JP7042817B2 - Side chain amino group-containing vinyl alcohol polymer - Google Patents

Description

The present invention relates to a novel modified vinyl alcohol-based polymer having an amino group in the side chain and a method for producing the modified vinyl alcohol-based polymer.

Vinyl alcohol-based polymers have excellent interfacial properties and strength properties as one of the few crystalline water-soluble polymers, and are therefore used in various applications such as raw materials for films and fibers. In many applications, vinyl alcohol-based polymers are required to be easily dissolved in water and have excellent handleability, but after reacting with a cross-linking agent, they exhibit high water resistance, contrary to water solubility. Is required.

As a method for improving the reactivity of the vinyl alcohol-based polymer with the cross-linking agent, a method of introducing a functional group into the vinyl alcohol-based polymer can be considered. Examples of the modified vinyl alcohol-based polymer into which such a functional group is introduced include a vinyl alcohol-based polymer having an amino group.

Conventionally, as a vinyl alcohol-based polymer having an amino group, a vinyl alcohol-vinyl amine copolymer obtained by copolymerizing and hydrolyzing vinyl acetate and vinyl formamide is known. However, since the amino group is directly bonded to the main chain of the copolymer, this copolymer has a problem that the function of the amino group is not sufficiently exhibited due to the steric hindrance of the main chain. In addition, the amide group hydrolysis step requires stricter conditions than the vinyl ester saponification step in the production of a normal vinyl alcohol-based polymer, so that there is a problem that the hue deteriorates.

Patent Document 1 proposes a method of introducing an amino group at a position away from the main chain in order to make the reactivity of the amino group function effectively. However, the side chain amino group-containing vinyl alcohol-based polymer described in Patent Document 1 requires a deprotection step of an oxazolidinone group in the manufacturing process, and deterioration of the hue is unavoidable due to the step. Therefore, the fields to which the side chain amino group-containing vinyl alcohol polymer can be applied are limited.

Further, Patent Document 2 proposes a vinyl alcohol-based polymer having an amino group bonded to a phenyl group, but since a compound containing sulfur is used in the manufacturing process, there is a problem of odor and sulfur oxides. It had manufacturing problems such as the need for a removal process.

Japanese Unexamined Patent Publication No. 2013-53267 Japanese Unexamined Patent Publication No. 11-49913

The present invention has been made to solve the above problems, and to obtain a molded product such as a film having a good hue, excellent reactivity with a cross-linking agent, and excellent water resistance by reaction with a cross-linking agent. It is an object of the present invention to provide a side chain amino group-containing vinyl alcohol-based polymer that can be obtained.

As a result of diligent studies to solve the above problems, the present inventors have a good hue by introducing a specific structure containing an amino group into the side chain of the vinyl alcohol polymer, and the cross-linking agent can be used. The present invention has been completed by finding that a vinyl alcohol-based polymer containing a side chain amino group having excellent reactivity can be obtained.

［式（１）中、Ｘは、置換基を有していてもよい２価の脂肪族炭化水素基、置換基を有していてもよい２価の脂環式炭化水素基、置換基を有していてもよい２価の芳香族炭化水素基、またはそれらの基がアミド結合、エステル結合およびエーテル結合からなる群から選択される少なくとも１種の結合を介して２つ以上結合された基を表す。Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい脂環式炭化水素基、置換基を有していてもよい芳香族炭化水素基、またはＸと環を形成した構造を表し、Ｒ^２は、水素原子、メチル基、またはＸと環を形成した構造を表す。］
［２］ＡＳＴＭ Ｄ１９２５にしたがって測定されるイエローインデックス（ＹＩ）が５０以下である、［１］に記載の側鎖アミノ基含有ビニルアルコール系重合体；
［３］Ｘ、Ｒ^１およびＲ^２の合計炭素数が１５以下である、［１］または［２］に記載の側鎖アミノ基含有ビニルアルコール系重合体；
［４］Ｒ^１が水素原子である、［１］～［３］のいずれかに記載の側鎖アミノ基含有ビニルアルコール系重合体；
［５］Ｘが置換基を有していてもよい２価の脂肪族炭化水素基であるか、またはＸとＲ^２が環構造を形成している、［１］～［４］のいずれかに記載の側鎖アミノ基含有ビニルアルコール系重合体；
［６］Ｘが置換基を有していてもよい２価の脂肪族炭化水素基である、［５］に記載の側鎖アミノ基含有ビニルアルコール系重合体；
［７］Ｒ^２がメチル基である、［１］～［６］のいずれかに記載の側鎖アミノ基含有ビニルアルコール系重合体；
［８］［１］～［７］のいずれかに記載の側鎖アミノ基含有ビニルアルコール系重合体と耐水化剤とを含むビニルアルコール系重合体組成物；
［９］下記式（２）で表わされる構成単位を含むビニルアルコール系重合体に対し、下記式（３）で表わされるアミン化合物を付加反応させる、［１］～［７］のいずれかに記載の側鎖アミノ基含有ビニルアルコール系重合体の製造方法；

[式（２）中、Ｒ^３は、水素原子またはメチル基を表す。]

[式（３）中、Ｘ、Ｒ^１およびＲ^２は、式（１）と同義である。]
を提供することにより解決される。That is, the above problem is
[1] A side chain amino group-containing vinyl alcohol-based polymer containing 0.001 to 10 mol% of the structural units represented by the following formula (1) with respect to all the structural units;

[In the formula (1), X is a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, and a substituent. A divalent aromatic hydrocarbon group that may have, or a group in which two or more of these groups are attached via at least one bond selected from the group consisting of amide bonds, ester bonds and ether bonds. Represents. R ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and an aromatic hydrocarbon which may have a substituent. Represents a structure forming a ring with a hydrogen group or X, and R ² represents a structure forming a ring with a hydrogen atom, a methyl group, or X. ]
[2] The side chain amino group-containing vinyl alcohol-based polymer according to [1], which has a yellow index (YI) of 50 or less as measured according to ASTM D1925;
[3] The side chain amino group-containing vinyl alcohol-based polymer according to [1] or [2], wherein the total carbon number of X, R ¹ and R ² is 15 or less;
[4] The side chain amino group-containing vinyl alcohol-based polymer according to any one of [1] to [3], wherein R ¹ is a hydrogen atom;
[5] Either [1] to [4], wherein X is a divalent aliphatic hydrocarbon group which may have a substituent, or X and R ² form a ring structure. A vinyl alcohol-based polymer containing a side chain amino group according to the above;
[6] The side chain amino group-containing vinyl alcohol-based polymer according to [5], wherein X is a divalent aliphatic hydrocarbon group which may have a substituent;
[7] The side chain amino group-containing vinyl alcohol-based polymer according to any one of [1] to [6], wherein R ² is a methyl group;
[8] A vinyl alcohol polymer composition containing the side chain amino group-containing vinyl alcohol polymer according to any one of [1] to [7] and a water resistant agent;
[9] Described in any one of [1] to [7], wherein an amine compound represented by the following formula (3) is subjected to an addition reaction with a vinyl alcohol-based polymer containing a structural unit represented by the following formula (2). Method for producing a vinyl alcohol-based polymer containing a side chain amino group;

[In formula (2), R ³ represents a hydrogen atom or a methyl group. ]

[In equation (3), X, R ¹ and R ² are synonymous with equation (1). ]
Will be resolved by providing.

The side chain amino group-containing vinyl alcohol polymer of the present invention has a good hue and excellent reactivity with a cross-linking agent. Therefore, it is suitably used for various uses of vinyl alcohol-based polymers, and is particularly preferably used in applications where hue is important.

Hereinafter, the present invention will be described in detail based on the embodiments. The embodiments described below are not limited to the present invention, and various modifications can be made without impairing the gist of the present invention.

[Constituent unit represented by equation (1)]
The side chain amino group-containing vinyl alcohol polymer of the present invention contains 0.001 to 10 mol% of the structural units represented by the following formula (1) with respect to all the structural units.

［式（１）中、Ｘは、置換基を有していてもよい２価の脂肪族炭化水素基、置換基を有していてもよい２価の脂環式炭化水素基、置換基を有していてもよい２価の芳香族炭化水素基、またはそれらの基がアミド結合、エステル結合およびエーテル結合からなる群から選択される少なくとも１種の結合を介して２つ以上結合された基を表す。Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよい脂環式炭化水素基、置換基を有していてもよい芳香族炭化水素基、またはＸと環を形成した構造を表し、Ｒ^２は、水素原子、メチル基、またはＸと環を形成した構造を表す。］

[In the formula (1), X is a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, and a substituent. A divalent aromatic hydrocarbon group that may have, or a group in which two or more of these groups are attached via at least one bond selected from the group consisting of amide bonds, ester bonds and ether bonds. Represents. R ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and an aromatic hydrocarbon which may have a substituent. Represents a structure forming a ring with a hydrogen group or X, and R ² represents a structure forming a ring with a hydrogen atom, a methyl group, or X. ]

The amino group present in the repeating unit of the polymer has reactivity with various compounds such as epoxy, aldehyde, ketone, azetidine and oxazoline. Therefore, the side chain amino group-containing vinyl alcohol polymer of the present invention can be made water resistant and gel can be produced by reacting with a cross-linking agent having an amine-reactive functional group. Further, in the side chain amino group-containing vinyl alcohol polymer of the present invention, since the amino group is not directly bonded to the main chain, the steric hindrance around the amino group is small, and the reactivity of the amino group can be fully utilized. .. In addition, since the side chain amino group-containing vinyl alcohol polymer of the present invention has a good hue, it can be suitably used even in an application field where hue is particularly important.

In the formula (1), X has a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, and a substituent. A divalent aromatic hydrocarbon group which may be, or a group in which two or more of these groups are bonded via at least one bond selected from the group consisting of an amide bond, an ester bond and an ether bond. show.

Examples of the divalent aliphatic hydrocarbon group which may have a substituent include an alkylene group which may have a substituent. Examples of the divalent alicyclic hydrocarbon group which may have a substituent include a cycloalkylene group which may have a substituent. Examples of the divalent aromatic hydrocarbon group which may have a substituent include an arylene group which may have a substituent.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene group.

The alkylene group may have a substituent, and examples of such a substituent include a branched structure such as a methyl group and an ethyl group; a vinyl group, an allyl group, a methyl vinyl group, a propenyl group, a butenyl group and a pentenyl group. , Hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and other alkenyl groups; ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, phenylethynyl group and other alkynyl groups; phenyl Aryl groups such as groups, naphthyl groups, anthryl groups and phenanthryl groups; complex groups such as pyridyl group, thienyl group, frill group, pyrrolyl group, imidazolyl group, pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group and benzoimidazolyl group. Aromatic ring group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group , Cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group and other alkoxy groups; methylthio group, ethylthio group, propylthio group, butylthio group and other alkylthio groups; phenylthio group, naphthylthio group and the like. Arylthio group; trisubstituted silyloxy group such as tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group; acyloxy group such as acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, benzoyloxy group; methoxy Carbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group An alkoxycarbonyl group such as a group and an octyloxycarbonyl group; an alkylsulfinyl group such as a methylsulfinyl group and an ethylsulfinyl group; an arylsulfinyl group such as a phenylsulfinyl group; Sulfonyl group, ethoxysulfonyl group, phenyloxysulfonyl group and other sulfonic acid ester groups; amino group; hydroxyl group Cyan group; Nitro group; Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; and the like. Among them, from the viewpoint of reactivity, a branched structure, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group and a hydroxyl group are particularly preferable, and a branched structure, an alkoxy group and a hydroxyl group are more preferable.

The amino group, which is an example of the above-mentioned substituent, 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 ⁴ (R ⁴ is an arbitrary monovalent substituent), and R ⁴ includes an alkyl group, an aryl group, an acetyl group, a benzoyl group, and the like. Examples thereof include a benzenesulfonyl group and a tert-butoxycarbonyl group. Examples of the secondary amino group include a secondary amino group in which ^R4 is an alkyl group such as a methylamino group, an ethylamino group, a propylamino group and an isopropylamino group, a phenylamino group, a naphthylamino group and the like. As described above, a secondary amino group in which ^R4 is an aryl group and the like can be mentioned. Further, the hydrogen atom of the alkyl group or aryl group in ^R4 may be further substituted with an acetyl group, a benzoyl group, a benzenesulfonyl group, a tert-butoxycarbonyl group or the like.

The tertiary amino group is a di-substituted amino group represented by -NR ⁴ R ⁵ (R ⁴ and R ⁵ are arbitrary monovalent substituents), and the R ⁵ is the same as that of R ⁴ . It can be used and R ⁴ and R ⁵ may be the same or different from each other. Specific examples of the tertiary amino group include ^R4 and ^R5 from an alkyl group and an aryl group such as a dimethylamino group, a diethylamino group, a dibutylamino group, an ethylmethylamino group, a diphenylamino group and a methylphenylamino group. Examples thereof include a tertiary amino group which is at least one selected from the group.

Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group and the like. These cycloalkylene groups may have a substituent, and as the substituent, the same substituents as those exemplified in the above description of the alkylene group can be used.

Examples of the arylene group include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a fluorenylene group and the like. These arylene groups may have a substituent, and as the substituent, the same substituents as those exemplified in the above description of the alkylene group can be used.

As X in the formula (1), from the viewpoint of reactivity, a divalent aliphatic hydrocarbon group which may have a substituent or a divalent alicyclic hydrocarbon which may have a substituent may be used. It is preferably a group, and more preferably a divalent aliphatic hydrocarbon group which may have a substituent. Among the aliphatic hydrocarbon groups which may have a substituent, a divalent alkylene group which may have a substituent is preferably used as X, and the alkylene group has 1 to 1 to carbon atoms. 15 is preferable, and 1 to 10 is more preferable. Among the alkylene groups, at least selected from the group consisting of a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, an isopentylene group and a neopentylene group. One is more preferably used. Among the alicyclic hydrocarbon groups which may have a substituent, the cycloalkylene group which may have a substituent is preferably used as X. Among the cycloalkylene groups, at least one selected from the group consisting of a cyclopropylene group, a cyclobutylene group and a cyclopentylene group is more preferably used.

In the formula (1), R ¹ has a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and a substituent. Represents a optionally aromatic hydrocarbon group, or a structure that forms a ring with X.

The aliphatic hydrocarbon group which may have a substituent may have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Examples include an alkynyl group. Examples of the alicyclic hydrocarbon group which may have a substituent include a cycloalkyl group which may have a substituent. Examples of the aromatic hydrocarbon group which may have a substituent include an aryl group which may have a substituent and an arylalkyl group which may have a substituent.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group and a neopentyl group. Examples thereof include a tert-pentyl group, an n-hexyl group, an isohexyl group, a 2-ethylhexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and an n-decyl group. These alkyl groups may have a substituent, and as the substituent, the same substituents as those exemplified in the description of the alkylene group can be used, and an alkyl group such as a methyl group or an ethyl group can be used. As a branched structure, one having an alkoxy group and one having a hydroxyl group are preferably adopted.

Examples of the alkenyl group include a vinyl group, an allyl group, a methyl vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like. These alkenyl groups may have a substituent, and as such a substituent, the same substituents as those exemplified in the description of the alkylene group can be used.

Examples of the alkynyl group include an ethynyl group, a propynyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, a phenylethynyl group and the like. These alkynyl groups may have a substituent, and as such a substituent, the same substituents as those exemplified in the description of the alkylene group can be used.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptanyl group, a cyclooctanyl group, a cyclononanyl group, a cyclodecanyl group, a cycloundecanyl group, a cyclododecanyl group and the like. These cycloalkyl groups may have a substituent, and as such a substituent, the same substituents as those exemplified in the description of the alkylene group can be used.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like. These aryl groups may have a substituent, and as such a substituent, the same substituents as those exemplified in the description of the alkylene group, the above-mentioned alkyl group, alkenyl group, alkynyl group and the like are used. be able to.

Examples of the arylalkyl group include a benzyl group, a 4-methoxybenzyl group, a phenethyl group, a diphenylmethyl group and the like. These arylalkyl groups may have a substituent, and as such a substituent, the same substituents as those exemplified in the description of the alkylene group can be used.

The ^R1 in the formula (1) is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent from the viewpoint of reactivity. It is preferably present, more preferably an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent, and even more preferably a hydrogen atom. Among the aliphatic hydrocarbon groups which may have a substituent, an alkyl group which may have a substituent is preferably used as ^R1 , and the alkyl group has 1 to 15 carbon atoms. Preferably, 1 to 10 is more preferable, and 1 to 5 is even more preferable. Among the alkyl groups, at least one selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group. Species are more preferably used, and at least one selected from the group consisting of methyl and ethyl groups is particularly preferably used. Among the alicyclic hydrocarbon groups which may have a substituent, the cycloalkyl group which may have a substituent is preferably used as ^R1 . Among the cycloalkyl groups, at least one selected from the group consisting of a cyclopropyl group, a cyclobutyl group and a cyclopentyl group is more preferably used.

From the viewpoint of reactivity, R ² in the formula (1) is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

In the formula (1), X and R ¹ or X and R ² may form a ring structure. For example, X and R ¹ or X and R ² may form a piperidine ring, X and R ¹ or X and R ² may form a pyrrolidine ring, X and R ¹ or X and R. ² may form a piperazine ring. Among them, it is preferable that X and R ² form a ring structure, X and R ² form a piperidine ring, X and R ² form a pyrrolidine ring, and X and R ² form a piperazine ring. The formed one is more preferable.

Further, from the viewpoint of water solubility, the total carbon number of X, ^R1 and ^R2 is important, and the total carbon number is preferably 15 or less, more preferably 13 or less, and 11 or less. Is even more preferable. When the total number of carbon atoms is 15 or less, it is possible to suppress thickening or hydrogel formation due to hydrophobic interaction between side chains in an aqueous solution, which tends to facilitate molding in processes such as coating. It is in. The total number of carbon atoms is preferably 2 or more.

The content of the structural unit represented by the formula (1) in the side chain amino group-containing vinyl alcohol polymer of the present invention is 0.001 to 10 mol% with the total structural unit as 100 mol%. When the content of the structural unit represented by the formula (1) is in the range of 0.001 to 10 mol%, the water resistance of the film crosslinked by the crosslinking agent is exhibited. If the content of the structural unit represented by the formula (1) is less than 0.001 mol%, the effect of denaturing the vinyl alcohol polymer by the structural unit represented by the formula (1) becomes insufficient. When the content of the structural unit represented by the formula (1) exceeds 10 mol%, the crystallinity of the vinyl alcohol-based polymer is lowered, the water resistance of the crosslinked film is lowered, and the crosslinked film is made hydrophobic. The water solubility also deteriorates. The content of the structural unit represented by the formula (1) is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and particularly preferably 0.3 mol% or more. The content of the structural unit represented by the above formula (1) is preferably 7 mol% or less, more preferably 5 mol% or less. The side chain amino group-containing vinyl alcohol polymer of the present invention may have one or more structural units represented by the formula (1). When having two or more kinds of the constituent units, it is important that the total content of these two or more kinds of constituent units is in the above range. In the present invention, the structural unit in the polymer means a repeating unit that constitutes the polymer. For example, the following vinyl alcohol unit and the following vinyl ester unit are also constituent units.

[Constituent unit represented by equation (2)]
The side chain amino group-containing vinyl alcohol polymer of the present invention preferably contains 0 to 10 mol% of the structural units represented by the following formula (2) with respect to all the structural units.

[式（２）中、Ｒ^３は、水素原子またはメチル基を表す。]

[In formula (2), R ³ represents a hydrogen atom or a methyl group. ]

In formula (2), R ³ represents a hydrogen atom or a methyl group. From the viewpoint of facilitating the synthesis of a vinyl alcohol-based polymer into which the structural unit represented by the formula (2) has been introduced [hereinafter, may be abbreviated as "lactone ring-containing vinyl alcohol-based polymer"] ^, R3 is It is preferably a hydrogen atom.

The content of the structural unit represented by the formula (2) in the side chain amino group-containing vinyl alcohol polymer of the present invention is preferably 0 to 10 mol% with the total structural unit as 100 mol%. When the content of the structural unit represented by the formula (2) is 10 mol% or less, the crystallinity of the vinyl alcohol polymer tends to be difficult to decrease, and the water resistance of the crosslinked film tends to be difficult to decrease, which is 8 mol. % Or less, more preferably 7 mol% or less. On the other hand, the content of the structural unit represented by the formula (2) is more preferably 0.005 mol% or more, further preferably 0.01 mol% or more, and 0.1 mol% or more. It is particularly preferable to have. The side chain amino group-containing vinyl alcohol polymer of the present invention may have one or two structural units represented by the formula (2). When having two kinds of the structural units, it is preferable that the total content of these structural units is in the above range.

[Vinyl alcohol unit]
The content of the vinyl alcohol unit in the side chain amino group-containing vinyl alcohol polymer of the present invention is not particularly limited, but from the viewpoint of solubility in water, the total constituent units in the polymer are set to 100 mol%, preferably 50. It is mol% or more, more preferably 70 mol% or more, still more preferably 75 mol% or more, and particularly preferably 80 mol% or more. The content of the vinyl alcohol unit is preferably 99.95 mol% or less, more preferably 99.90 mol% or less, with 100 mol% of all the constituent units in the polymer.

The vinyl alcohol unit can be derived from the vinyl ester unit by hydrolysis, alcohol decomposition, or the like. Therefore, the vinyl ester unit may remain in the vinyl alcohol-based polymer depending on the conditions for converting the vinyl ester unit to the vinyl alcohol unit. Therefore, the side chain amino group-containing vinyl alcohol-based polymer of the present invention may contain the vinyl ester unit derived from the above.

Examples of the vinyl ester of the vinyl ester unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl caproate, vinyl caprylate, vinyl laurate, and palmitin. Examples thereof include vinyl acetate, vinyl stearate, vinyl oleate, vinyl benzoate and the like, and among these, vinyl acetate is preferable from an industrial point of view.

The side chain amino group-containing vinyl alcohol polymer of the present invention is preferably represented by the following formula (A).

[式（Ａ）中、Ｘ、Ｒ^１およびＲ^２は式（１）と同義であり、Ｒ^３は式（２）と同義であり、ａ、ｂ、ｃ及びｄは、全構成単位に対する各構成単位の含有率を表し、ａは５０～９９．９５モル％であり、ｂは０．０５～３０モル％であり、ｃは０～１０モル％であり、ｄは０．００１～１０モル％である。]

[In the formula (A), X, R ¹ and R ² are synonymous with the formula (1), R ³ is synonymous with the formula (2), and a, b, c and d are each for all the constituent units. Representing the content of constituent units, a is 50 to 99.95 mol%, b is 0.05 to 30 mol%, c is 0 to 10 mol%, and d is 0.001 to 10 mol%. %. ]

In the above formula (A), a is preferably 50 to 99.95 mol%, with 100 mol% of all the constituent units in the polymer. a is more preferably 70 mol% or more, further preferably 75 mol% or more, and particularly preferably 80 mol% or more. On the other hand, a is more preferably 99.90 mol% or less.

In the above formula (A), b is preferably 0.05 to 30 mol%, with 100 mol% of all the constituent units in the polymer. b is more preferably 0.1 mol% or more, further preferably 0.2 mol% or more, and particularly preferably 0.5 mol% or more. On the other hand, b is more preferably 25 mol% or less, still more preferably 20 mol% or less.

In the above formula (A), c is preferably 0 to 10 mol%, with 100 mol% of all the constituent units in the polymer. c is more preferably 0.005 mol% or more, further preferably 0.01 mol% or more, and particularly preferably 0.1 mol% or more. On the other hand, c is more preferably 8 mol% or less, still more preferably 7 mol% or less.

In the above formula (A), d is 0.001 to 10 mol%, where 100 mol% is the total structural unit in the polymer. When d is in the range of 0.001 to 10 mol%, the water resistance of the film crosslinked by the cross-linking agent is developed. d is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more. On the other hand, d is preferably 7 mol% or less, more preferably 5 mol% or less, with the total constituent units in the polymer being 100 mol% or less.

The side chain amino group-containing vinyl alcohol polymer of the present invention is a structural unit represented by the formula (1), a structural unit represented by the formula (2), a vinyl alcohol unit and a vinyl alcohol unit as long as the effect of the present invention can be obtained. It can further have a structural unit other than the vinyl ester unit. The structural unit is, for example, an unsaturated monomer copolymerizable with vinyl ester and convertible to the structural unit represented by the formula (1), or an ethylenically unsaturated monomer copolymerizable with vinyl ester. It is a structural unit derived from a polymer or the like. The ethylenically unsaturated monomer is, for example, α-olefins such as ethylene, propylene, n-butyl, isobutylene, 1-hexyl; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate. , Acrylic acid esters such as i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof. Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacryl Methacrylate esters such as octadecyl acid; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamide propanesulfonic acid and its salts, acrylamidepropyldimethylamine and its salts (eg 4). Grade salt); methacrylamide, N-methylmethacrylate, N-ethylmethacrylate, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts (eg, quaternary salts); methylvinyl ether, ethylvinyl ether, n. -Vinyl ethers such as 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, 2,3-diacetoxy-1-vinyloxypropane; acrylonitrile, methacrylo Vinyl cyanide such as nitriles; 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; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate.

Arrangement order of the structural unit represented by the formula (1), the structural unit represented by the formula (2), the vinyl alcohol unit, and any other structural unit in the side chain amino group-containing vinyl alcohol polymer of the present invention. Is not particularly limited, and the side chain amino group-containing vinyl alcohol-based polymer of the present invention may be any of a random copolymer, a block copolymer, an alternating copolymer and the like.

The viscosity average degree of polymerization of the side chain amino group-containing vinyl alcohol polymer of the present invention measured in accordance with JIS K6726 is not particularly limited, and is preferably 100 to 5,000, more preferably 200 to 4,000. Is. When the viscosity average degree of polymerization is 100 or more, the mechanical strength of the film tends to be excellent when it is made into a film. When the viscosity average degree of polymerization is 5,000 or less, the industrial production of the side chain amino group-containing vinyl alcohol-based polymer tends to be easy.

[Production method]
The method for producing the side chain amino group-containing vinyl alcohol polymer of the present invention is not particularly limited. For example, a method of hydrolyzing or hydrolyzing a vinyl ester after copolymerizing an unsaturated monomer having a structural unit represented by the formula (1) with a vinyl ester, or a structural unit represented by the formula (1). After copolymerizing the convertible unsaturated monomer and the vinyl ester, the vinyl ester is hydrolyzed or alcohol-decomposed, and the structural unit that can be converted into the structural unit represented by the formula (1) is represented by the formula (1). A method of converting to the indicated structural unit, a method of introducing a reaction point into a vinyl alcohol-based polymer, and a method of introducing the structural unit represented by the formula (1) by a post-reaction using the reaction point as a base point are used. Above all, from the viewpoint of ease of production, a method using a post-reaction using the reaction point introduced into the vinyl alcohol polymer as a base point is preferable. Examples of the method include a method in which an amine compound represented by the following formula (3) is subjected to a dehydration condensation reaction with a vinyl alcohol polymer introduced with a carboxylic acid. Further, a vinyl alcohol-based polymer introduced with a carboxylic acid ester, a vinyl alcohol-based polymer introduced with a carboxylic acid halide, a vinyl alcohol-based polymer introduced with a carboxylic acid anhydride, a vinyl alcohol-based polymer introduced with a lactone ring, etc. , A method of reacting a vinyl alcohol-based polymer having a functional group reactive with an amine compound with an amine compound represented by the following formula (3) can be mentioned. In particular, a method of reacting a vinyl alcohol-based polymer having a structural unit represented by the following formula (2) with an amine compound represented by the following formula (3) has a relatively high reaction efficiency, and is therefore more preferable. be.

[式（２）中、Ｒ^３は、水素原子またはメチル基を表す。]

[In formula (2), R ³ represents a hydrogen atom or a methyl group. ]

[式（３）中、Ｘ、Ｒ^１およびＲ^２は、式（１）と同義である。]

[In equation (3), X, R ¹ and R ² are synonymous with equation (1). ]

The amine compound represented by the formula (3) is not particularly limited. For example, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1,2-diamino-2-methylpropane, 2-methyl-1,3- Propanediamine, 1,2-diaminobutane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 1 , 7-Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1-methyl-1,8-diaminooctane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane , Bis (3-aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-dimethylpropane, 2,2'-oxybis (ethylamine) ), 1,3-Diamino-2-propanol, α, ω-bis (3-aminopropyl) polyethylene glycol ether, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1, Two or more 1s in molecules such as 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4- (2-aminoethyl) cyclohexylamine, isophoronediamine, 1,4-phenylenediamine, etc. Compounds with secondary amines and salts thereof; N-methylethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, bis (hexamethylene) triamine, 3-methylaminopropylamine, iminobispropylamine, N , N'-bis (3-aminopropyl) -1,3-propylene diamine, N, N'-bis (3-aminopropyl) -1,4-butylenediamine, 2-aminomethylpiperidin, 4-aminomethylpiperidine , Compounds having one or more primary amines and one or more secondary amines in the molecule, such as 2-aminomethylpiperazin, and salts thereof; one in the molecule, such as N- (2-aminoethyl) piperazine. Compounds having the above primary amines, one or more secondary amines, and one or more tertiary amines and salts thereof; N, N'-dimethylethylenediamine, N, N'-dimethyl-1,3-propanediamine. , 2-Piperazine carboxylic acid, N, N'-dimethyl-1,6-diaminohexa Examples thereof include compounds having two or more secondary amines in the molecule, such as 2-methylpiperazine, 2,6-dimethylpiperazine, 2,5-dimethylpiperazine, and homopiperazine, and salts thereof. Among them, from the viewpoint of industrial availability and reactivity, and the reactivity of the obtained side chain amino group-containing vinyl alcohol-based polymer, a compound having two or more primary amines in the molecule, one in the molecule. From the group consisting of the above compounds having a primary amine and one or more secondary amines, and compounds having one or more primary amines, one or more secondary amines and one or more tertiary amines in the molecule. At least one selected is preferably selected from the group consisting of compounds having two or more primary amines in the molecule, and compounds having one or more primary amines and one or more secondary amines in the molecule. At least one is more preferable.

Among the amine compounds represented by the formula (3), ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine and 1,2-diamino-2-methyl Propane, 2-methyl-1,3-propanediamine, 1,2-diaminobutane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2- Methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1-methyl-1,8-diaminooctane, 1,10-diaminodecane, 1,11 -Diaminoundecane, 1,12-diaminododecane, bis (3-aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-dimethyl Propane, 2,2'-oxybis (ethylamine), 1,3-diamino-2-propanol, α, ω-bis (3-aminopropyl) polyethylene glycol ether, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4- (2-aminoethyl) cyclohexylamine, isophoronedimine, 1,4-phenylenediamine, N-methylethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, bis (hexamethylene) triamine, 3-methylaminopropylamine, iminobispropylamine, N, N'-bis (3-aminopropyl) )-1,3-propylene diamine, N, N'-bis (3-aminopropyl) -1,4-butylenediamine, 2-aminomethylpiperidin, 4-aminomethylpiperidin, 2-aminomethylpiperazine are preferred. , 2-Diaminopropane, 1,2-diaminobutane, 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, 1-methyl-1,8-diaminooctane, N-methylethylenediamine, 3-methyl Aminopropylamine, 2-aminomethylpiperidin, 4-aminomethylpiperidin, 2-aminomethylpiperazine are more preferred, 1,2-diaminopropane, 1,2-diaminobutane, 1,3-diaminopentane, 2-methyl- 1,5 -Diaminopentane, 1-methyl-1,8-diaminooctane, N-methylethylenediamine, 3-methylaminopropylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 2-aminomethylpiperazine are more preferred.

The method for producing the lactone ring-containing vinyl alcohol-based polymer is not particularly limited, but for example, a vinyl ester and a structural unit represented by the formula (2) [hereinafter, may be simply abbreviated as “lactone ring unit”] are used. Examples thereof include a method including a step of copolymerizing with an unsaturated monomer having a lactone, and a method including a step of copolymerizing a vinyl ester with an unsaturated monomer that can be converted into a lactone ring unit. In particular, from the viewpoint of ease of production, a method including a step of copolymerizing a vinyl ester and an unsaturated monomer that can be converted into a lactone ring unit is preferable. More specifically, the vinyl ester is copolymerized with an unsaturated monomer that can be converted into a lactone ring unit, and the vinyl ester unit of the obtained copolymer is converted into a vinyl alcohol unit, while the lactone ring is converted. Examples thereof include a method of converting a unit derived from an unsaturated monomer that can be converted into a unit into a lactone ring unit. In particular, the vinyl ester and the carboxylic acid derivative having an unsaturated double bond are copolymerized, and the ester bond of the vinyl ester unit of the obtained copolymer is hydrolyzed or condensed with alcohol, and the carboxylic acid derivative portion is combined with the vinyl ester. The method of condensing is simple and is preferably used.

Examples of the carboxylic acid derivative having an unsaturated double bond include a carboxylic acid having an unsaturated bond and a salt thereof, a carboxylic acid ester having an unsaturated bond, a carboxylic acid halide having an unsaturated bond, and a carboxylic acid having an unsaturated bond. An acid anhydride is preferably used, and a carboxylic acid having an unsaturated bond and a salt thereof, and a carboxylic acid ester having an unsaturated bond are more preferable. Examples of the carboxylic acid having an unsaturated bond and its salt, and the carboxylic acid ester having an unsaturated bond include methacrylic acid and its salt; methylacrylic acid, ethylacrylic acid, n-propyl acrylate, i-propyl acrylate, and the like. Acrylic acid esters such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, methacrylic acid. Methacrylic acid esters such as ethyl, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate. Class: At least one selected from the group consisting of unsaturated dicarboxylic acids such as methacrylic acid, methacrylic acid, and methacrylic acid and salts thereof or esters thereof is preferable.

The copolymerization method in the step of copolymerizing a vinyl ester and an unsaturated monomer convertible into a lactone ring unit [hereinafter, may be simply abbreviated as "copolymerization step"] is not particularly limited, and is a bulk polymerization method. , A conventionally known method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, and a dispersion polymerization method can be adopted. From an industrial point of view, preferred polymerization methods are a solution polymerization method, an emulsion polymerization method and a dispersion polymerization method. In the polymerization operation, any of a batch method, a semi-batch method and a continuous method can be adopted.

For example, in the solution polymerization method, alcohols such as methanol, ethanol and isopanol; hydrocarbons such as hexane and heptane; water and the like are preferably used as the solvent, and among these, alcohol is preferable, and methanol and ethanol are more preferable. , Methanol is more preferred. The amount of the solvent used is not particularly limited, but from the viewpoint of productivity and the like, the amount of the solvent is preferably 1000 parts by mass or less, and more preferably 200 parts by mass or less with respect to 100 parts by mass of the vinyl ester. Further, it is preferable that the solvent is 5 parts by mass or more with respect to 100 parts by mass of the vinyl ester.

Examples of the polymerization initiator in the copolymerization step include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy). Azo-based polymerization initiators such as -2,4-dimethylvaleronitrile); peroxide-based polymerization initiators such as benzoyl peroxide and n-propylperoxycarbonate, among these, azo-based polymerization initiators. , And more preferably 2,2'-azobisisobutyronitrile.

The amount of the polymerization initiator used is not particularly limited, but is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 10 parts by mass, based on 100 parts by mass of the total of the vinyl ester and the unsaturated monomer that can be converted into the lactone ring unit. Is 0.01 to 1 part by mass.

In the copolymerization step, other monomers may be copolymerized together with the unsaturated monomer that can be converted into a vinyl ester and a lactone ring unit. Examples of such other monomers include those described above as monomers giving other structural units that can be contained in the vinyl alcohol unit.

The amount of the unsaturated monomer that can be converted into the lactone ring unit may be appropriately determined according to the content of the target lactone ring unit, the type of the unsaturated monomer that can be converted into the lactone ring unit, and the like. However, based on the total number of moles of all the monomers used in the copolymerization step, the unsaturated monomer that can be converted into a lactone ring unit is preferably 0.1 to 10 mol%, preferably 0.5. More preferably, it is ~ 7 mol%.

In the copolymerization step, a chain transfer agent may coexist for the purpose of adjusting the degree of polymerization of the obtained lactone ring-containing vinyl alcohol-based polymer. Examples of the chain transfer agent include aldehydes such as acetaldehyde, propionaldehyde, butyl aldehyde and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone and cyclohexanone; mercaptans such as 2-hydroxyethanethiol and dodecyl mercaptan; trichloroethylene and perchloroethylene and the like. Examples thereof include halogenated hydrocarbons of the above, and among these, aldehydes and ketones are preferably used. The amount of the chain transfer agent used can be appropriately determined depending on the chain transfer constant of the chain transfer agent used and the degree of polymerization of the target lactone ring-containing vinyl alcohol-based polymer, but is generally converted into a vinyl ester and a lactone ring unit. It is preferably 0.1 to 10% by mass based on the total mass of possible unsaturated monomers.

Further, in the copolymerization step, even if the end of the lactone ring-containing vinyl alcohol polymer and the end of the side chain amino group-containing vinyl alcohol polymer are modified by the presence of thiols such as thiol acetic acid and mercaptopropionic acid. good.

The polymerization temperature in the copolymerization step may be appropriately determined according to the type of the polymerization initiator and the characteristics of the target copolymer, and is preferably 0 to 100 ° C, more preferably 40 to 80 ° C.

The atmosphere in the copolymerization step is preferably an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.

After completion of the reaction, the polymer can be recovered according to a known method. For example, a fractional precipitation method can be adopted, and acetone, hexane, heptane, or the like can be used as the precipitation agent.

The vinyl ester unit of the copolymer of the vinyl ester and the unsaturated monomer that can be converted into the lactone ring unit can be converted into the vinyl alcohol unit by hydrolysis or condensed alcohol decomposition, and can also be converted into the lactone ring unit. A vinyl alcohol-based polymer containing a lactone ring can be obtained by condensing with the carboxylic acid derivative portion of the saturated monomer. Specifically, for example, by adopting a so-called saponification step in which the copolymer is brought into contact with an acidic substance or an alkaline substance, and a subsequent drying step, a part or all of the introduced carboxylic acid derivative portion is adjacent to each other. By condensing with the hydroxyl group, it is converted into a lactone ring. The saponification step and the drying step can be carried out according to a known method for producing polyvinyl alcohol.

The saponification step can be carried out, for example, by dissolving the copolymer in a solvent containing water and / or alcohol and adding an acidic or alkaline substance. At this time, in order to improve the solubility of the copolymer and the acidic substance or the alkaline substance, a solvent such as tetrahydrofuran, dioxane, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene or acetone may be used in combination. In particular, from the viewpoint of ease of production of the lactone ring-containing vinyl alcohol polymer, it is preferable to adopt a saponification step of adding an alkaline substance. When water and / or alcohol is used as the solvent in the above-mentioned copolymerization step, the reaction solution in the copolymerization step can be used as it is as the solution in the saponification step.

Examples of the alcohol used for dissolving the copolymer include methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol and the like. Among the alcohols, alcohols having 1 to 4 carbon atoms are preferable, and methanol is more preferable.

The amount of the solvent used (total amount of the solvent used) is not particularly limited, but is preferably 1 to 50 times by mass, more preferably 2 to 10 times by mass with respect to the mass of the copolymer.

Examples of the acidic substance that can be used in the saponification step include p-toluenesulfonic acid. Examples of the alkaline substance that can be used in the saponification step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkali metal alkoxides such as sodium methylate. The amount of the acidic substance or alkaline substance used is preferably 0.0001 to 2 mol, preferably 0.001 to 1.2 mol, with respect to 1 mol of the vinyl ester unit of the copolymer. Is more preferable.

The reaction temperature in the saponification step is preferably 0 to 180 ° C, more preferably 20 to 80 ° C. The reaction time is preferably 0.01 to 20 hours, more preferably 0.1 to 3 hours, although it depends on the reaction rate.

Although it depends on the type of solvent used, the saponified product often precipitates in the form of particles as the reaction proceeds. After completion of the reaction, the precipitated saponified product can be recovered by a known method. For example, the lactone ring-containing vinyl alcohol-based polymer can be recovered by filtering the precipitated particles, washing them with an alcohol such as methanol, and then drying them.

The method for reacting the lactone ring-containing vinyl alcohol polymer with the amine compound represented by the formula (3) is not particularly limited, and can be selected depending on the required characteristics of the target side chain amino group-containing vinyl alcohol polymer. For example, a method in which an amine compound represented by the formula (3) is mixed and reacted with a melted lactone ring-containing vinyl alcohol-based polymer; the amine compound represented by the formula (3) is dissolved and contains a lactone ring. A method of reacting in a slurry state in a solvent in which the vinyl alcohol-based polymer is insoluble; a method of impregnating a lactone ring-containing vinyl alcohol-based polymer with an amine compound represented by the formula (3) and reacting in a solid state; A method in which a gasified amine compound is brought into contact with a ring-containing vinyl alcohol-based polymer and reacted; a lactone ring-containing vinyl alcohol-based polymer, in a solution state in which all the amine compounds represented by the formula (3) are uniformly dissolved. A method for reacting; and the like can be mentioned, and a suitable method can be appropriately adopted in consideration of the reactivity and the isolation property of the vinyl alcohol-based polymer containing a side chain amino group.

When the reaction between the lactone ring-containing vinyl alcohol polymer and the amine compound represented by the formula (3) is carried out in a slurry state or a uniform solution state, the concentration of the lactone ring-containing vinyl alcohol polymer during the reaction is not particularly limited. 1, 1% by mass to 50% by mass is preferable, 2% by mass to 40% by mass is more preferable, and 3% by mass to 30% by mass is further preferable. When it is 1% by mass or more, it is easy to suppress a decrease in the reaction rate due to a dilute concentration of the lactone ring-containing vinyl alcohol polymer. When it is 50% by mass or less, there is a tendency that poor stirring can be suppressed.

The solvent used for the reaction between the lactone ring-containing vinyl alcohol-based polymer and the amine compound represented by the formula (3) is not particularly limited, but water; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, Alcohols such as sec-butanol, tert-butanol; aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane, cyclohexane; aromatic hydrocarbons such as benzene and toluene; chloroform, chlorobenzene, dichlorobenzene Fat or aromatic halides such as; nitriles such as acetonitrile, benzonitrile; ethers such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, 1,4-dioxane; acetone, methyl isopropyl ketone, methyl Ketones such as isobutylketone; esters such as ethyl acetate and ethyl propionate; N-alkyllactams such as N-methyl-2-pyrrolidone; N, N, N-dimethylformamide, N, N-dimethylacetamide and the like, Examples thereof include N-dialkylamides; sulfoxides such as dimethylsulfoxide; and sulfolanes such as sulfolanes. Further, the amine compound represented by the formula (3) may be used as a substrate and a solvent. Of these, alcohols, aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, ethers, ketones, and amine compounds represented by the formula (3) are particularly preferable from the viewpoint of reactivity. Two or more kinds of solvents may be used in combination. For example, in a slurry reaction, a solvent in which the lactone ring-containing vinyl alcohol polymer does not dissolve and a lactone ring-containing vinyl alcohol-based weight such as N, N-dialkyllactams and sulfoxides are used. It may be used in combination with a solvent that swells the coalescence.

The temperature of the reaction between the lactone ring-containing vinyl alcohol polymer and the amine compound represented by the formula (3) is not particularly limited, but from the viewpoint of reactivity, 20 to 150 ° C. is preferable, and 30 to 140 ° C. is more preferable. It is preferable, 40 to 130 ° C. is more preferable, and 50 to 120 ° C. is most preferable. Further, the reaction system may be pressurized or depressurized as needed.

The method for taking out the side chain amino group-containing vinyl alcohol-based polymer after the reaction between the lactone ring-containing vinyl alcohol-based polymer and the amine compound represented by the formula (3) is not particularly limited, and can be carried out by a known method. For example, in the case of a homogeneous reaction in which a lactone ring-containing vinyl alcohol polymer is dissolved in a solvent and reacted, a lactone ring-containing vinyl alcohol polymer and a side chain amino group-containing vinyl alcohol polymer can be used as the reaction solution. It may be taken out by adding it to an insoluble solvent (poor solvent) and precipitating it. At this time, the reaction solution and the poor solvent may be mixed and the precipitated resin may be cut at the same time using a mixer to form a slurry, or the reaction solution may be taken out in a fibrous form by a wet spinning device or a dry wet spinning device. Alternatively, a method of micronization by a spray-drying method, or a method of extruding from a court method or a die to form a film can also be adopted. The removed resin may be washed with an organic solvent or water that does not dissolve the resin, or may be dried with a blower dryer or the like. When the reaction is carried out in a slurry state or a solid state in which the lactone ring-containing vinyl alcohol polymer does not dissolve, the resin may be separated by solid-liquid separation by filtration, centrifugal deflation, drying or the like after the reaction. The separated resin may be washed with an organic solvent or water that does not dissolve the resin, or may be dried with a blower dryer or the like. When a gasified amine compound represented by the formula (3) is reacted with a lactone ring-containing vinyl alcohol polymer, the amine compound is replaced with air, nitrogen, argon or other gas after the reaction. It may be removed.

[Vinyl alcohol polymer containing side chain amino group]
Since the side chain amino group-containing vinyl alcohol-based polymer obtained in the present invention is used for applications such as fibers and films in which appearance is important, it is preferable that the hue of the polymer is good. From this point of view, the yellow index (YI) of the side chain amino group-containing vinyl alcohol polymer obtained in the present invention is preferably 50 or less. The yellow index (YI) is measured according to ASTM D1925. For example, in a side chain amino group-containing vinyl alcohol-based polymer, by reducing the content of carbon-carbon double bonds in the main chain, the YI is small and the side chain amino group-containing vinyl alcohol-based polymer has an excellent hue. You can get a coalescence. YI is more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less. YI is usually 3 or more. Here, YI uses a spectrocolorimeter (D65 light source, CM-A120 white calibration plate, normal reflection measurement SCE) to prevent the powder of the vinyl alcohol polymer containing a side chain amino group from being pressed down. It is obtained by measuring the sample spread on the chalet. Specifically, it is a value measured according to the method described in the example.

The side chain amino group-containing vinyl alcohol-based polymer obtained in the present invention may further have another functional group introduced as long as the amino group is introduced into the side chain. For example, an amine compound represented by the formula (3) is added to a lactone ring-containing vinyl alcohol-based polymer to introduce a specific structure containing an amino group in the side chain, and the polymer has an acid, an alkali, or another functional group. Further, various other functional groups can be introduced by reacting the amine compound with the vinyl alcohol-based polymer containing a lactone ring. For example, introduction of a carboxylic acid group by reaction with an acid compound such as hydrochloric acid or carbonic acid; introduction of a carboxylic acid base by reaction with an alkali metal compound such as sodium hydroxide or potassium hydroxide; introduction of an amide group by reaction with ammonia. Introduction of alkyl group by reaction with alkylamine compound; Introduction of alkenyl group by reaction with alkenylamine compound; Introduction of alkynyl group by reaction with alkynylamine compound; Introduction of aryl group by reaction with arylamine compound; Introduction of hydroxyl group by reaction with amine compound having silyl group; Introduction of silyl group by reaction with amine compound having silyl group; Introduction of frill group by reaction with amine compound having frill group; With amine compound having thiol group Examples thereof include introduction of a thiol group by a reaction.

The side chain amino group-containing vinyl alcohol-based polymer obtained in the present invention utilizes its properties to form a composition alone or with other components added, according to known methods such as molding, spinning, and emulsification. It can be used in various applications in which alcohol-based polymers are used. For example, various applications of surfactants, paper coating agents, paper internalizers and paper modifiers such as pigment binders, adhesives such as wood, paper, aluminum foil and inorganic substances, non-woven binders, paints, warp glue. It can be used for agents, fiber processing agents, adhesives for hydrophobic fibers such as polyester, other various films, sheets, bottles, fibers, thickeners, flocculants, soil modifiers, hydrogels and the like.

The side chain amino group-containing vinyl alcohol-based polymer obtained in the present invention contains a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, and a coloring, depending on the application thereof, as long as the effect of the present invention is not impaired. Agents, UV absorbers, light stabilizers, antioxidants, antioxidants, flame retardants, plasticizers, other thermoplastics, lubricants, fragrances, defoamers, deodorants, bulking agents, release agents, release Additives such as a mold, a reinforcing agent, a fungicide, a preservative, and a crystallization rate retarder can be appropriately blended as needed.

[Vinyl alcohol polymer composition containing a side chain amino group-containing vinyl alcohol polymer and a water resistant agent]
Since the side chain amino group-containing vinyl alcohol polymer of the present invention has an amino group having a high degree of freedom introduced into the side chain, it is highly reactive, especially with a water resistant agent such as a cross-linking agent. .. Therefore, by blending a water resistant agent with the side chain amino group-containing vinyl alcohol polymer of the present invention, a vinyl alcohol polymer composition that gives a product having excellent water resistance can be obtained.

Therefore, a vinyl alcohol-based polymer composition containing a side-chain amino group-containing vinyl alcohol-based polymer and a water-resistant agent is a preferred embodiment of the present invention.

Examples of the water resistant agent contained in the vinyl alcohol-based polymer composition of the present invention include zirconyl nitrate, ammonium zirconium carbonate, zirconyl chloride, zirconyl acetate, zirconyl sulfate, aluminum sulfate, aluminum nitrate, titanium lactate, and titanium diisopropoxy. Acid anhydrides such as bis (triethanol aminate) and pyromellitic acid dianhydride, divinyl sulfone compounds, melamine-based resins, methylol melamine, methylolated bisphenol S, polyvalent vinyl compounds, polyvalent (meth) acrylate compounds, poly Examples thereof include valent epoxy compounds, aldehyde compounds, polyvalent isocyanate compounds, water-soluble oxidizing agents, polyamide polyamine epichlorohydrin resins and the like.

The above-mentioned polyvalent (meth) acrylate compound is not particularly limited, but for example, "NK ester" manufactured by Shin-Nakamura Chemical Co., Ltd. (701A, A-200, A-400, A-600, A-1000, A- B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, 1G, 2G, 3G, 4G, A-PG5054E, etc.) and the like.

The above-mentioned polyhydric epoxy compound is not particularly limited, but for example, "Denacol" (EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512) manufactured by Nagase ChemteX Corporation. EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-201, EX-211, EX-212, EX-252, EX-810, EX-811, EX- 850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-931, EX-721, EX-203, EX-711, EX-221, etc.), bisphenol A diglycidyl ether, bisphenol A diβ methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether , Chlorinated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, Glycidyl ether type such as epoxy urethane resin; glycidyl ether ester type such as p-oxybenzoic acid glycidyl ether ester; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid Glycidyl ester type such as diglycidyl ester and dimer acid diglycidyl ester; glycidyl amine type such as glycidyl aniline, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, triglycidyl aminophenol; linear such as epoxidized polybutadiene and epoxidized soybean oil. Aliphatic epoxy resin; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3) , 4-Epoxy-6-methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxyside, diglycidyl Examples thereof include alicyclic epoxy resins such as clopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, and limonene dioxide.

The above-mentioned aldehyde compound is not particularly limited, and is, for example, monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, and benzaldehyde, glioxal, malonaldehyde, glutaaldehyde, pimerindialdehyde, suberindialdehyde, and dialdehyde. Examples thereof include dialdehydes such as starch.

The above-mentioned polyhydric isocyanate compound is not particularly limited, but for example, "Duranate" manufactured by Asahi Kasei Chemicals Co., Ltd. (WB40-100, WB40-80D, WE50-100, WT30-100, WT20-100, etc.); tolylene diisocyanate. (TDI); Hydrogenated TDI; Trimethylol Propane-TDI Adduct (eg, Bayer, "Desmodur L"); Triphenylmethane triisocyanate; Methylene (bisphenyl isocyanate) (MDI); Hydrogenated MDI; Polymerized MDI; Hexamethylene Diisocyanate; xylylene diisocyanate; 4,4'-dicyclohexylmethane diisocyanate; isophorone diisocyanate and the like. Isocyanates dispersed in water using an emulsifier can also be used.

The above-mentioned water-soluble oxidizing agent is not particularly limited, and for example, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like. Examples thereof include t-butyl hydroperoxide, potassium bromide, t-butyl peracetate, and t-butyl perbenzoate.

The water resistant agent may be used alone or in combination of two or more. The content of the water resistant agent is not particularly limited, but can be determined according to the type of the side chain amino group-containing vinyl alcohol polymer. For example, from the viewpoint of the water resistance of the film after the reaction with the water resistant agent, the amount is preferably 0.1 part by mass to 200 parts by mass, preferably 0.5 part by mass with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol-based polymer. It is more preferably from 1 part to 100 parts by mass, and particularly preferably 1 part to 80 parts by mass.

The vinyl alcohol-based polymer composition of the present invention further comprises a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antioxidant, and the like. Flame retardants, plasticizers, other thermoplastics, lubricants, fragrances, defoamers, deodorants, bulking agents, release agents, mold release agents, reinforcing agents, fungicides, preservatives, crystallization rate retarders Additives such as these can be appropriately added as needed.

The vinyl alcohol-based polymer composition of the present invention can be used for the same purpose in the same manner as the composition containing a known vinyl alcohol-based polymer and a water resistant agent. For example, it is effectively used as a coating agent for inorganic materials or organic materials such as paper and various resin base materials, particularly as a surface coating agent for paper and a surface coating agent for various resin films. Here, examples of the resin film include films such as polyester, polystyrene, polyamide, polyvinyl chloride, polymethylmethacrylate, cellulose acetate, polycarbonate, and polyimide. Further, the vinyl alcohol-based polymer composition of the present invention is extremely effectively used for a coating layer of a recording material, particularly a heat-sensitive recording material that cannot be heat-treated at a high temperature, particularly an overcoat layer. The vinyl alcohol-based polymer composition of the present invention is an adhesive or binder for inorganic or organic substances, vehicles for paints, dispersants such as pigment dispersions, polymerization stabilizers and post-additives for crosslinkable emulsions, gelatin blends or photosensitive. It can be widely used for image-forming materials such as resins, substrates for hydrogels such as cell-fixed gels or enzyme-fixed gels, and applications in which water-soluble resins have been conventionally used. Further, it can be used for molded products such as films, sheets and fibers.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "%" and "parts" in Examples and Comparative Examples represent "% by mass" and "parts by mass", respectively.

[Calculation of denaturation rate]
Using a nuclear magnetic resonance apparatus "LAMBDA 500" manufactured by Nippon Denshi Co., Ltd., ¹ H-NMR of a vinyl alcohol-based polymer containing a side chain amino group was measured at room temperature, and an amide proton (7.6 to 7.7 ppm) or a formula was used. The modification rate was calculated from the integrated value of the proton peak characteristic of the amine compound shown in (2). For example, in Example 1, the denaturation rate was calculated from the integrated value of the peak derived from the methyl proton appearing at 1.0 ppm. Here, the modification rate corresponds to the content of the structural unit represented by the formula (1) with respect to all the structural units constituting the side chain amino group-containing vinyl alcohol-based polymer. In the NMR analysis, in order to clarify the structure of the target product, various temperature conditions, measurements with nuclides, and measurements using additives may be combined.

[Measurement of hue (yellow index; YI)]
YI (ASTM D1925), which is a powder of a vinyl alcohol-based polymer containing a side chain amino group obtained in Examples or Comparative Examples, is used as a spectrocolorimeter "CM-8500d" manufactured by Konica Minolta Co., Ltd. by the following method. Measured using (light source: D65, CM-A120 white calibration plate, CM-A126 petri dish set used, normal reflection measurement SCE, measurement diameter φ30 mm). 5 g of the sample was added to the petri dish, and the powder was lightly tapped on the side surface without pressing the powder to shake it, and the powder was spread evenly and evenly. In this state, a total of 10 measurements were performed (each time the petri dish was shaken once and then remeasured), and the average value was taken as YI of the resin.

[Water resistance evaluation of film]
An azetidine-based cross-linking agent (polyamide polyamine epichlorohydride) represented by the following formula (4) is added to an aqueous solution (concentration: 5% by mass) containing a side chain amino group-containing vinyl alcohol-based polymer obtained in the following Example or Comparative Example. Phosphorus resin (hereinafter, may be referred to as PAE; "WS4020" manufactured by Starlight Polymer Co., Ltd.), ethylene glycol diglycidyl ether represented by the following formula (5) (hereinafter, may be referred to as EGDGE; Nagase Chemtex). "Denacol EX-810" manufactured by Nagase Chemtex Co., Ltd. or one of the polyglycerol polyglycidyl ethers represented by the following formula (6) ("Denacol EX-512" manufactured by Nagase Chemtex), which is a vinyl alcohol-based weight containing a side chain amino group. The amino group of the coalescence and the above-mentioned cross-linking agent were dissolved in an equimolar ratio to prepare a coating liquid. The coating liquid was applied to a 15 cm × 15 cm mold prepared by bending the end of a polyethylene terephthalate film. The film was cast and sufficiently volatilized the solvent at room temperature and atmospheric pressure to obtain a film having a thickness of about 50 μm. The obtained evaluation film was immersed in boiling water for 1 hour, removed from water, and taken out from water at 40 ° C. 12 The mass (W1) was measured after time vacuum drying. From the obtained mass (W1) and the mass before immersion (W2), the elution rate under boiling conditions was calculated according to the following formula, and this elution rate was calculated. Was used as an index of water resistance after crosslinking. When the evaluation film was dissolved during immersion in water, it was evaluated as "unmeasurable".
Elution rate (% by mass) = 100 × ([W2]-[W1]) / [W2]

[Synthesis Example 1]
A reactor equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a dropping funnel and a reaction substrate addition port was charged with 640 parts by mass of vinyl acetate, 254 parts by mass of methanol, and 1.05 parts by mass of methyl acrylate, and nitrogen bubbling. The inside of the system was replaced with nitrogen for 30 minutes. Separately, a methanol solution of methyl acrylate (concentration: 20% by mass) was prepared as a solution for sequentially adding comonomer, and nitrogen bubbling was performed for 30 minutes. When the temperature of the reactor was raised to 60 ° C., 0.06 parts by mass of 2,2'-azobisisobutyronitrile was added and polymerization was started at 60 ° C. During the progress of the polymerization reaction, the prepared methanol solution of methyl acrylate was added dropwise into the system so that the monomer composition (molar ratio of vinyl acetate and methyl acrylate) in the polymerization solution became constant. The polymerization was terminated when the polymerization rate of vinyl acetate reached 30 mol%, and the unreacted vinyl acetate monomer was removed from the system to obtain a methanol solution of the copolymer.

Methanol was further added to the obtained copolymer in methanol so that the concentration of the copolymer was 10% by mass. Next, while maintaining the temperature at 60 ° C., a methanol solution of sodium hydroxide having a concentration of 10% by mass was added at a ratio of 10 mmol of sodium hydroxide to 1 mol of vinyl acetate unit in the copolymer for 2 hours. , Made caustic. As the saponification progressed, the saponified product was deposited in the form of particles. After neutralizing the alkali by adding methyl acetate, the obtained particulate saponified product is separated from the solution, washed well with methanol, and dried in a hot air dryer at 50 ° C. for 12 hours to obtain a copolymer. rice field.

When the obtained copolymer was analyzed by ¹ H-NMR, a lactone ring-containing vinyl having a structure in which R3 is a hydrogen atom in the formula ( ² ) was introduced in an amount of 5 mol% with respect to the number of moles of all the constituent units. It turned out to be an alcohol-based polymer. In the lactone ring-containing vinyl alcohol-based polymer, the ratio of the number of moles of vinyl alcohol units to the total number of moles of vinyl alcohol units and vinyl acetate units was 99 mol% or more. Further, the degree of polymerization of the obtained polymer was determined from the ultimate viscosity [η] (unit: deciliter / g) measured in water at 30 ° C. by the following formula and found to be 1500.
Degree of polymerization = ([η] × 10 ³ / 8.29) ^{(1 / 0.62)}

[Example 1]
100 parts by mass of the lactone ring-containing vinyl alcohol-based polymer obtained in Synthesis Example 1 was added to a reactor equipped with a stirrer, a reflux condenser and a reaction substrate addition port. To this, 567 parts by mass of methanol and 40.4 parts by mass of 1,2-diaminopropane were mixed and added, the temperature was raised to 65 ° C., and the mixture was stirred for 5 hours. Then, the reaction solution was filtered, and the resin collected by filtration was transferred to a reactor. After adding 1000 parts by mass of methanol and stirring at room temperature for 30 minutes, the solution was filtered. This was repeated twice and then vacuum dried at 40 ° C. for 12 hours to obtain a desired side chain amino group-containing vinyl alcohol polymer. As a result of measuring ¹ H-NMR of the obtained side chain amino group-containing vinyl alcohol polymer, it was found that the structure represented by the formula (1) was contained in 0.7 mol%. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 4.3 mol%. Further, as YI and a water resistant agent, PAE (compound represented by the formula (4)) was used in an amount of 10.1 parts by mass (as a 25% by mass aqueous solution) with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. Table 1 shows the evaluation results of the water resistance of each case.

[Example 2]
100 parts by mass of the lactone ring-containing vinyl alcohol-based polymer obtained in Synthesis Example 1 was added to a reactor equipped with a stirrer and an addition port for the reaction substrate. To this, 300 parts by mass of methanol and 11.5 parts by mass of 3-methylaminopropylamine were mixed and added, the temperature was raised to 60 ° C. while reducing the pressure inside the reactor, and the mixture was stirred until the entire amount of methanol was volatilized. After the methanol was volatilized, the temperature was raised to 80 ° C. and the mixture was stirred for 2 hours. Then, after allowing to cool to room temperature, 1000 parts by mass of methanol was added to the reactor, the mixture was stirred at room temperature for 30 minutes, and then the solution was filtered. This was repeated twice and then vacuum dried at 40 ° C. for 12 hours to obtain a desired side chain amino group-containing vinyl alcohol polymer. EGDGE (compound represented by the formula (5)) which is a water resistant agent with respect to the amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI and 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. ) Is used in 9.5 parts by mass, and the evaluation results of water resistance are shown in Table 1. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 2.5 mol%.

[Example 3]
To a reactor equipped with a stirrer, a reflux condenser and a reaction substrate addition port, 100 parts by mass of the lactone ring-containing vinyl alcohol polymer obtained in Synthesis Example 1 and 400 parts by mass of dimethyl sulfoxide were added, and the concentration was 20% by mass. Solution was prepared. To this, 19.2 parts by mass of 3-methylaminopropylamine was added, the temperature was raised to 80 ° C., and the mixture was stirred for 12 hours. Then, the solution was added dropwise to methanol to isolate the polymer, and the polymer was vacuum dried at 40 ° C. for 12 hours to obtain a desired side chain amino group-containing vinyl alcohol-based polymer. The amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI, and the compound represented by PAE (formula (4)) which is a water resistant agent with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. ) Is used in 28.8 parts by mass (as 25% by mass), and the evaluation results of water resistance are shown in Table 1. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 3.0 mol%.

[Example 4]
Same as Example 1 except that 300 parts by mass of methanol was used, 5.6 parts by mass of 1,3-diaminopentane was used instead of 1,2-diaminopropane, and the reaction time was 3 hours. Reaction, post-treatment and analysis were performed. EX-512 (formula (6)) which is a water resistant agent with respect to the amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI and 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer is shown. Table 1 shows the evaluation results of water resistance when 2.5 parts by mass of the compound) was used. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 4.8 mol%.

[Example 5]
In Example 1, 1,4-dioxane was used instead of methanol, 19.2 parts by mass of 3-methylaminopropylamine was used instead of 1,2-diaminopropane as the amine compound, and the reaction temperature was 100 ° C. The reaction, post-treatment and analysis were carried out in the same manner as in Example 1 except that the reaction time was set to 1 hour. The amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI, and the compound represented by PAE (formula (4)) which is a water resistant agent with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. ) Is used in 14.4 parts by mass (as 25% by mass), and the evaluation results of water resistance are shown in Table 1. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 4.0 mol%.

[Comparative Example 1]
60 parts of PAE (compound represented by the formula (4)) as a water resistant agent was added to YI of the lactone ring-containing vinyl alcohol polymer obtained in Synthesis Example 1 and 100 parts by mass of the lactone ring-containing vinyl alcohol polymer. Table 1 shows the evaluation results of water resistance when using 0.6 parts by mass (as 25% by mass). The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 5.0 mol%.

[Comparative Example 2]
According to the method of Example 1 described in JP-A-2013-53267, oxazolidinone group-containing polyvinyl acetate was synthesized, subsequently converted to oxazolidinone group-containing polyvinyl alcohol, and further induced to amino group-containing polyvinyl alcohol. 41.8 parts by mass (25 parts by mass) of PAE (compound represented by the formula (4)) which is a water resistant agent with respect to the modified amount of the obtained amino group-containing polyvinyl alcohol, YI and 100 parts by mass of the amino group-containing polyvinyl alcohol. The evaluation results of water resistance when used as%) are shown in Table 1. The vinyl alcohol unit was 97.0 mol%, and the vinyl ester unit was 0.1 mol%.

[Comparative Example 3]
In Example 1, 300 parts by mass of 1,4-dioxane was used instead of methanol, and 9.1 parts by mass of 2- (2-aminoethylamino) ethanol was used as the amine compound instead of 1,2-diaminopropane. The reaction, post-treatment and analysis were carried out in the same manner as in Example 1 except that the reaction temperature was 100 ° C. and the reaction time was 4 hours. The amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI, and the compound represented by PAE (formula (4)) which is a water resistant agent with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. ) Is used in 36 parts by mass (25% by mass), and the evaluation results of water resistance are shown in Table 1. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the constituent unit represented by the formula (2) was 3.5 mol%.

As is clear from the evaluation results of Examples 1 to 6, the side chain amino group-containing vinyl alcohol polymer of the present invention has a good hue and can be made water resistant by mixing with a water resistant agent. I understand. Therefore, the side chain amino group-containing vinyl alcohol-based polymer of the present invention can be used for a wide range of uses of polyvinyl alcohol.

As in Comparative Example 1, polyvinyl alcohol containing no side chain amino group could not be made water resistant even when mixed with a water resistant agent. Further, in the method of deprotecting the copolymerized monomer having an amino group protected after copolymerizing with vinyl acetate as in Comparative Example 2, deterioration of hue is unavoidable. Further, as in Comparative Example 3, when the number of carbon atoms of the substituent of the side chain amino group was 2 or more and the volume was high, the reactivity of the introduced amino group was low and the water resistance could not be sufficiently obtained.

Claims (9)

A side chain amino group-containing vinyl alcohol-based polymer represented by the following formula ( A ).

[In the formula ( A ), X is a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, and a substituent. A divalent aromatic hydrocarbon group that may have, or a group in which two or more of these groups are attached via at least one bond selected from the group consisting of amide bonds, ester bonds and ether bonds. Represents. R ¹ is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and an aromatic hydrocarbon which may have a substituent. Represents a structure forming a ring with a hydrogen group or X, and R ² represents a structure forming a ring with a hydrogen atom, a methyl group, or X. R ³ represents a hydrogen atom or a methyl group. a, b, c and d represent the content of each constituent unit with respect to all the constituent units, a is 50 to 99.95 mol%, b is 0.05 to 30 mol%, and c is 0. It is 005 to 10 mol%, and d is 0.001 to 10 mol%. ] The side chain amino group-containing vinyl alcohol-based polymer according to claim 1, wherein the yellow index (YI) measured according to ASTM D1925 is 50 or less. The side chain amino group-containing vinyl alcohol-based polymer according to claim 1 or 2, wherein the total carbon atoms of X, R ¹ and R ² are 15 or less. The side chain amino group-containing vinyl alcohol-based polymer according to any one of claims 1 to 3, wherein R ¹ is a hydrogen atom. The invention according to any one of claims 1 to 4, wherein X is a divalent aliphatic hydrocarbon group which may have a substituent, or X and R ² form a ring structure. Side chain amino group-containing vinyl alcohol-based polymer. The side chain amino group-containing vinyl alcohol-based polymer according to claim 5, wherein X is a divalent aliphatic hydrocarbon group which may have a substituent. The side chain amino group-containing vinyl alcohol-based polymer according to any one of claims 1 to 6, wherein ^R2 is a methyl group. A vinyl alcohol polymer composition comprising the side chain amino group-containing vinyl alcohol polymer according to any one of claims 1 to 7 and a water resistant agent. The side chain according to any one of claims 1 to 7, wherein an amine compound represented by the following formula (3) is subjected to an addition reaction with a vinyl alcohol-based polymer containing a structural unit represented by the following formula (2). A method for producing an amino group-containing vinyl alcohol polymer.

[In formula (2), R ³ represents a hydrogen atom or a methyl group. ]

[In equation (3), X, R ¹ and R ² are synonymous with equation ( A ). ]