JP6697268B2 - Polymer and method for producing the same - Google Patents

Description

  The present invention relates to a hydroxyl group-containing polymer modified with a lactam compound and a method for producing the same. The present invention also relates to a method of modifying a hydroxyl group-containing polymer with a lactam compound.

  Polyvinyl alcohol obtained by polymerizing vinyl acetate and then saponifying (hereinafter sometimes abbreviated as PVA) is a water-soluble polymer having excellent film forming properties and gas barrier properties. PVA resin is a sizing agent for fiber processing, an adhesive for paper and wood, a surface strength improver for high-quality paper, paperboard, corrugated liner paper, an undercoat agent for release paper, a film, a binder for various inorganic materials, and emulsion stabilization. Widely used as an agent.

  In recent years, functions which conventional PVA resins do not have such as water resistance, solubility in cold water, and emulsification characteristics have been demanded, and PVA having various modified groups introduced therein has been developed. Examples thereof include acetoacetyl group-containing PVA, aromatic amino group-containing PVA, diacetone acrylamide group-containing PVA, and carboxylic acid group-containing PVA. These PVA may be obtained by copolymerizing an aliphatic vinyl ester with a monomer having a modifying group, or by reacting PVA with a compound having a functional group such as an epoxy group, an isocyanate group, a vinyl sulfone group or an aldehyde group. Manufactured. However, the denaturing method by the heterogeneous reaction has a problem in that the method is complicated and a large-scale device is required. Further, when carrying out the copolymerization, there is a problem in collecting the unreacted copolymerization monomer. As described above, a method of freely introducing a modifying group into the PVA resin has not been proposed, and there is a limit in imparting a desired function to the PVA resin.

  Similarly, ethylene-vinyl alcohol copolymer made from vinyl acetate as a raw material (hereinafter sometimes abbreviated as EVOH) has excellent gas barrier properties, oil resistance and solvent resistance, and is excellent in food packaging materials, automobile fuel containers, and various types. It is preferably used for films and sheets. EVOH is widely used as an intermediate layer of a packaging material. For example, a laminated structure of 3 types and 5 layers in which polyolefin (PO) is used as an outer layer and EVOH is used as an intermediate layer and they are adhered with an adhesive resin layer is proposed. ing. However, molding of the laminated structure requires a high level of technology, and sometimes molding is difficult. Therefore, by providing EVOH with adhesiveness to polyolefin, a laminated structure of two kinds and three layers without an adhesive resin layer is required.

  As a formulation for modifying EVOH, a method is known in which an epoxy compound and an EVOH resin are reacted inside an extruder (Patent Document 1). Various modified EVOHs can be produced by using epoxy compounds having various substituents. However, there are problems such as difficulty in producing an epoxy compound having a substituent having low oxidation resistance and poor storage stability of the epoxy compound, and a method for functionalizing an EVOH resin is under development.

  Further, polyvinyl acetal can be obtained by an acetalization reaction in water under acidic conditions using PVA and an aldehyde compound. Various polyvinyl acetals have been proposed because the film made of polyvinyl acetal is tough and has a unique structure having both a hydrophilic hydroxy group and a hydrophobic acetal group. Among them, polyvinyl formal produced from PVA and formaldehyde, polyvinyl acetoacetal produced from PVA and acetaldehyde, and polyvinyl butyral produced from PVA and butyraldehyde (hereinafter sometimes abbreviated as PVB) are commercially important. Is.

  In particular, a film made of PVB has both penetration resistance and adhesion to glass, and is widely used as an interlayer film for safety glass for automobiles and construction. Further, PVB resins are widely used as binders for various printing inks, paints, adhesives, binders for ceramic molding, etc., and are particularly important commercially. However, in recent years, PVB resins having various functions have been demanded for various uses.

  For example, PVB is used as a binder for ceramic molding in the process of manufacturing a multilayer capacitor or a circuit board of an IC chip, and is used for manufacturing a ceramic green sheet (hereinafter sometimes abbreviated as a green sheet). Widely used as a binder. A circuit board for a multilayer capacitor or an IC chip is manufactured by, for example, a method of forming electrodes on a green sheet, stacking and pressing the electrodes, and then simultaneously firing the electrodes and ceramics.

  As a method for producing the green sheet, a method of applying PVB, ceramic powder, and a ceramic slurry containing an organic solvent as a main component on a carrier film and then drying the applied slurry is used.

  The monolithic ceramic capacitor is obtained by laminating a green sheet having an electrode layer formed on the surface thereof and a green sheet having no electrode layer formed thereon, press-bonding the sheets, and then firing. 2. Description of the Related Art In recent years, as electronic devices have become more multifunctional and smaller, there has been a demand for larger capacity and smaller size of multilayer ceramic capacitors. In response to this, an attempt has been made to apply a ceramic slurry obtained by using a fine ceramic powder having a particle diameter of 0.5 μm or less on a releasable support with a thickness of 5 μm or less.

  On the other hand, in order to achieve both a large capacity and a small size of the monolithic ceramic capacitor, it is necessary to make the green sheet thin and multilayer, and for that purpose, improvement of the binder resin is indispensable. As the performance required for the conventional ceramic molding binder, a ceramic slurry having excellent dispersibility and storage stability can be obtained, the amount of carbon residue after firing is small, and the adhesiveness during thermocompression bonding is good. There are things like that. In the case of producing a thin film green sheet, in addition to this, the binder for ceramic molding has an appropriate sheet strength that can be peeled from the substrate, adhesiveness during thermocompression bonding, and shape stability after press bonding. It is required to obtain a thin film green sheet having plasticity.

  As a general formulation used for producing a green sheet, a method is known in which a plasticizer such as a phthalate ester is added to a ceramic slurry to impart flexibility and adhesiveness (Patent Document 2). However, when a thin-film ceramic green sheet was produced by using this method, the sheet strength was insufficient and the shape stability after press-pressing was deteriorated. Furthermore, storage stability deteriorated due to plasticizer bleeding out from the green sheet. Thus, it was difficult to apply the above method to the production of thin film ceramic green sheets.

  In addition, it is being studied to increase the strength of a small-sized thin film green sheet. For example, a polyvinyl acetal resin having a degree of polymerization of more than 1000 and not more than 4500, and obtained by acetalizing PVA having a vinyl ester unit content of less than 1 mol% with a monoaldehyde, the degree of acetalization being 60 to 83 mol%. A slurry composition containing is proposed (Patent Document 3). However, the slurry composition has a problem that the solution viscosity is high and the storage stability is poor.

International Publication No. 02/092643 Japanese Patent Laid-Open No. 2001-0889245 International Publication No. 2011/092963

  The present invention has been made to solve the above problems, and an object thereof is to provide a hydroxyl group-containing polymer having various properties. In particular, when used as a binder for ceramic molding, a hydroxyl group-containing polymer capable of obtaining a ceramic green sheet having both excellent mechanical stability and adhesiveness as well as a ceramic slurry having excellent storage stability is provided. The purpose is to do.

  The above problem can be solved by providing a polymer containing the following structural units (I), (II), (III) and (IV) and satisfying the following formulas (1) to (4).

（式中、ｎは１〜２０の整数である。Ｒ^１の炭素数は２５０以下である。Ｒ^１は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、置換基を有してもよいアシル基又はカルボキシル基である。ただし、Ｒ^１にメチル基は含まれない。）

(In the formula, n is an integer of ¹ to 20. The carbon number of R ¹ is 250 or less. R ¹ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent Optionally an amino group, an optionally substituted amide group, an optionally substituted acyl group or a carboxyl group, provided that R ¹ does not include a methyl group.)

（式中、Ｒ^１は、上記構造単位（Ｉ）と同じである。）

(In the formula, R ¹ is the same as the above structural unit (I).)

0.001 ≦ a + b ≦ 98 (1)
0.06 ≦ a / (a + b) ≦ 1 (2)
1 ≦ c ≦ 99.99 (3)
0 ≦ d ≦ 98 (4)

In the formula,
a: Content of the structural unit (I) with respect to all monomer units (mol%)
b: Content of the structural unit (II) with respect to all monomer units (mol%)
c: Content of the structural unit (III) with respect to all monomer units (mol%)
d: Content of the above structural unit (IV) with respect to all monomer units (mol%)
Is.

  It is preferable that the polymer further contains the following structural unit (V) and satisfies the following formula (5).

0.001 ≦ e ≦ 98 (5)

In the formula,
e: Content (mol%) of the structural unit (V) with respect to all monomer units
Is.

  It is also preferable that the polymer further contains the following structural unit (VI) and satisfies the following formula (6).

（式中、Ｒ^２は炭素数１〜１０のアルキル基又は水素原子を表す。）

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

0.001 ≦ 2f ≦ 98 (6)

In the formula,
f: Content of the above structural unit (VI) with respect to all monomer units (mol%)
Is.

At this time, it is more preferable that R ² is a propyl group.

It is preferable that the polymer satisfies the following formula (2 ′).
0.15 ≦ a / (a + b) ≦ 0.97 (2 ′)

R ¹ in the structural unit (I) is preferably the following group (VII), and more preferably the following group (VIII).

（式中、Ｒ^３は、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアシル基、置換基を有してもよいアルキルシリル基、置換基を有してもよいアルキルシリルオキシ基、置換基を有してもよいアシロキシ基、置換基を有してもよいアルコキシカルボニル基、置換基を有してもよいアルキルスルフィニル基、置換基を有してもよいアリールスルフィニル基、置換基を有してもよいスルホン酸エステル基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、水酸基、カルボキシル基、シアノ基、ニトロ基、ハロゲン原子又は水素原子である。）

(In the formula, R ³ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aryl which may have a substituent. Group, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an alkylsilyl group which may have a substituent, an alkylsilyloxy group which may have a substituent, a substituent An acyloxy group which may have a group, an alkoxycarbonyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, and a substituent Sulfonic acid ester group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted amino group, optionally substituted group Amido group, hydroxyl group, carboxyl group, cyano group , A nitro group, a halogen atom or a hydrogen atom.)

（式中、ｐは０又は１を示し、ｑは２〜１００の整数を表す。）

(In the formula, p represents 0 or 1, and q represents an integer of 2 to 100.)

R ¹ in the structural unit (I) preferably has an aliphatic hydrocarbon unit having 5 or more carbon atoms. It is also suitable that R ¹ in the structural unit (I) has a (poly) oxyalkylene unit. It is also preferable that R ¹ in the structural unit (I) has an amide group. It is also preferable that R ¹ in the structural unit (I) has a carboxyl group. It is also preferable that R ¹ in the structural unit (I) has an ester group. It is also preferable that R ¹ in the structural unit (I) has no aromatic ring.

  The above problems can also be solved by providing a method for producing the above polymer in which a raw material polymer containing the above structural unit (III) is reacted with the following compound (IX).

（式中、ｎ及びＲ^１は、上記構造単位（Ｉ）と同じである。）

(In the formula, n and R ¹ are the same as the above structural unit (I).)

  At this time, it is preferable that the raw material polymer is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or polyvinyl acetal. It is also preferable to react the raw material polymer with the compound (IX) in a molten state. It is also preferable to react the raw material polymer with the compound (IX) in the presence of at least one catalyst selected from the group consisting of titanium compounds, zirconium compounds and aluminum compounds.

  A ceramic slurry containing the polymer, ceramic powder and an organic solvent is a preferred embodiment of the present invention. A ceramic green sheet obtained by using the ceramic slurry is also a preferred embodiment of the present invention.

  The above-mentioned subject is a hydroxyl group-containing polymer and the following compound (X)

（式中、ｎは１〜２０の整数である。Ｒ^４の炭素数は２５０以下である。Ｒ^４は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、置換基を有してもよいアシル基又はカルボキシル基である。）

(In the formula, n is an integer of 1 to 20. The carbon number of R ⁴ is 250 or less. R ⁴ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent Optionally an amino group, an optionally substituted amide group, an optionally substituted acyl group or a carboxyl group.)

And react with the following group (XI)

（式中、ｎ及びＲ^４は、上記化合物（Ｘ）と同じである。）
を形成させる水酸基含有重合体の変性方法を提供することによっても解決される。

(In the formula, n and R ⁴ are the same as those in the compound (X).)
It is also solved by providing a method for modifying a hydroxyl group-containing polymer to form

  The polymer of the present invention has the property that it does not appear in the existing hydroxyl group-containing polymer. Among them, the ceramic slurry obtained by using the polymer of the present invention has excellent storage stability, and the ceramic green sheet obtained by using the slurry has both excellent mechanical strength and adhesiveness. By using such a ceramic green sheet, a small-sized high-capacity multilayer ceramic capacitor can be obtained.

3 is a ¹ H-NMR chart of N- (4-n-decylbenzoyl) -ε-caprolactam obtained in Synthesis Example 2. 9 is a ¹ H-NMR chart of polyvinyl butyral as a raw material (upper stage) and polyvinyl butyral (lower stage) containing the obtained structural units (I) to (IV) and (VI) in Example 7. 20 is a ¹ H-NMR chart of EVOH (upper stage) as a raw material and EVOH (lower stage) containing the obtained structural units (I) to (V) in Example 20. 3 is a ¹ H-NMR chart of polyvinyl alcohol containing the structural units (I) to (IV) obtained in Example 22.

  The polymer of the present invention contains the following structural units (I), (II), (III) and (IV) and satisfies the following formulas (1) to (4).

（式中、ｎは１〜２０の整数である。Ｒ^１の炭素数は２５０以下である。Ｒ^１は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、置換基を有してもよいアシル基又はカルボキシル基である。ただし、Ｒ^１にメチル基は含まれない。）

(In the formula, n is an integer of ¹ to 20. The carbon number of R ¹ is 250 or less. R ¹ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent Optionally an amino group, an optionally substituted amide group, an optionally substituted acyl group or a carboxyl group, provided that R ¹ does not include a methyl group.)

（式中、Ｒ^１は、上記構造単位（Ｉ）と同じである。）

(In the formula, R ¹ is the same as the above structural unit (I).)

0.001 ≦ a + b ≦ 98 (1)
0.06 ≦ a / (a + b) ≦ 1 (2)
1 ≦ c ≦ 99.99 (3)
0 ≦ d ≦ 98 (4)

In the formula,
a: Content of the structural unit (I) with respect to all monomer units (mol%)
b: Content of the structural unit (II) with respect to all monomer units (mol%)
c: Content of the structural unit (III) with respect to all monomer units (mol%)
d: Content of the above structural unit (IV) with respect to all monomer units (mol%)
Is.

  The polymer of the present invention contains structural units (I) and (III) as essential components, and structural units (II) and (IV) as optional components. The polymer can be obtained by a method of reacting a raw material polymer containing the structural unit (III) with a lactam compound [compound (IX) below], which will be described later. At this time, the structural unit (III) in the raw polymer reacts with the compound (IX) to form the structural unit (I) or the structural unit (II).

The polymer of the present invention contains the structural unit (I) as an essential component. By containing the structural unit (I), various functions are imparted to the polymer. In particular, when the polymer of the present invention is used as a binder for ceramic molding, a ceramic slurry having excellent storage stability and a ceramic green sheet having both excellent mechanical strength and adhesiveness can be obtained. It is considered that the amide group in the structural unit (I) contributes to these effects. It is considered that the amide group appropriately raises the glass transition temperature of the polymer, thereby improving the adhesiveness when used as a binder for ceramic molding. It is also considered that R ¹ in the structural unit (I) also contributes to these effects.

  In the structural unit (I), n is an integer of 1-20. When n exceeds 20, the yield of the polymer of the present invention may decrease. n is preferably 11 or less. From the viewpoint of increasing the molar ratio of the structural unit (I) to the structural unit (II) by selectively forming the structural unit (I) during the production of the polymer, n is more preferably 5 or less. On the other hand, n is preferably 2 or more, and more preferably 4 or more from the viewpoint of further improving the reactivity between the structural unit (III) and the compound (IX) when producing the polymer of the present invention.

In the structural unit (I), R ¹ has 250 or less carbon atoms. The carbon number of R ¹ is preferably 150 or less. On the other hand, the carbon number of R ¹ is preferably 5 or more.

In the structural unit (I), R ¹ has an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Alkynyl group, optionally substituted alkoxy group, optionally substituted alkylthio group, optionally substituted amino group, optionally substituted amide group, substituted It is an acyl group or a carboxyl group which may have a group. However, R ¹ does not include a methyl group.

From the viewpoint of further improving the reactivity between the structural unit (III) and the compound (IX) when producing the polymer of the present invention, R ¹ is preferably an aryl group which may have a substituent. is there. Examples of the aryl group used as R ¹ include a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group, and a phenyl group is preferable. The aryl group may have a substituent, and examples of the substituent include an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and an alkynyl which may have a substituent. A group, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an alkylsilyl group which may have a substituent, a substituent Alkylsilyloxy group which may have, acyloxy group which may have a substituent, alkoxycarbonyl group which may have a substituent, alkylsulfinyl group which may have a substituent, which has a substituent Optionally substituted arylsulfinyl group, optionally substituted sulfonate ester group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted Even if it has an amino group or a substituent There amide group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and halogen atoms. The aryl group used as R ¹ may have a plurality of substituents, in which case they may be linked to each other.

Examples of the substituent of the aryl group used as R ¹ include an acyl group such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a dodecanoyl group, a pivaloyl group; an alkylsilyl group such as a trimethylsilyl group; a trimethylsilyloxy group. Acyloxy group such as acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, benzoyloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group Group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyl Alkoxycarbonyl group such as sulfonyloxy group; Alkylsulfinyl group such as methylsulfinyl group and ethylsulfinyl group; Arylsulfinyl group such as phenylsulfinyl group; Methylsulfonyloxy group, ethylsulfonyloxy group, phenylsulfonyloxy group, methoxysulfonyl group Sulfonate groups such as ethoxysulfonyl group and phenyloxysulfonyl group; arylthio groups such as phenylthio group and naphthylthio group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. In the aryl group used as R ^1, alkenyl group substituents, alkynyl group, alkoxy group, alkylthio group, an amino group, the amide group include those used for R ¹ to be described later. In the aryl group used as R ^1, the alkyl group of the substituent include those or methyl group used as R ¹ described later.

The following group (VII) is suitable as the aryl group used as R ¹ .

（式中、Ｒ^３は、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシ基、置換基を有してもよいアシル基、置換基を有してもよいアルキルシリル基、置換基を有してもよいアルキルシリルオキシ基、置換基を有してもよいアシロキシ基、置換基を有してもよいアルコキシカルボニル基、置換基を有してもよいアルキルスルフィニル基、置換基を有してもよいアリールスルフィニル基、置換基を有してもよいスルホン酸エステル基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、水酸基、カルボキシル基、シアノ基、ニトロ基、ハロゲン原子又は水素原子である。）

(In the formula, R ³ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aryl which may have a substituent. Group, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an alkylsilyl group which may have a substituent, an alkylsilyloxy group which may have a substituent, a substituent An acyloxy group which may have a group, an alkoxycarbonyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, and a substituent Sulfonic acid ester group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted amino group, optionally substituted group It is an amide group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom or a hydrogen atom.)

Specific examples of the aryl group used as R ¹ include the following.

  When it is desired to improve the water solubility of the obtained polymer, the following group (VIII) is suitable as the above group (VII).

（式中、ｐは０又は１を示し、ｑは２〜１００の整数を表す。）

(In the formula, p represents 0 or 1, and q represents an integer of 2 to 100.)

In the structural unit (I), the alkyl group used as R ¹ may be a linear or branched alkyl group or a cyclic cycloalkyl group. The alkyl group preferably has 1 to 50 carbon atoms. More preferably, the alkyl group has 5 or more carbon atoms. On the other hand, the alkyl group preferably has 30 or less carbon atoms, more preferably 15 or less carbon atoms.

The alkenyl group used as R ¹ may be linear or branched. The alkenyl group preferably has 2 to 50 carbon atoms. More preferably, the alkenyl group has 5 or more carbon atoms. On the other hand, the alkenyl group preferably has 30 or less carbon atoms, and more preferably 15 or less carbon atoms.

The alkynyl group used as R ¹ may be linear or branched. The alkynyl group preferably has 2 to 50 carbon atoms. The carbon number of the alkynyl group is more preferably 5 or more. On the other hand, the alkynyl group preferably has 30 or less carbon atoms, and more preferably 15 or less carbon atoms.

The alkyl group used as R ^1, the alkenyl group, the alkynyl group may have a substituent, and examples of the substituent include the substituents exemplified in the description of the aryl group used as R ¹ Other than the alkyl group, alkenyl group and alkynyl group, polyoxyalkylene groups such as polyoxyethylene group, etc. may be mentioned.

The alkoxy group used as R ¹ may be linear or branched. The alkoxy group preferably has 1 to 50 carbon atoms. The number of carbon atoms in the alkoxy group is more preferably 5 or more. On the other hand, the alkoxy group preferably has 30 or less carbon atoms, and more preferably 15 or less carbon atoms. The alkoxy group may have a substituent, and examples of the substituent include those other than the alkyl group, the alkenyl group and the alkynyl group among the substituents exemplified in the description of the aryl group used as R ^1. , And polyoxyalkylene groups such as polyoxyethylene groups.

The alkylthio group used as R ¹ may be linear or branched. The alkylthio group preferably has 1 to 50 carbon atoms. It is more preferable that the alkylthio group has 5 or more carbon atoms. On the other hand, the alkylthio group preferably has 30 or less carbon atoms, and more preferably 15 or less carbon atoms. The alkylthio group may have a substituent, and examples of the substituent include those other than the alkyl group, the alkenyl group and the alkynyl group among the substituents exemplified in the description of the aryl group used as R ^1. , And polyoxyalkylene groups such as polyoxyethylene groups.

The amino group used as R ¹ may be a secondary amino group or a tertiary amino group in addition to the primary amino group (—NH ₂ ). The secondary amino group is a mono-substituted amino group represented by -NHR ⁵ (R ⁵ is an arbitrary monovalent substituent), and R ⁵ is an alkyl group which may have a substituent or a substituted group. Examples include alkenyl group which may have a group, alkynyl group which may have a substituent, aryl group which may have a substituent, acetyl group, benzoyl group, benzenesulfonyl group and tert-butoxycarbonyl group. Be done. Examples of the alkyl group for R ⁵ include a methyl group and those used as R ¹ described above. In R ^5, aryl group, alkenyl group, include those used as R ¹ described above as an alkynyl group. The tertiary amino group is a di-substituted amino group represented by -NR ⁵ R ⁶ (R ⁵ and R ⁶ are arbitrary monovalent substituents), and R ⁶ is the same as R ^5. R ⁵ and R ⁶ may be the same or different from each other. The amino group preferably has 0 to 50 carbon atoms. The carbon number of the amino group is more preferably 30 or less, further preferably 15 or less.

Examples of the amide group used as R ¹ include an amide group represented by —C (═O) NR ⁷ R ⁸ (R ⁷ and R ⁸ are hydrogen atoms or arbitrary substituents). Examples of the substituent used as R ⁷ and R ⁸ include an alkyl group which may have a substituent and an aryl group which may have a substituent. Examples of the alkyl group include a methyl group and the alkyl group used as R ¹ described above, and examples of the aryl group include those used as R ¹ described above. R ⁷ and R ⁸ may be the same or different from each other. The amide group preferably has 1 to 50 carbon atoms. The carbon number of the amide group is more preferably 30 or less, further preferably 15 or less.

Examples of the acyl group used as R ¹ include an acyl group represented by —C (═O) R ⁹ (R ⁹ is a hydrogen atom or any substituent). Examples of the substituent used as R ⁹ include an alkyl group which may have a substituent and an aryl group which may have a substituent. Examples of the alkyl group include a methyl group and the alkyl group used as R ¹ described above, and examples of the aryl group include those used as R ¹ described above. The acyl group preferably has 1 to 50 carbon atoms. The acyl group preferably has 30 or less carbon atoms, and more preferably 15 or less carbon atoms.

Specific examples of the group used as R ¹ include the following.

（ａ−１６におけるＲ^１０は、置換基を有してもよいアルキル基又は置換基を有してもよいアリール基である。）

(R ¹⁰ in a-16 is an alkyl group which may have a substituent or an aryl group which may have a substituent.)

From the viewpoint of further improving the plasticity of the obtained polymer, it is preferable that R ¹ in the structural unit (I) has an aliphatic hydrocarbon unit having 5 or more carbon atoms, and an aliphatic hydrocarbon having 15 or more carbon atoms. It is more preferred to have hydrogen units.

From the viewpoint of further increasing the polarity of the obtained polymer, it is preferable that R ¹ in the structural unit (I) has a (poly) oxyalkylene unit. Examples of the oxyalkylene unit that constitutes the (poly) oxyalkylene unit include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. These may be used alone or in combination of two or more. .. It is more preferred that R ¹ in structural unit (I) has a polyoxyethylene unit. The number of repeating oxyalkylene units in the polyoxyalkylene unit is preferably 1 to 100, and more preferably 3 to 50.

From the viewpoint of further improving the glass transition point of the obtained polymer, it is preferable that R ¹ in the structural unit (I) has an amide group. From the viewpoint of further improving the water solubility of the obtained polymer, it is preferable that R ¹ in the structural unit (I) has a carboxyl group. From the viewpoint of imparting polarity to the obtained polymer and improving the affinity with a solvent, it is preferable that R ¹ in the structural unit (I) has an ester group. In addition, when the polymer of the present invention is used as a binder for ceramic molding, it is preferable that R ¹ in the structural unit (I) does not have an aromatic ring from the viewpoint of further reducing the carbon residue after firing. is there.

The polymer of the present invention contains the structural unit (II) as an optional component. As described above, during the production of the polymer of the present invention, the structural unit (III) in the raw material polymer reacts with the lactam compound [compound (IX)] to form the structural unit (II). Sometimes. In the structural unit (II), R ¹ is the same as the structural unit (I). R ¹ in the structural unit (II) is believed to exert a similar effect as R ¹ in the structural unit (I).

  The polymer of the present invention contains the structural unit (III) as an essential component. The structural unit (III) is a vinyl alcohol monomer unit. The structural unit (III) has an effect of improving the mechanical strength of a molded article obtained by using the polymer of the present invention, an effect of improving the gas barrier property, and the like.

  The polymer of the present invention contains the structural unit (IV) as an optional component. The structural unit (IV) is a vinyl acetate monomer unit. The structural unit (IV) has an effect of preventing the viscosity from becoming too high when the polymer of the present invention is used in a ceramic slurry.

The polymer of the present invention satisfies the following formulas (1) to (4).
0.001 ≦ a + b ≦ 98 (1)
0.06 ≦ a / (a + b) ≦ 1 (2)
1 ≦ c ≦ 99.99 (3)
0 ≦ d ≦ 98 (4)

In the formula,
a: Content of the structural unit (I) with respect to all monomer units (mol%)
b: Content of the structural unit (II) with respect to all monomer units (mol%)
c: Content of the structural unit (III) with respect to all monomer units (mol%)
d: Content of the above structural unit (IV) with respect to all monomer units (mol%)
Is.

  In the above formula (1), a + b represents the content (mol%) of the structural units (I) and (II) with respect to all the monomer units in the polymer of the present invention. In the present invention, a + b may be referred to as a modification rate (mol%). If a + b is less than 0.001, the effect of the present invention cannot be obtained. As for a + b, 0.01 or more is preferable, 0.1 or more is more preferable, and 0.5 or more is further preferable. On the other hand, when a + b exceeds 98, the content of the structural unit (III) becomes too small, which causes problems such as reduction in strength of a molded product obtained using the polymer of the present invention. The value of a + b is preferably 70 or less, more preferably 50 or less, further preferably 30 or less, and particularly preferably 20 or less.

In the above formula (2), a / (a + b) is the content (mol%) of the structural unit (I) with respect to the content (mol%) of the structural units (I) and (II) in the polymer of the present invention. The ratio of If a / (a + b) is less than 0.06, the effect of the present invention cannot be obtained. A / (a + b) is preferably 0.15 or more. It is more preferable that a / (a + b) satisfies the following formula (2 ′).
0.15 ≦ a / (a + b) ≦ 0.97 (2 ′)

  In the above formula (3), c represents the content (mol%) of the structural unit (III) with respect to all the monomer units in the polymer of the present invention. When c is less than 1, problems such as a decrease in strength of a molded product obtained by using the polymer of the present invention occur. c is preferably 15 or more, and more preferably 20 or more. On the other hand, when c exceeds 99.99, the effect of the present invention cannot be obtained. c is preferably 99.9 or less, more preferably 99 or less.

  In the above formula (4), d represents the content (mol%) of the structural unit (IV) with respect to all the monomer units in the polymer of the present invention. From the viewpoint of easy production of the polymer, d is preferably 0.01 or more. On the other hand, from the viewpoint of further improving the glass transition point of the obtained polymer, d is preferably 30 or less.

  The polymer of the present invention preferably has a degree of polymerization of 150 to 5,000. When the degree of polymerization exceeds 5,000, the productivity of the polymer of the present invention may decrease, which may be impractical. Further, if the degree of polymerization is less than 150, the mechanical strength of a molded article obtained using the polymer of the present invention may be insufficient. As the degree of polymerization of the polymer of the present invention, a viscosity average degree of polymerization measured according to JIS K6726 is used.

  The polymer of the present invention preferably further contains the following structural unit (V) and satisfies the following formula (5). The structural unit (V) is an ethylene monomer unit. Such a polymer has particularly excellent gas barrier properties and excellent melt moldability. In formula (5), e represents the content (mol%) of the structural unit (V) with respect to all the monomer units in the polymer of the present invention. From the viewpoint of further improving the gas barrier property of the obtained polymer, e is more preferably 70 or less, further preferably 60 or less, and particularly preferably 50 or less. On the other hand, from the viewpoint of further improving the polymer melt moldability to be obtained, e is more preferably 0.01 or more, still more preferably 1 or more, and particularly preferably 18 or more.

0.001 ≦ e ≦ 98 (5)

In the formula,
e: Content (mol%) of the structural unit (V) with respect to all monomer units
Is.

  When the polymer of the present invention contains the structural unit (V), the content c (mol%) of the structural unit (III) is preferably 98 or less, and more preferably 80 or less. ..

  The melt index (MI; measured at 210 ° C. under 2.16 kg load) of the polymer containing the structural unit (V) is preferably 0.1 g / 10 minutes or more, more preferably 0.5 g / 10 minutes or more. And preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, most preferably 30 g / 10 min or less.

  It is also preferable that the polymer of the present invention further contains the following structural unit (VI) and satisfies the following formula (6). In Formula (6), f represents the content rate (mol%) of the following structural unit (VI) with respect to all the monomer units in the polymer of this invention. Further, 2f represents the ratio of the acetalized structural unit (III) to all the monomer units in the polymer of the present invention (the ratio may be referred to as the degree of acetalization). Such a polymer exhibits particularly excellent performance when used as a binder for ceramic molding. From the viewpoint of improving dimensional stability after molding, 2f is more preferably 1 or more, and further preferably 8 or more. On the other hand, 2f is more preferably 85 or less from the viewpoint of further improving the mechanical strength of a molded article obtained by using the polymer of the present invention.

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

0.001 ≦ 2f ≦ 98 (6)

In the formula,
f: Content of the above structural unit (VI) with respect to all monomer units (mol%)
Is.

  When the polymer of the present invention contains the structural unit (VI), the content c (mol%) of the structural unit (III) is preferably 98 or less, and more preferably 90 or less. ..

In the structural unit (VI), R ² is preferably a propyl group or a hydrogen atom, and more preferably a propyl group.

  The degree of polymerization of the polymer containing the structural unit (VI) is determined from the viscosity average degree of polymerization measured according to JIS K6726 of PVA used for producing the polymer. That is, since the degree of polymerization does not change due to acetalization or modification with the compound (IX), the degree of polymerization of PVA and the degree of polymerization of the polymer obtained by acetalizing it and then modifying it with the compound (IX). Are the same.

  The polymer of the present invention may further contain another structural unit as long as the effect of the present invention is not impaired. In the polymer of the present invention, the content of the other structural units with respect to all the monomer units is usually 10 mol% or less, preferably 1 mol% or less. Examples of other structural units include α-olefins such as propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylic acid esters; methacrylic acid esters; acrylamide; N-methylacrylamide, N-ethylacrylamide, N , N-dimethylacrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts or quaternary salts thereof, acrylamide derivatives such as N-methylolacrylamide and its derivatives; methacrylamide; N-methylmethacryl Methacrylamide derivatives such as amide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts or quaternary salts thereof, N-methylolmethacrylamide and its derivatives; 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 ether, stearyl vinyl ether, vinyl ethers such as 2,3-diacetoxy-1-vinyloxypropane; acrylonitrile, Nitriles such as methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl acetate, 2,3-diacetoxy-1-allyloxypropane, chloride Allyl compounds such as allyl; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts thereof or esters thereof; vinyl silyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like formed by copolymerization An example is a monomer unit. These may be used alone or in combination of two or more.

As a method for producing the polymer of the present invention, for example, a method of reacting a raw material polymer containing the structural unit (III) with the following compound (IX) is suitable. The acyclic amide compound and the compound in which a hydrogen atom or an alkyl group is bonded to the nitrogen atom of the cyclic amide have insufficient reactivity with the above structural unit (III). On the other hand, the following compound (IX), which is a lactam compound having a structure in which a carbonyl group is bonded to the nitrogen atom of the cyclic amide, has sufficient reactivity with the above structural unit (III), The polymer can be obtained in high yield. Further, since the reaction of the following compound (IX) with the raw material polymer containing the structural unit (III) is carried out under mild conditions, various groups can be adopted as R ¹ in the compound (IX). Therefore, various groups can be introduced into the polymer, so that the polymer can be provided with a desired function.

（式中、ｎ及びＲ^１は、上記構造単位（Ｉ）と同じである。）

(In the formula, n and R ¹ are the same as the above structural unit (I).)

  Compound (IX) can be produced by a known method. For example, a method of reacting an acid chloride with a cyclic amide compound in the presence of an amine can be mentioned. Examples of the solvent used in the reaction include toluene and tetrahydrofuran. Usually, the reaction temperature is 25 to 110 ° C., and the reaction time is 1 to 24 hours.

  The raw material polymer may be any polymer containing the structural unit (III). If necessary, a polymer further containing the structural unit (IV) is used as a raw material polymer. PVA, EVOH, polyvinyl acetal and the like are preferably used as the raw material polymer containing the structural unit (III).

  The PVA used as a raw material polymer is produced by polymerizing vinyl acetate and saponifying with an alkali. The method of manufacturing the PVA will be described below.

  The temperature at which vinyl acetate is polymerized is preferably 0 ° C. or higher and 200 ° C. or lower, and more preferably 30 ° C. or higher and 140 ° C. or lower. When the temperature at which the polymerization is carried out is lower than 0 ° C, it is difficult to obtain a sufficient polymerization rate. As a method for controlling the temperature adopted during the polymerization to 0 ° C. or higher and 200 ° C. or lower, for example, a method of controlling the polymerization rate to balance the heat generated by the polymerization with the heat released from the surface of the reactor Another example is a method of controlling with an external jacket using a suitable heat medium, but the latter method is preferable from the viewpoint of safety.

  The polymerization method adopted for polymerizing vinyl acetate may be batch polymerization, semi-batch polymerization, continuous polymerization or semi-continuous polymerization. As the polymerization method, any 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 them, 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 preferably adopted. An emulsion polymerization method is adopted for the purpose of producing a polymer having a high degree of polymerization. As the 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. Further, these solvents can be used in combination of two or more kinds.

  As the initiator used for the polymerization, conventionally known azo type initiators, peroxide type initiators, redox type initiators and the like are appropriately selected according to the polymerization method. Examples of the azo-based initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4). -Dimethylvaleronitrile) and the like, and examples of the peroxide-based initiator include a carbonate compound such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t -Butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy decanate, and other perester compounds; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxy Examples thereof include acetate. Further, the above initiator may be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide or the like to form an initiator. Examples of the redox-based initiators include those obtained by combining the above-mentioned peroxide with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid and Rongalit.

  When the polymerization is carried out at a high temperature, the PVA may be colored due to the decomposition of vinyl acetate. In that case, an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 ppm or more and 100 ppm or less (relative to the mass of the vinyl acetate monomer) for the purpose of preventing coloration.

  In the polymerization of vinyl acetate, other monomers may be copolymerized within the range not impairing the gist of the present invention. As the vinyl compound used for the copolymerization, a compound having an unsaturated bond capable of radical polymerization is used, and these may be used alone or in combination of two or more kinds. For example, olefin monomers other than ethylene, vinylamide monomers, vinyl ether monomers, halogenated vinyl monomers, aromatic vinyl monomers and the like can be mentioned. Examples of the vinyl compound to be copolymerized include α-olefins such as propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylic acid esters; methacrylic acid esters; acrylamide; N-methylacrylamide, N-ethylacrylamide, Acrylamide derivatives such as N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts or quaternary salts thereof, N-methylolacrylamide and its derivatives; methacrylamide; N-methyl Methacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid and salts thereof, methacrylamidopropyldimethylamine and salts thereof or quaternary salts thereof, N Methacrylic amide derivatives such as methylol methacrylamide and its derivatives; 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 ether, stearyl vinyl ether, 2 , Vinyl ethers such as 3-diacetoxy-1-vinyloxypropane; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride Allyl compounds such as allyl acetate, 2,3-diacetoxy-1-allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid Examples thereof include acids and salts or esters thereof; vinylsilane compounds such as vinyltrimethoxysilane; and isopropenyl acetate.

  Further, in the polymerization of vinyl acetate, the polymerization may be carried out in the presence of a chain transfer agent for the purpose of adjusting the degree of polymerization of the obtained polyvinyl acetate, etc. within a range not impairing the spirit of the present invention. Examples of the chain transfer agent 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. Examples thereof include phosphinic acid salts such as monohydrate. Of these, aldehydes and ketones are preferably used. 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 desired degree of polymerization of polyvinyl acetate. Generally, 0.1% by mass or more and 10% by mass or less of vinyl acetate is desirable.

  PVA can be obtained by saponifying the polyvinyl acetate obtained by the above method in an alcohol solvent.

  Alkaline substances are usually used as catalysts for the saponification reaction of polyvinyl acetate, and examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. The amount of the alkaline substance used is preferably in the range of 0.002 to 0.2 in terms of molar ratio based on the vinyl acetate monomer unit in polyvinyl acetate, and in the range of 0.004 to 0.1. It is particularly preferable that The saponification catalyst may be added all at once at the beginning of the saponification reaction, or a part of the catalyst may be added at the beginning of the saponification reaction and the rest may be additionally added during the saponification reaction.

  Examples of the solvent that can be used in the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, and dimethylformamide. Of these solvents, methanol is preferably used. At this time, the water content of methanol is adjusted to preferably 0.001 to 1% by mass, more preferably 0.003 to 0.9% by mass, and particularly preferably 0.005 to 0.8% by mass.

  The saponification reaction is preferably carried out at a temperature of 5 to 80 ° C, more preferably 20 to 70 ° C. The saponification reaction is preferably carried out for 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. The saponification reaction can be performed by either a batch method or a continuous method. After completion of the saponification reaction, the remaining catalyst may be neutralized, if necessary. Examples of usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.

  It is preferable that the viscosity average degree of polymerization of PVA used as a raw material polymer is 150 to 5000 as measured according to JIS K6726.

  The production of polyvinyl acetal used as a raw material polymer containing the structural unit (III) will be described below. The polyvinyl acetal is obtained by acetalizing PVA, and the PVA used as a raw material polymer containing the structural unit (III) is used.

  The acetalization of PVA can be performed, for example, under the following reaction conditions. After heating at 80 to 100 ° C to dissolve PVA in water, the PVA is gradually cooled over 10 to 60 minutes to obtain a 3 to 40 mass% aqueous solution of PVA. When the temperature has dropped to −10 to 30 ° C., an aldehyde and an acid catalyst are added to the aqueous solution, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. At that time, polyvinyl acetal having reached a certain degree of acetalization is precipitated. After that, the reaction liquid is heated to 25 to 80 ° C. over 30 to 300 minutes and maintained at that temperature for 10 minutes to 24 hours (this temperature is set as the reaction temperature at the time of driving). Next, if necessary, a neutralizing agent such as alkali is added to the reaction solution to neutralize the acid catalyst, and the polyvinyl acetal is obtained by washing with water and drying.

  As the acid catalyst used in the acetalization reaction, either an organic acid or an inorganic acid can be used. For example, acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like can be mentioned. Of these, hydrochloric acid, sulfuric acid and nitric acid are preferably used.

  In the present invention, examples of the aldehyde used in the acetalization reaction include known aldehydes having a hydrocarbon group and alkyl acetals thereof. Among the aldehydes having a hydrocarbon group, aliphatic aldehydes and alkyl acetals thereof include formaldehyde (including paraformaldehyde), acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, isovaleraldehyde, hexylaldehyde and 2-ethyl. Butyraldehyde, pivalaldehyde, octyl aldehyde, 2-ethylhexyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde, etc. , Cyclohexanaldehyde, methylcyclohexanaldehyde, dimethylcyclohexanaldehyde, cyclohexane Cetaldehyde and the like are cyclic unsaturated aldehydes and their alkyl acetals, such as cyclopentene aldehyde and cyclohexene aldehyde, and aromatic or unsaturated bond-containing aldehydes and their alkyl acetals are benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde and methoxybenzaldehyde. , Phenylacetaldehyde, phenylpropyl aldehyde, cumin aldehyde, naphthyl aldehyde, anthra aldehyde, cinnam aldehyde, croton aldehyde, acrolein aldehyde, 7-octen-1-al, etc., and heterocyclic aldehydes and their alkyl acetals are furfural aldehyde, methyl. Furfural aldehyde and the like can be mentioned. Among these aldehydes, aldehydes having 1 to 8 carbon atoms are preferable, aldehydes having 4 to 6 carbon atoms are more preferable, and n-butyraldehyde is particularly preferable. In the present invention, it is also possible to use polyvinyl acetal obtained by using two or more aldehydes in combination.

  The production of EVOH used as a raw material polymer containing the structural unit (III) will be described below. The EVOH can be obtained by radically polymerizing ethylene and vinyl acetate to obtain an ethylene-vinyl acetate copolymer and then saponifying it.

  The polymerization method for producing an ethylene-vinyl ester copolymer by copolymerizing ethylene and vinyl acetate may be batch polymerization, semi-batch polymerization, continuous polymerization or semi-continuous polymerization. As the polymerization method, known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method can be adopted. A bulk polymerization method or a solution polymerization method in which the polymerization proceeds in the absence of solvent or in a solvent such as alcohol is usually adopted. In order to obtain an ethylene-vinyl ester copolymer having a high degree of polymerization, adoption of the emulsion polymerization method is one of the options.

  As the solvent used in the solution polymerization method, alcohol is preferably used, and for example, lower alcohols such as methanol, ethanol and propanol are more preferably used. The amount of the solvent used in the polymerization reaction solution may be selected in consideration of the viscosity average polymerization degree of the target EVOH and the chain transfer of the solvent, and the mass ratio of the solvent contained in the reaction solution to all the monomers ( (Solvent / all monomers) is selected from the range of 0.01 to 10, preferably 0.05 to 3.

  The polymerization initiator used when copolymerizing ethylene and vinyl acetate is selected from known polymerization initiators such as azo-based initiators, peroxide-based initiators and redox-based initiators according to the polymerization method. .. Examples of the azo-based initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4). -Dimethylvaleronitrile). Examples of peroxide-based initiators include percarbonate-based compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, α -Cumyl peroxyneodecanate, perester compounds such as acetyl peroxide; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like. You may use potassium persulfate, ammonium persulfate, hydrogen peroxide etc. in combination with the said initiator. The redox initiator is, for example, a polymerization initiator in which the above-mentioned peroxide initiator is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, and Rongalit. The amount of the polymerization initiator used cannot be generally determined because it varies depending on the polymerization catalyst, but it is adjusted according to the polymerization rate. The amount of the polymerization initiator used is preferably 0.01 to 0.2 mol% and more preferably 0.02 to 0.15 mol% with respect to the vinyl acetate monomer. The polymerization temperature is suitably room temperature to 150 ° C, preferably 40 ° C or higher and not higher than the boiling point of the solvent used.

  When copolymerizing ethylene and vinyl acetate, they may be copolymerized in the presence of a chain transfer agent as long as the effects of the present invention are not impaired. Examples of the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; phosphinate salts such as sodium phosphinate monohydrate. .. Of these, aldehydes and ketones are preferably used. The amount of the chain transfer agent added to the polymerization reaction liquid is determined according to the chain transfer coefficient of the chain transfer agent and the degree of polymerization of the intended ethylene-vinyl ester copolymer, but generally 100 mass% of vinyl acetate monomer. The amount is preferably 0.1 to 10 parts by mass.

  A known method can be adopted as a method for saponifying the ethylene-vinyl acetate copolymer. The saponification reaction is usually carried out in a solution of alcohol or hydrous alcohol. The alcohol preferably used at this time is a lower alcohol such as methanol and ethanol, and particularly preferably methanol. The alcohol or hydrous alcohol used in the saponification reaction may contain other solvents such as acetone, methyl acetate, ethyl acetate and benzene as long as the content is 40% by mass or less. The catalyst used for saponification is, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali catalyst such as sodium methylate, or an acid catalyst such as a mineral acid. The temperature for saponification is preferably in the range of 20 to 120 ° C, for example. When a gel-like product is deposited as the saponification progresses, EVOH can be obtained by crushing the product, washing and drying it.

  When copolymerizing ethylene and vinyl acetate, other monomers may be further copolymerized within the range not impairing the gist of the present invention. Examples of such a monomer include those described above as the vinyl compound to be copolymerized with vinyl acetate when producing PVA used as a raw material polymer.

  Examples of the method of reacting the starting polymer containing the structural unit (III) with the compound (IX) include a method of reacting the starting polymer and the compound (IX) in a molten state, or a starting polymer and a compound (IX) dissolved in an organic solvent. ) Are included, and the former is preferable.

  A known melt-kneader can be used as an apparatus used for melt-kneading the raw material polymer and the compound (IX). Examples thereof include a stirring blade type batch kneader, a kneader type kneader, a screw type kneader such as an extruder, and a static mixer type kneader. These devices may be connected and used continuously.

  When the raw material polymer and the compound (IX) are melt-kneaded using a screw-type kneader, a vacuum vent can be used if necessary. Since the impurities such as moisture are removed by the reduced pressure, the reaction is accelerated.

  Examples of the organic solvent used when reacting the raw material polymer dissolved in the organic solvent with the compound (IX) include dimethyl sulfoxide, N, N-dimethylformamide, dimethylacetamide, tetrahydrofuran, dioxane, toluene, alcohol solvents, water. And the like, and these may be used alone or in admixture of two or more.

  The amounts of both used when the raw material polymer and the compound (IX) are reacted can be appropriately adjusted according to the target modification rate. In reacting the raw material polymer with the compound (IX), the compound (IX) may be used alone or in combination of two or more kinds.

  In order to produce the polymer of the present invention more efficiently, it is also preferable to react the starting polymer containing the structural unit (III) with the compound (IX) in the presence of a catalyst. As the catalyst, an organic acid catalyst or a metal catalyst can be used. These may be used alone or in combination of two or more. Examples of the organic acid catalyst include organic carboxylic acids and organic sulfonic acids. Examples of the organic carboxylic acid include benzoic acid, paranitrobenzoic acid, and aliphatic carboxylic acid, and examples of the organic sulfonic acid include paratoluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like. Examples of the metal catalyst include tetrabutyl titanate, tetra-isopropyl titanate, tetra (2-ethylhexyl) titanate, titanium compounds such as TYZOR TE, zirconium compounds such as tetrabutyl zirconate, aluminum compounds, tin compounds, zinc compounds, molybdenum. Examples thereof include compounds, antimony compounds and organic alkali metal catalysts.

  Among them, a titanium compound, a zirconium compound and an aluminum compound are preferable as the catalyst used in the production method of the present invention, from the viewpoint of excellent handling balance, low toxicity, reactivity, non-coloring property, thermal stability and the like, and titanium compounds are preferable. And zirconium compounds are more preferred.

  The amount of the catalyst added is usually 0.001 to 1 part by mass, preferably 0.002 to 0.5 part by mass, and more preferably 0, based on 100 parts by mass of the raw material polymer and the compound (IX). 0.005-0.2 parts by mass. When the amount of the catalyst is less than 0.001 part by mass, the addition rate of the compound (IX) may be too slow. On the other hand, when it exceeds 1 part by mass, the obtained polymer may be colored or the thermal stability may be deteriorated.

  The reaction temperature is usually 50 to 300 ° C. When the reaction temperature is lower than 50 ° C, the addition rate of the compound (IX) may be too slow. On the other hand, when the temperature exceeds 300 ° C., a thermal decomposition reaction of the raw material may occur or the obtained polymer may be colored.

  In the polymer production method of the present invention, the order and method of adding the raw materials and the catalyst are not particularly limited. The amount of water contained in the raw material used in the method for producing a polymer of the present invention is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less. .. When the amount of water contained in the raw material exceeds 0.5% by mass, when the catalyst is used, the catalyst may be inactivated by hydrolysis and the reactivity may be lowered.

  In the above production method, various additives may be blended within a range that does not impair the effects of the present invention. Examples of such additives include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers and other polymers. The total amount of these additives is usually 50 parts by mass or less, and preferably 10 parts by mass or less, based on 100 parts by mass of the raw material polymer and the compound (IX). Examples of the additive include the following.

Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2'-methylene. -Bis- (4-methyl-6-t-butylphenol), octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6- t-butylphenol) and the like.

UV absorber: ethylene-2-cyano-3,3'-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzo Triazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy- 4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like.

Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc.

Antistatic agent: pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax, etc.

Lubricants: ethylene bis stearamide, butyl stearate, etc.

Coloring agent: carbon black, phthalocyanine, quinacridone, indoline, azo pigment, red iron oxide, etc.

Filler: glass fiber, asbestos, ballastonite, calcium silicate, etc.

  The polymer of the present invention is suitably used as a ceramic molding binder. The polymer of the present invention has a small amount of carbon residue after firing. Therefore, when the polymer of the present invention is used as a binder, a high-performance ceramic molded product having a small amount of carbon residue can be obtained.

  In addition to the polymer of the present invention, the binder for ceramic molding may optionally contain an adhesion improver, a plasticizer, and other conventionally known additives. The content of the additive in the ceramic molding binder is less than 50% by mass, preferably less than 20% by mass, more preferably less than 10% by mass, and further preferably substantially free of the component.

  The ceramic forming binder is preferably used for ceramic slurry and the like. The amount of the ceramic forming binder used cannot be unconditionally specified because it varies depending on the intended use of the ceramic green sheet, but is usually 3 to 30 parts by mass, preferably 5 to 100 parts by mass of the ceramic powder. 25 parts by mass.

  A ceramic slurry containing the polymer of the present invention, ceramic powder and an organic solvent is a preferred embodiment of the present invention. The ceramic slurry is excellent in dispersibility of ceramic powder and is also excellent in storage stability.

  The content of the polymer of the present invention in the ceramic slurry is preferably 3 to 30 parts by mass, and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the ceramic powder.

Examples of the ceramic powder include metal or non-metal oxides or non-oxide powders used for producing ceramics. Specific examples thereof include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoids, actinides, Ti, Zr, Hf, Bi, V, Nb. , Ta, W, Mn, Fe, Co, Ni, and other oxides, carbides, nitrides, borides, sulfides, and the like. Furthermore, when classifying specific examples of the oxide powders usually contain more metal elements referred to as double oxides from the crystal _{structure, NaNbO 3, SrZrO 3, PbZrO} 3, SrTiO 3 as taking a perovskite structure, BaZrO ₃ , PbTiO ₃ , BaTiO _3, etc. have spinel type structures, and MgAl ₂ O ₄ , ZnAl ₂ O ₄ , CoAl ₂ O ₄ , NiAl ₂ O ₄ , MgFe ₂ O _4, etc., have ilmenite type structures. Examples of MgTiO ₃ , MnTiO ₃ , FeTiO _{3 and the} like having a garnet type structure include GdGa ₅ O ₁₂ and Y ₆ Fe ₅ O ₁₂ . These ceramic powders may be used alone or as a mixture of two or more kinds.

  The organic solvent contained in the ceramic slurry includes alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; cellsolves such as methyl cellosolve and butyl cellosolve; ketones such as acetone and methyl ethyl ketone; aromas such as toluene and xylene. Group hydrocarbons; halogen-based hydrocarbons such as dichloromethane and chloroform are included. These may be used alone or in combination of two or more.

  The content of the organic solvent in the ceramic slurry is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the ceramic powder. When the content of the organic solvent is less than 2 parts by mass, the viscosity of the slurry becomes too high and the kneading property tends to decrease. The content is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more. On the other hand, when the content of the organic solvent is more than 200 parts by mass, the viscosity tends to be too low and the handling property at the time of forming the ceramic green sheet tends to deteriorate. The content is more preferably 170 parts by mass or less, still more preferably 150 parts by mass or less.

  The ceramic slurry may contain a plasticizer. As the plasticizer, without impairing the effects of the present invention, and there is no problem in compatibility with the polymer of the present invention, for example, a mono- or diester of an oligoalkylene glycol having a hydroxyl group at both ends and a carboxylic acid, A diester of dicarboxylic acid and alcohol can be used. These may be used alone or in combination of two or more. Specifically, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-n-heptanoate. Monoester or diester of oligoalkylene glycol having hydroxyl groups at both terminals such as tri or tetraethylene glycol and carboxylic acid; diester of dicarboxylic acid and alcohol such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dibutyl adipate ..

  When the plasticizer is added, the mass ratio of the plasticizer to the polymer of the present invention (plasticizer / polymer) in the ceramic slurry is preferably 0.01 to 2, and 0.05 to 1. It is more preferably 5. The plasticizer may be contained in the binder containing the polymer of the present invention in advance.

  The ceramic slurry contains, in addition to the polymer, ceramic powder, organic solvent, and plasticizer, a peptizer, an adhesion promoter, a dispersant, a tackifier, a storage stabilizer, a defoaming agent, and a heat, if necessary. Other additives such as degradation accelerators, antioxidants, surfactants, lubricants, other polymers may be included. The total amount of such other additives is preferably 50% by mass or less, and more preferably 20% by mass or less.

  The ceramic slurry can be manufactured, for example, by the following method. The binder for ceramic molding containing the polymer of the present invention is dissolved in an organic solvent, an additive such as a plasticizer is added to the solution as needed, and the mixture is stirred to produce a uniform vehicle. After adding the ceramic powder to the vehicle, it is uniformly dispersed to obtain a ceramic slurry. As a method for dispersing, various methods such as a method using a medium type disperser such as a bead mill, a ball mill, an attritor, a paint shaker and a sand mill, a kneading method, a method using three rolls can be used. At that time, as the dispersant, an anionic dispersant having a carboxylic acid group, a maleic acid group, a sulfonic acid group, a phosphoric acid group or the like in the molecule may be used, and particularly, an anionic dispersant containing no metal ion. Is preferably used.

  A preferred embodiment of the present invention is a ceramic green sheet obtained by using the above ceramic slurry. The ceramic green sheet has excellent surface smoothness and also excellent sheet strength. Further, the ceramic green sheet has a high surface gloss. Therefore, the ceramic green sheet of the present invention is suitably used as a material for various electronic components. Above all, it is preferably used as a material for a chip type multilayer capacitor, a circuit board of an IC chip, and the like. These are manufactured by forming electrodes on a ceramic green sheet, stacking and pressing the electrodes, and then firing the electrodes.

  Examples of the method for producing the ceramic green sheet include a method in which a ceramic slurry is applied onto a support film that has been subjected to a one-side release treatment, and then the organic solvent is dried to form a sheet. A roll coater, a blade coater, a die coater, a squeeze coater, a curtain coater or the like can be used for coating the ceramic slurry.

  As the support film used when manufacturing the ceramic green sheet, one made of a resin having heat resistance and solvent resistance and having flexibility is preferable. When the support film is made of a flexible resin, the ceramic slurry can be applied onto the support film. Then, the obtained ceramic green sheet forming film can be stored in a rolled state and supplied as needed.

  Examples of the resin that constitutes the support film include fluororesins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, PVA, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose. The thickness of the support film is preferably 20 to 100 μm. Further, it is preferable that the surface of the support film is subjected to a release treatment. By subjecting the surface of the support film to the release treatment, the peeling operation of the support film can be easily performed in the transfer step. A preferred specific example of the support film is a silicone-coated PET film.

  The thickness of the ceramic green sheet cannot be unconditionally specified because it depends on the purpose of use, but it is preferably in the range of 0.1 to 300 μm. The drying temperature for drying the coating film formed on the carrier film cannot be unconditionally specified because it varies depending on the thickness of the ceramic green sheet and the like, but is in the range of 25 to 200 ° C.

  In the production of the ceramic green sheet, a step of subjecting at least one surface of the ceramic green sheet to atmospheric pressure plasma treatment may be provided in order to improve adhesiveness.

  The polymer of the present invention is used not only as a binder for ceramic molding but also as a conductive paste.

（式中、ｎは１〜２０の整数である。Ｒ^４の炭素数は２５０以下である。Ｒ^４は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、置換基を有してもよいアシル基又はカルボキシル基である。）
とを反応させて、下記基（XI）

（式中、ｎ及びＲ^４は、上記化合物（Ｘ）と同じである。）
を形成させる水酸基含有重合体の変性方法である。水酸基含有重合体をラクタム系化合物である化合物（Ｘ）で変性させることにより、水酸基含有重合体に様々な機能を付与することが可能である。 The method for modifying the hydroxyl group-containing polymer of the present invention includes a hydroxyl group-containing polymer and the following compound (X)

(In the formula, n is an integer of 1 to 20. The carbon number of R ⁴ is 250 or less. R ⁴ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent Optionally an amino group, an optionally substituted amide group, an optionally substituted acyl group or a carboxyl group.)
And react with the following group (XI)

(In the formula, n and R ⁴ are the same as those in the compound (X).)
Is a method of modifying a hydroxyl group-containing polymer. Various functions can be imparted to the hydroxyl group-containing polymer by modifying the hydroxyl group-containing polymer with the compound (X) which is a lactam compound.

  The hydroxyl group-containing polymer used in the modification method of the present invention may be a polymer having a hydroxyl group. A polymer containing the above-mentioned structural unit (III) (vinyl alcohol monomer unit) or a polymer containing an allyl alcohol monomer unit is industrially produced as a raw material polymer used for producing the polymer of the present invention. Synthetic polymers, semi-synthetic polymers such as viscose rayon, natural polymers such as glycogen, amylopectin, and cellulose.

As the compound (X), the compound (IX) described above as the lactam compound used for producing the polymer of the present invention is used. Further, as the compound (X), a compound (IX) in which R ¹ is a methyl group is also used.

  As the method of reacting the hydroxyl group-containing polymer with the compound (X), the above-mentioned method is adopted as the method of reacting the starting polymer containing the structural unit (III) with the compound (IX).

  Hereinafter, the present invention will be described more specifically with reference to Examples.

(Synthesis of compound (IX))
Synthesis example 1
In a 2 liter glass container equipped with a reflux condenser, a thermometer, a dropping funnel, and an Ikari type stirring blade, 500 mL of toluene, 39.1 g of ε-caprolactam and 50.5 g of diisopropylethylamine were charged, and the content was 100 rpm. The temperature was raised to 110 ° C. with stirring. 75 g of 4-n-pentylbenzoyl chloride was added dropwise to the container over 15 minutes, and after completion of the addition, the mixture was cooled to room temperature. 500 mL of distilled water was added to the container and stirred, and the toluene layer was separated. The toluene layer was washed twice with 500 mL of distilled water, and then toluene was distilled off under reduced pressure to obtain a crude product. By recrystallizing the crude product with a toluene-hexane mixed solution, 90.3 g of the following compound [N- (4-n-pentylbenzoyl) -ε-caprolactam] was obtained (yield 91%).

Synthesis example 2
The following compound [N- (4-n-decylbenzoyl)-[epsilon]-was prepared in the same manner as in Synthesis Example 1 except that 99.8 g of 4-n-decylbenzoyl chloride was used instead of 4-n-pentylbenzoyl chloride. Caprolactam] was obtained (yield 90%). The chart obtained by ¹ H-NMR analysis of the compound is shown in FIG. 1. ¹ H-NMR analysis was performed in deuterated chloroform at room temperature.

Synthesis example 3
The following compound [N- (4-n-pentadecylbenzoyl)-was prepared in the same manner as in Synthesis Example 1 except that 124.72 g of 4-n-pentadecylbenzoyl chloride was used instead of 4-n-pentylbenzoyl chloride. 121.8 g of (ε-caprolactam) was obtained (yield 80%).

Synthesis example 4
The following compound [N- (2,4,6-trimethylbenzoyl] was used in the same manner as in Synthesis Example 1 except that 63.1 g of 2,4,6-trimethylbenzoyl chloride was used instead of 4-n-pentylbenzoyl chloride. )-[Epsilon] -caprolactam] was obtained (yield 92%).

Synthesis example 5
In a 2 liter glass container equipped with a reflux condenser, a thermometer, a dropping funnel, and an Ikari type stirring blade, 500 mL of toluene, 39.1 g of ε-caprolactam and 50.5 g of diisopropylethylamine were charged, and the content was 100 rpm. The temperature was raised to 110 ° C. with stirring. 57.9 g of 2-ethylhexanoyl chloride was added dropwise to the container over 15 minutes, and after completion of the addition, the temperature was cooled to room temperature. 500 mL of distilled water was added to the container and stirred, and the toluene layer was separated. The toluene layer was washed twice with 500 mL of distilled water, and then toluene was distilled off under reduced pressure to obtain a crude product. The crude product was distilled under reduced pressure (50 Pa, 130-140 ° C.) to obtain 66.2 g of the following compound [N- (2-ethylhexanoyl) -ε-caprolactam] (yield 80%).

Synthesis example 6
55.3 g of the following compound [N-tigryl-ε-caprolactam] was obtained in the same manner as in Synthesis Example 1 except that 42.2 g of tiglyl chloride was used instead of 2-ethylhexanoyl chloride. %).

Synthesis example 7
In a 5 L four-necked flask equipped with a mechanical stirrer, a cooling tube, and an internal thermometer, triethylene glycol monomethyl ether (331 g, 2.01 mol), NEt ₃ (190 g, 1.88 mol), N, N-diisopropylethylamine (DIPEA, 84.0 g, 65.0 mol) and THF (1.0 L) were added, and the mixture was cooled to 0 ° C with an ice bath. Methanesulfonic acid chloride (266 g, 2.32 mol) was added dropwise while keeping the internal temperature at 30 ° C or lower. After the dropwise addition was completed, the ice bath was removed, the mixture was stirred for another 1 hour, and saturated aqueous ammonium chloride solution (1 L) was added to stop the reaction. The aqueous layer was extracted with ethyl acetate (1st time: 1 L, 2nd time: 500 mL), and the combined organic phases were concentrated to give the following compound 1 as a brown oil (490 g, 2.02 mol, yield 100%). ). The following compound 1 was used for the next reaction.

The results of ¹ H-NMR analysis of the above compound are shown below. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C): d 4.42-4.33 (m, 2H), 3.81-3.73 (m, 2H), 3.72-3.60 (m, 6H), 3.60-3.51 (m, 2H ), 3.38 (s, 3H), 3.07 (s, 3H)

In a 2 L four-necked flask equipped with a mechanical stirrer, a cooling tube, and an internal thermometer, hydroxybenzoic acid (41.4 g, 300 mmol), potassium hydroxide (85 wt%; 154 g, 2.33 mol), MeOH (800 mL), water ( (800 mL) was added and the mixture was heated in an oil bath at 60 ° C. to dissolve it, then the above compound 1 (490 g, 2.02 mol) was added, and the mixture was refluxed for 26 hours. Potassium hydroxide (44.0 g, 667 mmol) was added to the mixture, and the mixture was heated in an oil bath at 60 ° C. for 1 hour, and then acidified by adding a 2N HCl aqueous solution (500 mL), and the aqueous layer was extracted with ethyl acetate (250 mL × 5 ), The combined organic phase was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. Diisopropyl ether (300 mL) was added to the residue for reprecipitation, and the resulting solid was washed with diisopropyl ether (200 mL × 2) to obtain the following compound 2 as a white solid (105 g, 370 mmol, yield 56%). The results of ¹ H-NMR analysis of the following compound 2 are shown below. The following compound 2 was used for the next reaction.

The results of ¹ H-NMR analysis of the above compound are shown below. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C): d 8.04 (d, ³ J _HH = 8.5 Hz, 2H), 6.95 (d, ³ J _HH = 8.0 Hz, 2H), 4.25-4.16 (m, 2H), 3.93-3.87 (m, 2H), 3.80-3.60 (m, 6H), 3.60-3.50 (m, 2H), 3.38 (s, 3H)

  The compound 2 (105 g, 370 mmol) and chloroform (500 mL) were added to a 2 L separable flask equipped with a mechanical stirrer, a dropping funnel, a condenser, and an internal thermometer, and the mixture was heated in an oil bath at 50 ° C. for dissolution. , DMF, and a solution of thionyl chloride (220 g, 1.85 mol) in toluene (500 mL) was added dropwise. After heating in an oil bath at 75 ° C. and stirring for 100 minutes, unreacted thionyl chloride and the solvent were distilled off under reduced pressure. The operation of adding toluene (100 mL) and distilling off under reduced pressure was repeated twice. The residue was dissolved in toluene (500 mL), a toluene (200 mL) solution of DIPEA (97 mL, 555 mmol) and ε-caprolactam (43.1 g, 381 mmol) was added, and the mixture was heated in an oil bath at 75 ° C and stirred for 1 hour. After cooling to room temperature, water (300 mL) was added, the organic phase was extracted with ethyl acetate (250 mL × 5), dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was adsorbed on silica gel (320 g) and eluted with 3.5 L of a mixed solution of ethyl acetate and methanol (ethyl acetate / MeOH = 20/1), and then the mixed solution was concentrated to give the following compound as a light brown solid. Obtained. (105 g, 370 mmol, yield 96%).

The results of ¹ H-NMR analysis of the above compound are shown below. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C): d 7.57 (d, ³ J _HH = 8.5 Hz, 2H), 6.89 (d, ³ J _HH = 8.0 Hz, 2H), 4.21-4.14 (m, 2H), 393-3.80 (m, 4H), 3.77-3.49 (m, 8H), 3.38 (s, 3H), 2.73-2.68 (m, 2H), 1.90-1.78 (m, 8H)

Synthesis example 8
Sodium hydride (60 wt%, 3.95 g, 98.7 mmol) and DMF (500 mL) were added to a 5 L three-necked flask equipped with a mechanical stirrer, a dropping funnel, a condenser, and an internal thermometer, and the internal temperature was 10 ° C. A DMF (1100 mL) solution of polyethylene glycol methyl ether (mPEG, molecular weight 2000, 158 g, 79.0 mmol) was added dropwise while keeping the following. A solution of methyl 4- (bromomethyl) -benzoate (15.1 g, 65.8 mmol) in DMF (300 mL) was added, and the mixture was stirred for 2 hours while warming to room temperature, then, 2-PrOH (7.6 mL) and saturated NH ₄ Cl. Aqueous solution (30 mL) was added and stirred for 10 minutes. After concentration, the residue was dissolved in water (500 mL), potassium hydroxide (21.7 g, 329 mmol) and water (200 mL) were added, and the mixture was heated in a 60 ° C. oil bath for 90 minutes. The mixture was acidified by adding 2N aqueous HCl solution (150 mL), the aqueous layer was extracted with dichloroethane (200 mL x 5), the combined organic phases were dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The resulting solid was washed with diisopropyl ether (200 mL) to obtain the following compound 3 as a white solid. (106 g, 50.0 mmol, yield 76%).

The results of ¹ H-NMR analysis of the above compound are shown below. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C): d 8.05 (d, ³ J _HH = 8.0 Hz, 2H), 7.44 (d, ³ J _HH = 8.0 Hz, 2H), 4.64 (s, 2H) , 3.75-3.54 (m, ~ 180H), 3.38 (s, 3H)

  The above compound 3 (19.5 g, 9.16 mmol) and chloroform (50 mL) were added to a 1 L four-necked flask equipped with a mechanical stirrer, a dropping funnel, a condenser, and an internal thermometer, and heated in an oil bath at 50 ° C. Then, 3 drops of DMF were added, and a solution of thionyl chloride (29.7 g, 250 mmol) in chloroform (50 mL) was added dropwise. The mixture was heated in an oil bath at 75 ° C., the above compound 3 (87.1 g, 40.8 mmol) and chloroform (400 mL) were added dropwise, and the mixture was further stirred for 8 hours. Unreacted thionyl chloride and the solvent were distilled off under reduced pressure, toluene (100 mL) was added, and the operation of distilling off under reduced pressure was repeated twice. The residue is dissolved in toluene (100 mL), DIPEA (9.69 g, 75.0 mmol) and ε-caprolactam (5.83 g, 51.5 mmol) in toluene (50 mL) are added, and the mixture is heated in an oil bath at 75 ° C. And stirred for 8 hours. After cooling to room temperature, water (150 mL) was added, the organic phase was extracted with a mixture of dichloroethane and acetone [(dichloroethane 200 mL / acetone 100 mL) x 5], and the combined organic phases were dried over sodium sulfate, and then depressurized. The solvent was distilled off underneath. The residue was adsorbed on silica gel (320 g), eluted with 3.5 L of a mixed solution of ethyl acetate and methanol (ethyl acetate / MeOH = 20/1), and then the mixed solution was concentrated. The concentrate was dried under reduced pressure at 60 ° C and cooled to 2 ° C to obtain the following compound as a brown solid. (75.9 g, 34.1 mmol, yield 68%).

上記化合物の^１Ｈ−ＮＭＲ分析の結果を以下に示す。¹H NMR (400 MHz, CDCl₃, 25 °C): d 7.52 (d, ³J_HH = 8.5 Hz, 2H), 7.36 (d, ³J_HH = 8.0 Hz, 2H), 4.39 (s, 2H), 3.72-3.48 (m,〜180H), 3.38 (s, 3H), 2.73-2.68 (m, 2H), 1.90-1.69 (m, 8H)

The results of ¹ H-NMR analysis of the above compound are shown below. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C): d 7.52 (d, ³ J _HH = 8.5 Hz, 2H), 7.36 (d, ³ J _HH = 8.0 Hz, 2H), 4.39 (s, 2H) , 3.72-3.48 (m, ~ 180H), 3.38 (s, 3H), 2.73-2.68 (m, 2H), 1.90-1.69 (m, 8H)

Synthesis example 9
97.6 g of the following compound was obtained in the same manner as in Synthesis Example 5 except that 69.9 g of 2- [2- (2-methoxyethoxy)] acetic acid chloride was used instead of 2-ethylhexanoyl chloride. 80%).

Synthesis example 10
A lithium diethylamide solution (0.5 mol / L, 1 L) was added to a 5 L separable flask equipped with a mechanical stirrer, a dropping funnel, a condenser, and an internal thermometer, and the mixture was cooled in an ice bath at 0 ° C., followed by diglycolic acid. A tetrahydrofuran solution (500 mL) of an anhydride (58 g, 500 mmol) was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 30 ° C for 1 hour. The reaction mixture was cooled in an ice bath at 0 ° C., distilled water (1 L) and 2N HCl aqueous solution (300 mL) were added, and the mixture was stirred, extracted with toluene (1 L) three times, and the combined organic phases were evaporated under reduced pressure. Thereby, a carboxylic acid precursor was obtained (71 g, 375 mmol). A solution of chloroform (1 L) and thionyl chloride (118 g, 1.0 mol) in toluene (1 L) was added dropwise to the carboxylic acid precursor. After heating in an oil bath at 75 ° C. and stirring for 100 minutes, unreacted thionyl chloride and the solvent were distilled off under reduced pressure. Toluene (500 mL) was further added and the operation of distilling off under reduced pressure was repeated twice. The residue was dissolved in toluene (500 mL), DIPEA (97 mL, 555 mmol) and ε-caprolactam (41.8 g, 370 mmol) in toluene (200 mL) were added, and the mixture was heated in an oil bath at 75 ° C. and stirred for 1 hour. After cooling to room temperature, water (300 mL) was added, the organic phase was extracted with ethyl acetate (250 mL x 5), dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was adsorbed on silica gel (320 g) and eluted with 3.5 L of a mixed solution of ethyl acetate and methanol (ethyl acetate / MeOH = 20/1), and then the mixed solution was concentrated to give the following compound as a light brown liquid. Obtained. (96.7 g, 340 mmol, yield 92%).

(Production and evaluation of polymer)
The polymer containing the structural units (III) and (IV) and the compound (IX) were melt-kneaded using a Labo Plastomill type melt-kneader manufactured by Toyo Seiki Seisakusho Co., Ltd. The rotation speed was 100 rpm. The block was preheated to a predetermined temperature before adding the polymer containing the structural units (III) and (IV) and the compound (IX), and the inside of the block was replaced with nitrogen to start the reaction.

The obtained polymer was dissolved in heavy dimethyl sulfoxide to which 1,3,5-trimethoxybenzene was added as an internal standard, and ¹ H-NMR analysis (80 ° C.) was performed. In the obtained ¹ H-NMR chart, the integral ratio of signals derived from hydrogen contained in the structural unit (I), the integral ratio of signals derived from hydrogen contained in the structural unit (II), and total vinyl in the main chain. The modification ratio (a + b) of the polymer was determined using the integral ratio of the units.

FIG. 2 is a ¹ H-NMR chart of polyvinyl butyral as a raw material (upper stage) and polyvinyl butyral (lower stage) containing the obtained structural units (I) to (IV) and (VI) in Example 7 described later. Is. The method of analyzing the ¹ H-NMR chart will be described with reference to FIG. 2 (latter stage). The signals at 6.08 ppm and 3.76 ppm are derived from 1,3,5-trimethoxybenzene. 7.85 ppm is a signal corresponding to the aromatic ring 2H content in the structural unit (II), and 7.74 ppm is a signal corresponding to the aromatic ring 2H content in the structural unit (I). The signals at 5.35 ppm and 5.11 ppm are unique signals generated when the secondary alcohol in the polyvinyl butyral main chain reacts with the compound (IX) to form an ester bond, and the former is structural unit (II). It corresponds to the main chain methine 1H in the inside, and the latter corresponds to the main chain methine 1H in the structural unit (I). From 1.7 ppm to 0.95 ppm, methylene 2H of all vinyl units in the main chain, saturated hydrocarbon sites in structural units (I) and (II), saturated hydrocarbon sites in unreacted reactants, and caprolactam saturation The signals derived from the hydrocarbon moieties are present in a superimposed state. From the integral ratios of these signals as a whole, the integral ratios of other signals [aromatic ring 2H in the above-mentioned structural units (I) and (II), 2.70 ppm (unreacted reactant), 2.29 ppm (caprolactam)] Subtracting the integral ratio of the signals derived from the saturated hydrocarbon sites in structural units (I) and (II), the saturated hydrocarbon sites of the unreacted reagent, and the saturated hydrocarbon sites of caprolactam, calculated separately using Can calculate the integral ratio of only all vinyl units in the main chain. The target modification ratio was 8.0 mol%, whereas the modification ratio determined from the NMR chart was 7.8 mol%.

In the obtained polymer, the ratio (%) of the content rate of the structural unit (I) to the total content rate of the structural unit (I) and the content rate of the structural unit (II) is determined by the ring-opening reaction selectivity ( Hereinafter, it is abbreviated as selectivity). The selectivity is represented by the following formula.

Selectivity (%) = 100 × a / (a + b)

a: Content of structural unit (I) with respect to all monomer units (mol%)
b: Content of structural unit (II) with respect to all monomer units (mol%)

The ¹ H-NMR chart of the above-mentioned polymer was obtained by converting the conversion rate of the compound (IX) obtained by reacting the compound (IX) represented by the following formula with the polymer containing the structural units (III) and (IV) with the compound (IX). Was calculated using.

Conversion rate (%) = 100 × [total amount (mol) of structural units (I) and (II) in the obtained polymer] / [addition amount (mol) of compound (IX)]

(Storage stability of ceramic slurry)
The storage stability of the obtained ceramic slurry was evaluated by the ratio of the viscosity η ₀ immediately after the production of the ceramic slurry and the viscosity η ₁ one month after the production. The evaluation criteria are shown below.
A: 0.95 <η ₁ / η ₀ <1.05
B: 0.85 <η ₁ / η ₀ ≦ 0.95 or 1.05 ≦ η ₁ / η ₀ <1.15
C: η ₁ / η ₀ ≦ 0.85 or 1.15 ≦ η ₁ / η ₀

The viscosity of the ceramic slurry was measured using a rotating rheometer (“ARES G2” manufactured by TA INSTRUMENT) under the following conditions.

FLOW SWEEP mode shear rate: 100 (1 / sec)
Diameter of rotating disk: 40mm
Rotating disc (upper side): flat plate Rotating disc (lower side) cone angle: 0.02 rad
Truncation gap: 0.0262mm

(Amount of carbon residue on the ceramic green sheet)
The amount of carbon residue (resin-derived residue) of the ceramic green sheet was evaluated using "Q5000IR" manufactured by TA INSTRUMENTS. The ceramic green sheets were heated in a platinum pan, and the carbon ratio r (wt%) in the residue was measured for evaluation. The evaluation criteria are shown below.
A: r ≦ 0.02
B: 0.02 <r ≦ 0.05
C: 0.05 <r ≦ 0.10

(Mechanical strength)
The obtained ceramic green sheet was peeled from the polyester film, the state was observed, and the evaluation was made according to the following three grades. The results are shown in Table 2.
A: No break or tear was observed.
B: Very few breaks and tears were observed.
C: Many breaks and tears were observed.

(Measurement of elongation at break)
The breaking elongation in the tensile test was performed using an autograph "AG-5000B" manufactured by Shimadzu Corporation, and a No. 2 dumbbell (thickness 1 mm) described in JIS K7113 was used as a test piece, and a tensile speed was 10 mm / It was measured at min and evaluated according to the following criteria. If the elongation at break is too large, there is a problem that the cross section is deformed when the laminate of the ceramic green sheets is cut, and the yield is deteriorated. Further, if it is not sufficiently plasticized and the elongation at break is small, the adhesiveness deteriorates.
A: Breaking elongation is 0.5% or more and less than 20% B: Breaking elongation is less than 0.5% or 20% or more

(Measurement of glass transition temperature)
The glass transition temperature was evaluated by measuring a chuck width of 10 mm, a sine frequency of 1 Hz, and a heating rate of 2 ° C./min with a UBM RHEOGEL-4000 using a test piece of length 20 mm × width 5 mm × thickness 20 μm. The glass transition temperature Tg (° C.) was determined under the conditions and evaluated according to the following criteria. Since thermocompression bonding of the ceramic green sheets is performed at 40 ° C. or higher and lower than 70 ° C., it is preferable that the glass transition temperature Tg falls within this temperature range in order to develop the adhesiveness between the green sheets.
A: 40 ≦ Tg <70
B: 40> Tg or Tg ≧ 70

Example 1
52 g of polyvinyl butyral (acetalization degree: 64.9 mol%, vinyl alcohol unit: 33.3 mol%, vinyl ester unit: 1.8 mol%, polymerization degree: 1000) in a Labo Plastomill type melt kneader, obtained in Synthesis Example 1 The compound (IX) (4.8 g) was charged and melt-kneaded at 230 ° C. for 5 minutes to obtain a polymer having structural units (I) to (IV) and (VI). Table 1 shows the selectivity of the obtained polymer and the conversion rate of the compound (IX), and Table 2 shows the composition of the obtained polymer.

  20 parts by mass of the obtained polymer (binder resin) was added to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, and then stirred and dissolved. To the obtained resin solution, 100 parts by mass of barium titanate (“BT-02” manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.2 μm) was added as a ceramic powder, and mixed by a ball mill for 24 hours to prepare a ceramic slurry. Obtained. The storage stability of the obtained ceramic slurry was evaluated. The results are shown in Table 2.

  The obtained ceramic slurry is coated on a polyester film which has been subjected to a mold release treatment, air-dried at room temperature for 1 hour, and then using a hot air dryer at a temperature of 80 ° C. for 3 hours, and then at a temperature of 120 ° C. for 2 hours. It was dried to obtain a ceramic green sheet having a thickness of about 20 μm. The obtained ceramic green sheets were evaluated (amount of carbon residue, mechanical strength, elongation at break, glass transition temperature). The results are shown in Table 2.

Example 2
52 g of polyvinyl butyral (acetalization degree: 64.9 mol%, vinyl alcohol unit: 33.3 mol%, vinyl ester unit: 1.8 mol%, polymerization degree: 1000) in a Labo Plastomill type melt kneader, obtained in Synthesis Example 1 Compound (IX) (4.8 g) and tetrabutoxy titanate (Ti (OBu) ₄ (52 mg) were charged and melt-kneaded at 190 ° C. for 5 minutes to obtain a polymer having structural units (I) to (IV) and (VI). Table 1 shows the selectivity of the obtained polymer and the conversion rate of the compound (IX), and Table 2 shows the composition of the obtained polymer.

Examples 3-19
A polymer was prepared and evaluated in the same manner as in Example 1 except that the type and the amount of the raw material compound (IX) and the raw material polyvinyl butyral and the reaction conditions were changed as shown in Table 1. Table 1 shows the selectivity of the obtained polymer and the conversion rate of the compound (IX), and Table 2 shows the composition of the obtained polymer. A ceramic slurry and a ceramic green sheet were produced and evaluated in the same manner as in Example 1 except that the polymer obtained in each example was used as the binder resin. The results are shown in Table 2.

Comparative Example 1
The same procedure as in Example 1 was repeated except that polyvinyl acetal having an acetalization degree of 64.9 mol%, a vinyl alcohol unit of 33.3 mol%, a vinyl ester unit of 1.8 mol% and a polymerization degree of 1000 was used as the binder resin. Then, the ceramic slurry and the ceramic green sheet were produced and evaluated. The results are shown in Table 2.

Comparative example 2
13 parts by mass of polyvinyl acetal having a degree of acetalization of 64.9 mol%, a vinyl alcohol unit of 33.3 mol%, a vinyl ester unit of 1.8 mol% and a polymerization degree of 1000, and di (2-ethylhexyl) phthalate (DOP) 7 1 part by mass was added to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, and then stirred to obtain a resin solution. A ceramic slurry and a ceramic green sheet were prepared and evaluated in the same manner as in Example 1 except that the resin solution thus obtained was used. The results are shown in Table 2.

Comparative Example 3
The same procedure as in Example 1 was repeated except that a polyvinyl acetal having a degree of acetalization of 70.6 mol%, a vinyl alcohol unit of 28.4 mol%, a vinyl ester unit of 1.0 mol% and a polymerization degree of 1700 was used as the binder resin. Then, the ceramic slurry and the ceramic green sheet were produced and evaluated. The results are shown in Table 2.

Comparative Example 4
13 parts by mass of polyvinyl acetal having an acetalization degree of 70.6 mol%, a vinyl alcohol unit of 28.4 mol%, a vinyl ester unit of 1.0 mol% and a polymerization degree of 1700, and di (2-ethylhexyl) phthalate (DOP) of 7 mass parts. Was added to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, and then stirred to obtain a resin solution. A ceramic slurry and a ceramic green sheet were prepared and evaluated in the same manner as in Example 1 except that the resin solution thus obtained was used. The results are shown in Table 2.

Comparative Example 5
13 parts by mass of polyvinyl acetal having an acetalization degree of 69.0 mol%, vinyl alcohol unit of 30.9 mol%, vinyl ester unit of 0.1 mol%, and polymerization degree of 4,200, and di (2-ethylhexyl) adipate (DOA) of 7 mass parts. Was added to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol and then stirred to obtain a resin solution. A ceramic slurry and a ceramic green sheet were prepared and evaluated in the same manner as in Example 1 except that the resin solution thus obtained was used. The results are shown in Table 2.

Example 20
51 g of ethylene-vinyl alcohol copolymer [ethylene monomer unit content 44 mol%, melt index 13 g / 10 min (210 ° C., 2.16 kg)] was obtained in Synthesis Example 5 in a Labo Plastomill type melt kneader. 6.61 g of compound (IX) (N- (2-ethylhexanoyl) -ε-caprolactam) was charged and melt-kneaded at 210 ° C. for 7 minutes to obtain a polymer having structural units (I) to (V). Obtained. FIG. 3 shows a ¹ H-NMR chart of the raw material EVOH (upper stage) and the obtained polymer (lower stage). A unique ester bond signal is observed in the lower 5.4 to 5.0 ppm when reacted with the hydroxyl group in the raw material. Table 3 shows the selectivity of the obtained polymer and the conversion rate of the compound (IX), and Table 4 shows the composition of the obtained polymer.

Example 21
48 g of EVOH [ethylene monomer unit content 44 mol%, melt index 13 g / 10 min (210 ° C., 2.16 kg)] in a Labo Plastomill type melt kneader, and the following compound (N-benzoyl-ε-caprolactam) 5 0.53 g was charged and melt-kneaded at 210 ° C. for 5 minutes to obtain a polymer having structural units (I) to (V). The selectivity of the obtained polymer and the conversion of N-benzoyl-ε-caprolactam are shown in Table 3, and the composition of the obtained polymer is shown in Table 4.

Example 22
In a 300 ml glass container equipped with a reflux condenser, a thermometer, a dropping funnel, and an Ikari type stirring blade, dimethyl sulfoxide 80 g, polyvinyl alcohol (polymerization degree 300, saponification degree 98.8 mol%) 20 g, N-benzoyl-ε were used. 19.7 g of caprolactam were charged and the contents were heated at 80 ° C. for 300 minutes with stirring at 100 rpm. The content was dropped into methanol (1 L), the precipitate was filtered off and dried under reduced pressure to obtain a modified polyvinyl alcohol having structural units (I) to (IV). FIG. 4 shows the ¹ H-NMR chart of the obtained polymer. A signal derived from an aromatic ring is observed at 8.0-7.4 ppm, and a characteristic signal is observed at 5.4-4.8 ppm when an ester bond is formed with the main chain. The selectivity of the obtained polymer and the conversion of N-benzoyl-ε-caprolactam are shown in Table 3, and the composition of the obtained polymer is shown in Table 4.

Claims (20)

A polymer containing the following structural units (I) and (III) as essential components, the following structural units (II) and (IV) as optional components , and satisfying the following formulas (1) to (4).

(In the formula, n is an integer of ¹ to 20. The carbon number of R ¹ is 250 or less. R ¹ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent It may be an amino group, provided that R ¹ does not include a methyl group.)

(In the formula, R ¹ is the same as the above structural unit (I).)

0.001 ≦ a + b ≦ 98 (1)
0.06 ≦ a / (a + b) ≦ 1 (2)
1 ≦ c ≦ 99.99 (3)
0 ≦ d ≦ 98 (4)
In the formula,
a: Content of the structural unit (I) with respect to all monomer units (mol%)
b: Content of the structural unit (II) with respect to all monomer units (mol%)
c: Content of the structural unit (III) with respect to all monomer units (mol%)
d: Content of the above structural unit (IV) with respect to all monomer units (mol%)
Is. The polymer according to claim 1, further comprising the following structural unit (V) and satisfying the following formula (5).

0.001 ≦ e ≦ 98 (5)
In the formula,
e: Content (mol%) of the structural unit (V) with respect to all monomer units
Is. The polymer according to claim 1, further comprising the following structural unit (VI) and satisfying the following formula (6).

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)
0.001 ≦ 2f ≦ 98 (6)
In the formula,
f: Content of the above structural unit (VI) with respect to all monomer units (mol%)
Is. The polymer according to claim 3, wherein R ² in the structural unit (VI) is a propyl group. The polymer according to claim 1, which satisfies the following formula (2 ′).
0.15 ≦ a / (a + b) ≦ 0.97 (2 ′) Polymers of R ¹ in the structural unit (I) is claimed in any one of claims 1 to 5 having no aromatic ring. The polymer according to any one of claims 1 to 5, wherein R ¹ in the structural unit (I) is the following group (VII).

(In the formula, R ³ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aryl which may have a substituent. Group, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an alkylsilyl group which may have a substituent, an alkylsilyloxy group which may have a substituent, a substituent An acyloxy group which may have a group, an alkoxycarbonyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, and a substituent Sulfonic acid ester group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted amino group, optionally substituted group It is an amide group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom or a hydrogen atom.) The polymer according to claim 7 , wherein R ¹ in the structural unit (I) is the following group (VIII).

(In the formula, p represents 0 or 1, and q represents an integer of 2 to 100.) The polymer according to any one of claims 1 to 7, R ¹ in the structural unit (I) has a 5 or more aliphatic hydrocarbon unit carbon. The polymer according to any one of claims 1-8 wherein R ¹ in the structural unit (I) has a (poly) oxyalkylene units. The polymer according to any one of claims 1 to 7, R ¹ in the structural unit (I) is an amide group. The polymer according to any one of claims 1 to 7, R ¹ in the structural unit (I) has a carboxyl group. The polymer according to any one of claims 1 to 7, R ¹ in the structural unit (I) has an ester group. The method for producing a polymer according to any one of claims 1 to 13, wherein a raw material polymer containing the structural unit (III) is reacted with the following compound (IX).

(In the formula, n and R ¹ are the same as the above structural unit (I).)   The method for producing a polymer according to claim 14, wherein the raw material polymer is polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, or a polyvinyl acetal.   The method for producing a polymer according to claim 14 or 15, wherein the raw material polymer and the compound (IX) are reacted in a molten state.   The polymer according to claim 14, wherein the raw material polymer is reacted with the compound (IX) in the presence of at least one catalyst selected from the group consisting of titanium compounds, zirconium compounds and aluminum compounds. Production method.   A ceramic slurry containing the polymer according to claim 1, ceramic powder and an organic solvent.   A ceramic green sheet obtained by using the ceramic slurry according to claim 18. Hydroxyl group-containing polymer and the following compound (X)

(In the formula, n is an integer of 1 to 20. The carbon number of R ⁴ is 250 or less. R ⁴ is an aryl group which may have a substituent or an alkyl group which may have a substituent. , An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent It may be an amino group .)
And react with the following group (XI)

(In the formula, n and R ⁴ are the same as those in the compound (X).)
A method for modifying a hydroxyl group-containing polymer to form a polymer.

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