and is used, for example, as a slurry for producing a green sheet, a step absorbing paste for electronic parts, a paste for electrodes, an ink, a paint, a composition for film forming, and the like. be able to.

When the resin composition of the present embodiment contains other components, the content of the modified polyvinyl acetal resin compound in the components excluding the solvent in the resin composition is preferably 1% by mass to 95% by mass. More preferably, it is by mass% to 30% by mass. When the content of the modified polyvinyl acetal resin compound is 1% by mass or more, the dispersibility is improved by containing the modified polyvinyl acetal resin compound, and the effect of lowering the viscosity becomes remarkable. When the content of the modified polyvinyl acetal resin compound is 95% by mass or less, it becomes easy to obtain a resin composition suitable for the intended use by adjusting the type and content of other components.

Other components that may be contained in the resin composition of the present embodiment include, for example, an insulating powder such as ceramic powder, a conductive powder such as metal powder, an organic powder, an antioxidant, an ultraviolet absorber, and a plasticizer. Examples thereof include agents, dyes, adhesive imparting agents, polymerizable monomers and / or oligomers, polymerization initiators such as thermal polymerization initiators and / or photopolymerization initiators, epoxy resins, curing agents for epoxy resins, and the like, and resin compositions. One type or a mixture of two or more types can be used depending on the intended use.

As the solvent, a solvent capable of dissolving the modified polyvinyl acetal resin compound can be used, and can be appropriately determined depending on the use of the resin composition. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, dipropyl ketone and diisobutyl ketone, alcohols such as methanol, ethanol, 1-propanol, 2-propanol and n-butanol, and aromatic hydrocarbons such as toluene and xylene. Kind, Methyl propionate, Ethyl propionate, Butyl propionate, Methyl butanoate, Ethyl butanoate, Butyl butanoate, Methyl pentanate, Ethyl pentanate, Butyl pentanate, Methyl hexanoate, Ethyl hexanoate, Butyl hexanoate, Esters such as 2-ethylhexyl acetate, 2-ethylhexyl butyrate, 2-methoxyethyl acetate, methylcellsolve, ethylcellsolve, butylcellsolve, terpineol, dihydroterpineol, butylcellsolve acetate, butylcarbitol acetate, terpineol acetate, Examples include dihydroterpineol acetate. Among these solvents, one or more selected from 1-propanol, 2-propanol, n-butanol, toluene, and 2-methoxyethyl acetate may be used in order to obtain a highly versatile resin composition. preferable.

The amount of the solvent used is the type of the solvent and the ratio of the structural units represented by the formulas (1) to (4) in the modified polyvinyl acetal resin compound so that the viscosity is appropriate according to the use of the resin composition. , R ₂ is appropriately determined according to the type of the group containing the ether bond, the degree of polymerization, and the type and content of the other components if they are contained.

Examples of the insulating powder that may be contained in the resin composition of the present embodiment include alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, magnesia, sialon, spinnemullite, and silicon carbide. , Silicon nitride, aluminum nitride, iron oxide, ferrite, boron oxide, boric acid, boric acid glass, borosilicate glass and the like, and can be appropriately determined depending on the use of the resin composition, and is not particularly limited. Only one kind of these insulating powders may be contained, or two or more kinds thereof may be contained.

Examples of the conductive powder that may be contained in the resin composition of the present embodiment include metal powders made of nickel, silver, gold, platinum, palladium, copper, various alloys, and the like, and are used for the resin composition. It can be determined as appropriate, and is not particularly limited. Only one kind of these conductive powders may be contained, or two or more kinds thereof may be contained.

Examples of the organic powder that may be contained in the resin composition of the present embodiment include pigments such as diazo pigments and phthalocyanine pigments, dyes, and the like, which are appropriately determined according to the use of the resin composition. It can be done, and it is not particularly limited. These organic powders may contain only one kind, or may contain two or more kinds.

When the resin composition of the present embodiment contains, for example, the modified polyvinyl acetal resin compound of the present embodiment, a solvent, and an insulating powder, it is suitable as a slurry for producing a green sheet or a step absorbing paste for electronic components. Can be used. In particular, a slurry for producing a green sheet used as a material for a green sheet which is a laminated ceramic electronic component, and a step for an electronic component used to fill a step between a convex portion composed of electrodes and the like and a region around the convex portion in the electronic component. It can be suitably used as an absorbent paste.

When the resin composition of the present embodiment contains an insulating powder, the modified polyvinyl acetal resin compound contained in the resin composition of the present embodiment mainly functions as a binder. The content of the insulating powder in the resin composition is preferably 100 parts by mass to 10,000 parts by mass with respect to 100 parts by mass of the modified polyvinyl acetal resin. When the content of the insulating powder is 100 parts by mass or more, it is easy to obtain a green sheet having sufficient mechanical strength by using the resin composition as a slurry for producing a green sheet. Further, when the content of the insulating powder is 100 parts by mass or more, it is easy to obtain an electronic component having sufficient mechanical strength by using the resin composition as a step absorbing paste for an electronic component. When the content of the insulating powder is 10,000 parts by mass or less, the dispersibility of the insulating powder becomes better, so that a slurry for producing a green sheet having excellent printability and coatability, or a step absorbing paste for electronic parts It becomes.

When the resin composition of the present embodiment is a slurry for producing a green sheet or a step absorbing paste for electronic parts, the viscosity of the resin composition is preferably 10 to 300,000 mPs · s, preferably 50 to 100,000 mPs. -S is more preferable, and 50 to 8,000 mPs · s is even more preferable. When the resin composition is used for the above purposes, good printability and coatability can be obtained when the viscosity is 10 to 300,000 mPs · s.

When the resin composition of the present embodiment contains, for example, the modified polyvinyl acetal resin compound of the present embodiment, a solvent, and a conductive powder, it can be suitably used as an electrode paste. In particular, it is suitable as an electrode paste used for forming an electrode of a laminated ceramic electronic component, a conductive portion of a laminated chip inductor, a conductive portion of a printed wiring board, and the like.

When the resin composition of the present embodiment contains a conductive powder, the modified polyvinyl acetal resin compound contained in the resin composition of the present embodiment mainly functions as a binder. The content of the conductive powder in the resin composition is preferably 100 parts by mass to 10,000 parts by mass with respect to 100 parts by mass of the modified polyvinyl acetal resin. When the content of the conductive powder is 100 parts by mass or more, a conductive member having sufficient conductivity can be obtained by using the resin composition as an electrode paste. Further, when the content of the conductive powder is 10,000 parts by mass or less, the dispersibility of the conductive powder becomes better, so that the paste for electrodes has more excellent printability and coatability.

When the resin composition of the present embodiment contains, for example, the modified polyvinyl acetal resin compound of the present embodiment, a solvent, and an organic powder, it can be suitably used as an ink or a paint. In particular, a resin composition containing a pigment and / or a dye as an organic powder is suitable as an ink for inkjet and a paint for spray painting.

When the resin composition of the present embodiment contains an organic powder, the content of the organic powder in the resin composition is preferably 10% by mass to 30% by mass. When the content of the organic powder in the resin composition is 10% by mass or more, a coating film having a desired color can be formed when the resin composition is used as an ink or a paint. When the content of the organic powder in the resin composition is 30% by mass or less, the dispersibility of the organic powder becomes better, so that the ink or paint has more excellent printability and coatability.
When the resin composition is used as a concentrated ink or paint, the content of the organic powder in the resin composition is preferably 15% by mass to 30% by mass. When the resin composition is used as a diluted ink or paint, the content of the organic powder in the resin composition is preferably 10% by mass to 15% by mass.

When the resin composition of the present embodiment is used as an ink or a paint, the content of the modified polyvinyl acetal resin compound in the resin composition is preferably 1% by mass to 95% by mass.
When the resin composition of the present embodiment is used as an ink or a paint, the content of the solvent in the resin composition is preferably 60% by mass to 85% by mass. When the blending amount of the solvent is within the above range, the ink or paint has more excellent printability and coatability.

When the resin composition of the present embodiment is composed of, for example, the modified polyvinyl acetal resin compound of the present embodiment and a solvent only, or the modified polyvinyl acetal resin compound of the present embodiment and the solvent, the polymerizable property. A composition for film molding, in the case of containing one or more selected from a polymerization initiator such as a monomer and / or oligomer, a thermal polymerization initiator and / or a photopolymerization initiator, an epoxy resin, and a curing agent for an epoxy resin. Can be suitably used as. In particular, as a film forming composition used for forming a hot melt type adhesive film (adhesive sheet), a hot melt type encapsulant film (encapsulating material sheet), an interlayer film for laminated glass, and the like. Suitable. When the resin composition of the present embodiment is a composition for film molding, the modified polyvinyl acetal resin compound contained in the resin composition mainly functions as an adhesive or a sealing resin.

The resin composition of the present embodiment can be produced by a method of mixing the modified polyvinyl acetal resin compound of the present embodiment, a solvent, and other components contained as necessary. When the resin composition of the present embodiment contains other components, the order in which the other components are mixed in the step of producing the resin composition is not particularly limited. For example, it may be produced by dissolving a modified polyvinyl acetal resin compound in a solvent to prepare an acetal solution, and then adding other components to the acetal solution and mixing them, or all the components contained in the resin composition. May be produced by a method of mixing all at once.

In the step of producing the resin composition of the present embodiment, a known method can be used as a method of mixing each component, and it can be appropriately determined according to the composition and viscosity of the resin composition. Specifically, for example, as a method of mixing the components contained in the resin composition, a method of mixing using various mixers such as a three-roll, a ball mill, and a bead mill can be used.

The resin composition of the present embodiment contains the modified polyvinyl acetal resin compound of the present embodiment. Therefore, a resin composition containing a polyvinyl acetal resin compound containing a vinyl alcohol unit represented by the formula (1) instead of the structural unit represented by the formula (4) in place of the modified polyvinyl acetal resin compound of the present embodiment. Compared with the product, the resin composition of the present embodiment has good dispersibility, low viscosity, and is easy to handle. Therefore, the resin composition of the present embodiment is excellent in moldability, printability and coatability.

Further, the modified polyvinyl acetal resin compound of the present embodiment is less likely to be adsorbed on the ceramic powder and / or the pigment as compared with, for example, the modified polyvinyl acetal resin compound having a group bonded by a urethane bond. Therefore, the resin composition of the present embodiment has a lower viscosity than the resin composition containing a modified polyvinyl acetal resin compound having a group bonded by a urethane bond and having the same degree of polymerization at the same concentration. It will be easy to handle.

[Multilayer ceramic electronic components]
Next, the laminated ceramic electronic component of the present embodiment will be described in detail.
The laminated ceramic electronic component of the present embodiment includes a green sheet made of a ceramic layer and an electrode layer formed on the green sheet. The electrode layer includes electrodes having a predetermined shape. The laminated ceramic electronic component of the present embodiment may be a laminated ceramic capacitor in which green sheets and electrode layers are alternately laminated.
The green sheet and the electrode layer of the laminated ceramic electronic component of the present embodiment include the modified polyvinyl acetal resin compound of the present embodiment.

The laminated ceramic electronic component of the present embodiment can be manufactured, for example, by the method shown below using the slurry for producing a green sheet and the paste for electrodes made of the resin composition of the present embodiment.
A slurry for producing a green sheet is applied onto a roll-shaped release-treated support member by a known method to form a coating film. Next, the solvent in the coating film is removed by a known method such as heating. This forms a ceramic green sheet.

Next, an electrode paste is printed on the surface of the ceramic green sheet to form an electrode having a predetermined shape. As a printing method of the electrode paste, for example, a known method such as screen printing or gravure printing can be used.
Next, the ceramic green sheet having the electrodes formed on the surface is cut into a predetermined shape and peeled off from the support member. Then, a plurality of ceramic green sheets on which the electrodes are formed are laminated and pressure-bonded by a known method to integrate them into a laminated body.
Then, the obtained laminate is degreased by a known method and fired. By the above steps, the laminated ceramic electronic component of the present embodiment can be obtained.

Since the laminated ceramic electronic component of the present embodiment can be produced by using the resin composition of the present embodiment containing the modified polyvinyl acetal resin compound of the present embodiment, it can be efficiently produced. More specifically, the slurry for producing a green sheet made of the resin composition of the present embodiment has good dispersibility of the insulating powder and is excellent in coatability. Therefore, by applying this to remove the solvent, a ceramic green sheet can be efficiently manufactured. Therefore, the ceramic green sheet containing the modified polyvinyl acetal resin compound of the present embodiment is excellent in productivity. Further, since the slurry for producing a green sheet has good dispersibility of the insulating powder, a ceramic green sheet with little variation in quality can be obtained by applying the slurry to remove the solvent. Therefore, the ceramic green sheet containing the modified polyvinyl acetal resin compound of the present embodiment has a good yield.

Further, the electrode paste made of the resin composition of the present embodiment has good dispersibility of the conductive powder and is excellent in printability. Therefore, by printing this on the surface of the ceramic green sheet, the electrodes can be efficiently formed. Further, since the electrode paste has good dispersibility of the conductive powder, by printing the paste, an electrode having little variation in quality can be obtained. Therefore, the laminated ceramic electronic component having an electrode containing the modified polyvinyl acetal resin compound of the present embodiment has excellent productivity and a good yield.

[Resin film]
Next, the resin film of the present embodiment will be described in detail.
The resin film of the present embodiment contains the modified polyvinyl acetal resin compound of the present embodiment. The resin film of the present embodiment is a film-shaped composition obtained from the resin composition of the present embodiment. The resin film of the present embodiment may be formed on a releasable film.

Applications of the resin film of the present embodiment include, for example, a hot melt type adhesive film (adhesive sheet) that is placed in a predetermined position and then melted and solidified by heat, and a hot melt type encapsulant film (adhesive sheet). Encapsulant sheet), interlayer film for laminated glass, and the like.

The content of the modified polyvinyl acetal resin compound in the resin film can be 1% by mass to 100% by mass, and can be appropriately determined depending on the use of the resin film. When the content of the modified polyvinyl acetal resin compound is 1% by mass or more, a resin film can be efficiently produced by using a resin composition having good moldability containing the modified polyvinyl acetal resin compound.

The resin film of the present embodiment can be produced by molding a film molding composition comprising the resin composition of the present embodiment by using a known molding method such as melt molding or cast molding.
Since the resin film of the present embodiment contains the modified polyvinyl acetal resin compound of the present embodiment, it can be produced by using a resin composition containing the modified polyvinyl acetal resin compound of the present embodiment and having good dispersibility and low viscosity. Therefore, the resin film of the present embodiment has good moldability and is excellent in productivity.

Although the embodiments of the present invention have been described in detail above, the configurations and combinations thereof in each embodiment are examples, and additions, omissions, substitutions, and the like of the configurations are added, omitted, substituted, and the like within the range not deviating from the gist of the present invention. Can be changed.

"Synthesis Example 1"
Using polyvinyl butyral (trade name; BM-S, manufactured by Sekisui Chemical Co., Ltd.) as the polyvinyl acetal resin, a modified polyvinyl acetal resin compound was synthesized under a nitrogen atmosphere by the method shown below.

To a 5 L round-bottomed flask, 510 g of the above polyvinyl butyral and 2000 mL of dehydrated dimethylformamide were added, and the mixture was heated to 50 ° C. with stirring to dissolve polyvinyl butyral to prepare a butyral solution. Then, 67 g of sodium hydride was added to the butyral solution and reacted at 50 ° C. for 5 hours to obtain a reaction solution. 90 g of chloromethyl ether was added dropwise to the obtained reaction solution, and the mixture was reacted at 70 ° C. overnight (16 hours) with stirring. After completion of the reaction, the reaction solution was cooled to room temperature and added dropwise to 5000 mL of ice water to obtain a precipitate. After collecting the precipitate by filtration, 5000 mL of water was added to the precipitate and the mixture was stirred overnight (16 hours) to wash the precipitate. The washed precipitate was collected by filtration and vacuum dried at 60 ° C. overnight (16 hours).

By the above steps, the desired modified polyvinyl butyral was obtained. The obtained modified polyvinyl butyral was weighed, and the yield was calculated from the theoretical yield. As a result, the yield was 82%.
Further, for the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured based on JIS K6728 "polyvinyl butyral test method". As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (13 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 1 contains 10 mol% of the vinyl alcohol unit represented by the formula (1) and 72 mol% of the vinyl acetal unit represented by the formula (2) (formula (2)). R ₁ in the group is a hydrogen atom or a hydrocarbon group, most of which are n-propyl groups), and the vinyl acetate unit represented by the formula (3) is represented by the formula (4) in an amount of 5 mol%. It can be considered that the ether modification unit to be subjected to contains 13 mol% (R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM)) and the average degree of polymerization is 860.

"Synthesis Example 2"
Using the same polyvinyl butyral as in Synthesis Example 1 as the polyvinyl acetal resin, a modified polyvinyl acetal resin compound was synthesized by the method shown below under a nitrogen atmosphere.
To a 5 L round-bottom flask, 2000 mL of a mixed solution of toluene and methyl ethyl ketone (MEK) mixed at a volume ratio of 1: 1 and 510 g of polyvinyl butyral were added, and heated to 50 ° C. with stirring to dissolve polyvinyl butyral. It was a butyral solution. Then, 0.38 g of dibutyltin diacetate and 50 g of phenyl isocyanate were added to the butyral solution and reacted at 50 ° C. for 5 hours to obtain a reaction solution. The obtained reaction solution was cooled to room temperature, and the mixture was added dropwise to 4500 mL of a mixed solution in which diethyl ether and hexane were mixed at a volume ratio of 1: 2 to obtain a precipitate. After collecting the precipitate by filtration, 5000 mL of water was added to the precipitate and the mixture was stirred overnight (16 hours) to wash the precipitate. The washed precipitate was collected by filtration and vacuum dried at 60 ° C. overnight (16 hours).

By the above steps, the desired modified polyvinyl butyral was obtained. The yield of the obtained modified polyvinyl butyral was calculated in the same manner as in Synthesis Example 1. As a result, the yield was 81%.
Further, for the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom possessed by the hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is -C (= O) -NH. -It is presumed that it was denatured to C ₅ H ₆ .

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 2 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 72 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 5 mol%, and the modification unit represented by the formula (4) is 13 mol% (R ₂ in the formula (4) is -C (= O) -NH-C ₅ H ₆ . It is contained and can be regarded as having an average degree of polymerization of 860.

"Synthesis Example 3"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that 2-methoxyethoxymethyl chloride was used instead of chloromethyl ether.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (13 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 3 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 72 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 5 mol%, and the ether modification unit represented by the formula (4) is 13 mol% (R ₂ in the formula (4) is −CH ₂ OCH ₂ CH ₂ OCH ₃ (MEM). It is contained and can be regarded as having an average degree of polymerization of 860.

"Synthesis Example 4"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that benzyl chloromethyl ether was used instead of chloromethyl ether.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (13 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 4 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 72 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 5 mol%, and the ether modification unit represented by the formula (4) is 13 mol% (R ₂ in the formula (4) is -CH ₂ OCH ₂ -C ₅ H ₆ (BOM). It can be considered that it is contained and the average degree of polymerization is 860.

"Synthesis Example 5"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that 2-methoxyethyl bromide was used instead of chloromethyl ether.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (13 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 5 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 72 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 5 mol%, and the ether modification unit represented by the formula (4) is 13 mol% (R ₂ in the formula (4) is −CH ₂ CH ₂ OCH ₃ (MOE). ), And can be considered to have an average degree of polymerization of 860.

"Synthesis Example 6"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that 3-bromopropylmethyl ether was used instead of chloromethyl ether.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 23 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (13 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 6 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 72 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 5 mol%, and the ether modification unit represented by the formula (4) is 13 mol% (R ₂ in the formula (4) is −CH ₂ CH ₂ CH ₂ OCH ₃ (MOP). It is contained and can be regarded as having an average degree of polymerization of 860.

"Synthesis Example 7"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 2 except that polyvinyl butyral (trade name; BH-3, manufactured by Sekisui Chemical Co., Ltd.) was used as the polyvinyl acetal resin.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (24 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 7 contains 10 mol% of the vinyl alcohol unit represented by the formula (1) and 65 mol% of the vinyl acetal unit represented by the formula (2) (formula (2)). R ₁ in the group is a hydrogen atom or a hydrocarbon group, most of which are n-propyl groups), and the vinyl acetate unit represented by the formula (3) is represented by 1 mol% and the formula (4). It can be considered that the modification unit to be modified contains 24 mol% (R ₂ in the formula (4) is -C (= O) -NH-C ₅ H ₆ ) and the average degree of polymerization is 1700. can.

"Synthesis Example 8"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that the same polyvinyl butyral as in Synthesis Example 7 was used as the polyvinyl acetal resin.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (24 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 8 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). Contains 1 mol% of the vinyl acetate unit represented by and 24 mol% of the ether modification unit represented by the formula (4) (R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM)). However, it can be considered that the average degree of polymerization is 1700.

"Synthesis Example 9"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 3 except that the same polyvinyl butyral as in Synthesis Example 7 was used as the polyvinyl acetal resin.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (24 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 9 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 1 mol%, and the ether modification unit represented by the formula (4) is 24 mol% (R ₂ in the formula (4) is −CH ₂ OCH ₂ CH ₂ OCH ₃ (MEM). Yes) It can be considered that it is contained and the average degree of polymerization is 1700.

"Synthesis Example 10"
Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 5, except that the same polyvinyl butyral as in Synthesis Example 7 was used as the polyvinyl acetal resin.
For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 10 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (10 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (24 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 10 contains 10 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 1 mol%, and the ether modification unit represented by the formula (4) is 24 mol% (R ₂ in the formula (4) is -CH ₂ OCH ₂ -C ₅ H ₆ (BOM). It can be considered that it is contained and the average degree of polymerization is 1700.

"Synthesis Example 11"
As the polyvinyl acetal resin, the same polyvinyl butyral as in Synthesis Example 7 was used, and the amount of phenyl isocyanate used was changed from 50 g to 25 g, and the reaction time was changed from 5 hours to 3 hours. Modified polyvinyl butyral was obtained by the same method.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 15 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (15 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (19 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 11 contains 15 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 1 mol%, and the modification unit represented by the formula (4) is 19 mol% (R ₂ in the formula (4) is -C (= O) -NH-C ₅ H ₆ . It is contained and can be regarded as having an average degree of polymerization of 1700.

"Synthesis Example 12"
As the polyvinyl acetal resin, the same polyvinyl butyral as in Synthesis Example 7 was used, and the amount of phenyl isocyanate used was changed from 50 g to 100 g, and the reaction time was changed from 5 hours to 10 hours. Modified polyvinyl butyral was obtained by the same method.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 5 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (5 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (29 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 12 contains 5 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). The vinyl acetate unit represented by the formula (4) is 1 mol%, and the modification unit represented by the formula (4) is 29 mol% (R ₂ in the formula (4) is -C (= O) -NH-C ₅ H ₆ . It is contained and can be regarded as having an average degree of polymerization of 1700.

"Synthesis Example 13"
Synthetic except that the same polyvinyl butyral as in Synthesis Example 7 was used as the polyvinyl acetal resin, the amount of sodium hydride used was changed from 67 g to 20 g, and the amount of chloromethyl ether used was changed from 90 g to 30 g. Modified polyvinyl butyral was obtained by the same method as in Example 1.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 20 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (20 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (14 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 13 contains 20 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). Contains 1 mol% of the vinyl acetate unit represented by and 14 mol% of the ether modification unit represented by the formula (4) (R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM)). However, it can be considered that the average degree of polymerization is 1700.

"Synthesis Example 14"
Synthetic except that the same polyvinyl butyral as in Synthesis Example 7 was used as the polyvinyl acetal resin, the amount of sodium hydride used was changed from 67 g to 35 g, and the amount of chloromethyl ether used was changed from 90 g to 60 g. Modified polyvinyl butyral was obtained by the same method as in Example 1.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 15 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (15 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (19 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 14 contains 15 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). Contains 1 mol% of the vinyl acetate unit represented by and 19 mol% of the ether modification unit represented by the formula (4) (R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM)). However, it can be considered that the average degree of polymerization is 1700.

"Synthesis Example 15"
As the polyvinyl acetal resin, the same polyvinyl butyral as in Synthesis Example 7 was used, the amount of sodium hydride used was changed from 67 g to 105 g, the amount of chloromethyl ether used was changed from 90 g to 190 g, and the reaction time was 12 Modified polyvinyl butyral was obtained by the same method as in Synthesis Example 1 except that the time was changed to 2 days.

For the obtained modified polyvinyl butyral, the amount of residual hydroxyl groups was measured in the same manner as in Synthesis Example 1. As a result, the amount of residual hydroxyl groups was 5 mol%. From this, the hydrogen atom having a hydroxyl group excluding the residual hydroxyl group amount (5 mol%) from the 34 mol% vinyl alcohol unit contained in the polyvinyl butyral used as a raw material is modified into a group containing an ether bond. Therefore, it is estimated that the ether modification unit (29 mol%) represented by the formula (4) has been obtained.

Therefore, the modified polyvinyl butyral obtained in Synthesis Example 15 contains 5 mol% of the vinyl alcohol unit represented by the formula (1), 65 mol% of the vinyl acetal unit represented by the formula (2), and the formula (3). Contains 1 mol% of the vinyl acetate unit represented by and 29 mol% of the ether modification unit represented by the formula (4) (R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM)). However, it can be considered that the average degree of polymerization is 1700.

"Example 1 to Example 19, Comparative Example 1 to Comparative Example 11"
Any of the above containing each structural unit (vinyl alcohol unit, vinyl acetal unit, vinyl acetate unit, ether modification unit) represented by the formulas (1) to (4) in the ratio shown in Tables 1 to 5. The modified polyvinyl butyral (modified polyvinyl acetal resin compound) produced in the synthesis example of No. 1 or the unmodified polyvinyl acetal resin (BM-S, BH-3) used as a raw material is dissolved in the solvents shown in Tables 1 to 5. Then, acetal solutions having the resin concentrations shown in Tables 1 to 5 were obtained.

The viscosity of the obtained acetal solution at a temperature of 20 ° C. was measured using a B-type viscometer. The results are shown in Tables 1 to 5.
Further, the ratio of the viscosity of the modified polyvinyl butyral acetal solution (relative ratio of viscosity) to the viscosity (reference) of the acetal solution of the unmodified polyvinyl acetal resin was calculated by the following formula. The results are shown in Tables 1 to 5.
Relative viscosity ratio (%) (viscosity of modified polyvinyl butyral acetal solution / viscosity of unmodified polyvinyl acetal resin acetal solution) x 100
The acetal solution of Comparative Example 5 had a viscosity of 50,000 mPa · s or more, but the relative viscosity ratio was calculated with the reference viscosity being 50,000 mPa · s.

The MOM, MEM and BOM in Tables 1 to 5 and the MOE and MOP in Tables 1 and 2 are groups containing the ether bonds shown below, respectively.
MOM (-CH ₂ OCH ₃ ), MEM (-CH ₂ OCH ₂ CH ₂ OCH ₃ ), BOM (-CH ₂ OCH ₂ -C ₅ H ₆ ), MOE (-CH ₂ CH ₂ OCH ₃ ), MOP (-CH 2 OCH 2 OCH 3) CH ₂ CH ₂ CH ₂ OCH ₃ )

As shown in Tables 1 to 5, modified polyvinyl containing 10 mol% to 35 mol% of the ether modification unit represented by the formula (4), and _R2 in the formula (4) is a group containing an ether bond. The acetal solution of the acetal resin compound (Examples 1 to 19) is an unmodified acetal solution containing no ether modification unit represented by the formula (4) and having the same degree of polymerization and the same resin concentration. In comparison with the above, the viscosity was low even when any of toluene, 1-propanol, 2-propanol, 2-methoxyethyl acetate and n-butanol was used as the solvent.

Further, as shown in Tables 1 to 5, the acetal solutions of Examples 1 to 19 are polymerized in which R ₂ in the formula ( ₄ ) is −C (= O) —NH—C ₅ H6. Even when compared with the acetal solution having the same degree and the same resin concentration, the viscosity was lower when any of toluene, 1-propanol, 2-propanol, 2-methoxyethyl acetate and n-butanol was used as the solvent.
Further, as shown in Table 5, a modified polyvinyl acetal containing 10 mol% to 35 mol% of the ether modification unit represented by the formula (4) and _R2 in the formula (4) is a group containing an ether bond. The acetal solution of the resin compound had a lower content of vinyl alcohol units and a higher content of ether modification units, the lower the viscosity when the degree of polymerization was the same and the resin concentration was the same.

"Example 20 to Example 21, Comparative Example 12 to Comparative Example 15"
Any of the above synthetic examples containing each structural unit (vinyl alcohol unit, vinyl acetal unit, vinyl acetate unit, ether modification unit) represented by the formulas (1) to (4) in the ratio shown in Table 6. The modified polyvinyl butyral (modified polyvinyl acetal resin compound) produced in 1 or the unmodified polyvinyl acetal resin (BH-3) used as a raw material was dissolved in 2-propanol as a solvent to obtain the resin concentration shown in Table 7. An acetal solution was obtained.

The obtained acetal solution and the ceramic powder shown in Table 7 are measured in a 1 L polypot so as to have the mass ratio shown in Table 7, zirconia beads are added, and the temperature is room temperature using a tabletop ball mill (rotation speed 80 r / min). Was mixed for 100 hours to obtain a resin composition. Then, the zirconia beads were removed by filtration, and the resin composition was recovered.
As the ceramic powder shown in Table 7, those shown below were used.
Ferrite (trade name; FRX-952, particle size 0.65 μm, manufactured by Toda Kogyo Co., Ltd.)
Titanium oxide (trade name; R-32, particle size 0.23 μm, manufactured by Sakai Chemical Industry Co., Ltd.)

The viscosity of the obtained resin composition at a temperature of 20 ° C. was measured using a B-type viscometer. The results are shown in Table 7.
Further, the ratio of the viscosity of the resin composition containing modified polyvinyl butyral (relative ratio of viscosity) to the viscosity (reference) of the resin composition containing unmodified polyvinyl acetal resin was determined by the following formula. The results are shown in Table 7.
Relative ratio of viscosity (%) (viscosity of resin composition containing modified polyvinyl butyral resin / viscosity of resin composition containing unmodified polyvinyl acetal resin) × 100

In Table 6, the MOM is -CH ₂ OCH ₃ .

As shown in Tables 6 and 7, a resin containing a modified polyvinyl butyral containing an ether modification unit represented by the formula (4) and in which R ₂ in the formula (4) is −CH ₂ OCH ₃ (MOM). The compositions (Examples 20 and 21) are compared with resin compositions (Comparative Examples 12 and 14) containing the same filler in the same content and the same unmodified polyvinyl acetal resin having the same degree of polymerization at the same resin concentration. And the viscosity was low.

Further, the resin compositions of Examples 20 and 21 each contain the same filler in the same content, and the degree of polymerization in which R ₂ in the formula ( ₄ ) is −C (= O) −NH—C ₅ H6 is The viscosity was lower than that of the resin composition (Comparative Examples 13 and 15) containing the same modified polyvinyl butyral resin at the same resin concentration.

Claims (5)

The vinyl alcohol unit represented by the following formula (1) is 0 mol% to 20 mol%,
The vinyl acetal unit represented by the following formula (2) is 30 mol% to 90 mol%,
The vinyl acetate unit represented by the following formula (3) is 0 mol% to 25 mol%,
A modified polyvinyl acetal resin compound containing 10 mol% to 35 mol% of an ether modification unit represented by the following formula (4).

(In formula (2), R ₁ is a hydrogen atom or a hydrocarbon group. In formula (4), R ₂ is a group containing an ether bond.) The modified polyvinyl acetal resin compound according to claim 1, wherein the vinyl alcohol unit represented by the formula (1) is 15 mol% or less. The modification according to claim 1 or 2, wherein R ₂ in the formula (4) is any one selected from a methoxymethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a methoxyethyl group, and a methoxypropyl group. Polypolyacetal resin compound. A resin composition containing the modified polyvinyl acetal resin compound according to any one of claims 1 to 3. A resin film containing the modified polyvinyl acetal resin compound according to any one of claims 1 to 3.