JPH11116636A - Amino acid-containing vinyl alcohol-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer capable of providing a composition which completely expresses properties of amino groups and has excellent water resistance, viscosity stability, etc., by containing a specific amount of a unit containing an amino group bonded to a heterocyclic ring. SOLUTION: This polymer contains 0. 01-30 mole % of a unit having an amino group bonded to a heterocyclic ring. The unit having the amino group bonded to the heterocyclic ring is preferably a unit expressed by the formula (R<1> to R<5> are each H or an <=8C hydrocarbon group; A is a divalent hydrocarbon group; S is a sulfur atom; X is a monovalent group having the amino group bonded to the heterocyclic ring). A resin composition comprising the polymer and a water resistant agent selected from a polyvalent epoxy compound, an aldehyde compound, etc., is excellent in water resistance. The polymer can be obtained by reacting a copolymer of a vinyl ester monomer and an epoxy group-containing vinyl monomer with a thiol having an amino group bonded to a heterocyclic ring and hydrolyzing the reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel vinyl alcohol-containing polymer containing an amino group and a resin composition having excellent water resistance using the same.

[0002]

2. Description of the Related Art Polyvinyl alcohol (hereinafter abbreviated as PVA) is a rare crystalline water-soluble polymer and has excellent interface properties and strength properties. In addition, it has an important position as a raw material for PVA-based films and PVA-based fibers. On the other hand, the pursuit of high functionality for controlling crystallinity or improving specific performance by introducing a functional group has been pursued, and various modified PVAs have been developed.

With respect to vinyl alcohol-based polymers containing amino groups, vinylamine copolymers (Japanese Patent Laid-Open No.
55702) Polymers containing quaternary ammonium salts (JP-A-56-14504, JP-A-56-11884)
No. 4) is known, but since the amino group is directly bonded to the main chain of PVA or is located very close to the main chain of PVA, the intramolecular interaction with the hydroxyl group in PVA or Because of the susceptibility to the molecular motion of the main chain of PVA, the properties of amino groups often cannot be fully utilized.
Aminobenzal compounds (Industrial Chemistry Magazine, Vol. 57,
870, 1954), but in many cases, the properties of the amino group cannot be fully utilized because the amino group is linked to the main chain of PVA by an acetal bond having low molecular mobility.

[0004] Also, PVA is widely used as various binders, adhesives or surface treatment agents, and is known to have excellent performance unrivaled by other water-soluble resins in terms of film forming properties and strength. Have been. However, since PVA is water-soluble, it has a drawback of low water resistance, particularly when dried at low temperatures,
Various methods are being considered. For example, a method is known in which PVA is crosslinked with glyoxal, glutaraldehyde or dialdehyde starch, a water-soluble epoxy compound, a methylol compound, or the like. However, in order to make PVA sufficiently water-resistant by this method, 100 ° C. or more,
In particular, it is necessary to heat-treat at a high temperature of 120 ° C. or more for a long time. Further, in order to achieve water resistance at a low temperature, strongly acidic conditions such as a pH of 2 or less are required. In this case, however, the viscosity stability of the PVA aqueous solution is poor and the water resistance is insufficient. ing. Further, a method of crosslinking a carboxyl group-containing PVA with a polyamide epichlorohydrin resin and a method of crosslinking an acetoacetyl group-containing PVA with a polyaldehyde compound such as glyoxal are known. However, the viscosity stability of an aqueous PVA solution is poor, and water resistance is poor. Is also insufficient.

[0005]

SUMMARY OF THE INVENTION Under such circumstances, an object of the present invention is to provide a novel PVA which can sufficiently exhibit the properties of an amino group. Furthermore, the present invention provides a water-resistant composition which is remarkably excellent in water resistance not only to cold water but also to hot water even when dried or heat-treated at a low temperature of room temperature to about 50 ° C., and has no problems such as viscosity stability. The purpose is to provide things.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a vinyl alcohol-based compound containing 0.01 to 30 mol% of a unit containing an amino group bonded to a heterocyclic ring. Polymer (hereinafter, amino group-containing PVA)
(Abbreviated). Further, it comprises the amino group-containing PVA (A) and at least one or more water-resistant agents (B) selected from polyhydric epoxy compounds, aldehyde compounds, polyvalent isocyanate compounds, amino resins, phenol resins and di (meth) acrylamide. They have also found a resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The amino group-containing PVA of the present invention comprises
A unit containing an amino group bonded to a heterocyclic ring in an amount of 0.01 to
It is a vinyl alcohol polymer containing 30 mol%.
A more preferred range of the content of the unit is 0.02 to 2
0 mol%, and a particularly preferable range is 0.05 to 15 mol%. When the content of the unit is less than 0.01 mol%, the effect of introduction is not sufficiently exhibited, and when it exceeds 30 mol%, the storage stability of the amino group-containing PVA solution decreases (for example, gelation). The distribution of the units in the amino group-containing PVA is not particularly limited. As the unit containing an amino group bonded to the heterocyclic ring, a unit represented by the following formula 3 is preferable.

[0008]

Embedded image

Here, R ¹ , R ² , R ³ , R ⁴ and R
⁵ represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, A represents a divalent hydrocarbon group, S represents a sulfur atom, and X represents a monovalent monovalent containing an amino group bonded to a heterocyclic ring. Represents a group.

R ¹ , R ² , R ³ ,
R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms. It is preferable that R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, and R ³ , R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon having 8 or less carbon atoms, preferably 6 or less carbon atoms. Note that R ³ and R ⁴ (or R ⁵ ) may form a ring together.

A in the unit represented by Formula 3 is a nitrogen atom,
It is a divalent hydrocarbon group which may contain an oxygen atom or a sulfur atom. For _{example, - (CH 2 CH 2)} n - (n =
1-10, preferably _{n = 1~8), - CH 2} OCH 2 -,
_{-OCH 2 -, - CONH-φ} -OCH 2 -, - CONH
CH ₂ —, —CONHCH ₂ OCH ₂ —, —CONHCH ₂
OCH ₂ CH ₂ —, —CONHCH ₂ OCH ₂ CH ₂ CH
_2- , -CONHCH ₂ OCH ₂ CH ₂ CH ₂ CH _2- , -C
ONHCH ₂ —φ (CH ₃ ) ₂ —CH ₂ — and the like.
Here, φ means a phenylene group.

X in the unit represented by Formula 3 contains an amino group (including a primary amino group, a secondary amino group, and a tertiary amino group and salts thereof and a quaternary ammonium salt) bonded to a heterocyclic ring. Is a monovalent group. As the monovalent group containing an amino group bonded to a heterocyclic ring, a group represented by the following formula 4 is preferable.

[0013]

Embedded image

Here, Z represents S, O, NH or CH ₂ . Specific examples of the heterocyclic ring include, for example, mono-hetero five-membered ring compounds such as furan, pyrrole and thiophene; di-hetero five-membered ring compounds such as oxazole, imidazole, thiazole, isoxazole, pyrazole and isothiazole; triazole, oxadiazole and thiadiazole And hetero- and tetra-hetero five-membered ring compounds such as tetrazole and tetrazole; hetero-six-membered ring compounds such as pyran, pyridine, oxazine and pyridazine; and condensates thereof with benzene rings and the like. The amino group bonded to the heterocyclic ring in the present invention does not form a heterocyclic ring but is bonded to the heterocyclic ring from outside the heterocyclic ring.

The amino group-containing PVA of the present invention contains a vinyl alcohol unit or a vinyl alcohol unit and a vinyl ester unit, excluding a unit containing an amino group bonded to a heterocyclic ring. Examples of the vinyl ester unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl trifluoroacetate, and vinyl 2-ethylhexanoate.

Further, within a range not to impair the gist of the present invention,
A monomer unit other than these may be contained. For example, olefins such as ethylene, propylene, 1-butene, and isobutene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (phthalic anhydride), maleic anhydride, and itaconic acid, and salts thereof Or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide,
Acrylamides such as 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide , 2-
Methacrylamidopropanesulfonic acid or a salt thereof,
Methacrylamides such as methacrylamidopropyldimethylamine or an acid salt or a quaternary salt thereof; N
N-vinylamides such as vinylpyrrolidone, N-vinylformamide and N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxy alkyl vinyl ethers Vinyl ethers such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxy vinyl silane; allyl acetate, allyl chloride, allyl alcohol, dimethyl allyl alcohol Is mentioned.

Although the molecular weight of the amino group-containing PVA of the present invention is not particularly limited, a 4% dimethyl sulfoxide (D
3 to 10,000 cp, preferably 3 to 5000 cp, as represented by the viscosity of the (MSO) solution at 20 ° C. (measured with a Brookfield viscometer).
cp is more preferred. Further, the content of the vinyl alcohol unit is preferably from 10 to 99.9 mol%, and from 50 to 99.9 mol%.
Molar% is more preferred.

The amino group-containing PVA of the present invention can be obtained by a method comprising reacting a copolymer of a vinyl ester monomer and a vinyl monomer having an epoxy group with a thiol having an amino group bonded to a heterocycle, followed by hydrolysis. Obtainable.

Examples of the vinyl monomer having an epoxy group include allyl glycidyl ether, methallyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, and 1,2-epoxy-9-decene. , 8-hydroxy-6,7-epoxy-1-octene, 8-acetoxy-6,7-epoxy-1-octene, N- (2,3-epoxy) propylacrylamide, N- (2,3-epoxy) Propyl methacrylamide, 4-acrylamidophenyl glycidyl ether,
3-acrylamidophenyl glycidyl ether, 4-
Methacrylamide phenyl glycidyl ether, 3-methacrylamide phenyl glycidyl ether, N-glycidoxymethyl acrylamide, N-glycidoxymethyl methacrylamide, N-glycidoxyethyl acrylamide, N-glycidoxyethyl methacrylamide, N
-Glycidoxypropylacrylamide, N-glycidoxypropylmethacrylamide, N-glycidoxybutylacrylamide, N-glycidoxybutylmethacrylamide, 4-acrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, 4- Methacrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, acrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride, methacrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride, glycidyl methacrylate and the like. .

Examples of the thiol having an amino group bonded to a heterocyclic ring include 2-amino-5-mercapto-1,3,4
-Thiadiazole, 2-amino-5-mercapto-1,
3,4-oxydiazole, 2-amino-5-mercapto-1,3,4-triazole, 2-amino-5-mercapto-1,3,4-methylenediazole, 2-mercapto-5-amino- 1,3,4-thiadiazole, 5-
Amino-3-mercapto-1,2,4-triazole,
3-Amino-5-mercapto-1,2,4-triazole, 3-mercapto-4-amino-1,2,4-triazole and 5-mercapto-4-amino-1,2,4-triazole. . Further, esters such as these acetates and benzoates can also be used.

The reaction between the thiol group or the thioester group and the epoxy group is carried out without a solvent or in a solvent that dissolves or swells the compound having the thiol group or the thioester group and the compound having the epoxy group. Examples of such a solvent include alcohols such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol; aromatics such as benzene, toluene and xylene; ethers such as tetrahydrofuran, dioxane and diethyl ether; and n-hexane. And the like. These may be used alone or as a mixture. The reaction conditions vary depending on the structure of the epoxy group and the structure of the thiol or thioester. When a solvent is used, the polymer concentration is 5 to 90%, and the concentration of the thiol group or thioester group / the concentration of the epoxy group is 1.0 to 5%. .
0 (molar ratio), the reaction temperature is 0 to 250 ° C, and the reaction time is 0.
01 to 20 hours. Here, in the reaction with thiol, basic compounds such as tertiary amines (eg, triethylamine, pyridine, etc.), phosphines (eg, tributylphosphine, triphenylphosphine, etc.), sodium hydroxide, tetraethylammonium hydroxide, sodium methylate, etc. It is effective as a reaction catalyst. In the reaction with a thioester, a quaternary ammonium salt such as tributylammonium chloride and tributylammonium bromide is effective as a reaction catalyst. In order to prevent thiol oxidation, the reaction system may be degassed or replaced with nitrogen, or an antioxidant may be added.

The hydrolysis subsequent to the reaction between the thiol group or thioester group and the epoxy group can be effected by a saponification reaction using a basic catalyst or an acid catalyst which is usually used in saponification of polyvinyl ester. That is, using a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate or an acidic catalyst such as p-toluenesulfonic acid, the reaction is carried out using an alcohol or glycol such as methanol, ethanol, propanol, butanol or ethylene glycol as a solvent. Is performed. In this case, a solvent such as tetrahydrofuran, dioxane, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, acetone, or water is appropriately mixed and used in order to improve the solubility of the vinyl ester polymer and the catalyst. The conditions of the saponification reaction are appropriately adjusted depending on the structure of the vinyl ester polymer to be used and the desired degree of saponification of the amino group-containing PVA, and usually, the catalyst concentration / vinyl ester unit concentration (molar ratio) is 0.001 to 0.001. 1.2, reaction temperature 20-180
C. and a reaction time in the range of 0.1 to 20 hours.

The amino group-containing PVA of the present invention can be used as a fiber sizing agent, a fiber treating agent, a fiber processing agent, a clear coating,
Paper coating agents such as clay coating, paper processing agents such as thermal paper overcoating agents, dispersants for organic and inorganic pigments, dispersion stabilizers for emulsion polymerization, dispersion stabilizers for PVC polymerization, binders for ceramics, image formation It is used as a material, a photosensitive resin, a raw material for polyvinyl acetal such as a formal resin and a butyral resin, a base material for a gel, a film, a fiber and the like. The amino group-containing PVA of the present invention can be used alone or unmodified PVA, other modified PVA, starch (and modified products thereof), cellulose derivatives, gums, gelatin, by utilizing the reactivity of the amino group bonded to the heterocycle. And various polymers such as casein. Further, it can be used in combination with a crosslinking agent such as a plasticizer, an epoxy compound, a dialdehyde, and an isocyanate.

Next, the water-proofing agent (B) constituting the resin composition of the present invention will be described. Examples of polyhydric epoxy compounds include 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, and chlorinated Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether,
Glycidyl ether type such as glycerin triglycidyl ether, pentaerythritol diglycidyl ether, epoxy urethane resin; glycidyl ether / ester type such as P-oxybenzoic acid glycidyl ether / ester; diglycidyl phthalate, diglycidyl tetrahydrophthalate Glycidyl ester type such as diglycidyl ester of hexahydrophthalic acid, diglycidyl acrylate, diglycidyl ester of dimer; glycidylamine type such as glycidylaniline, tetraglycidyldiaminodiphenylmethane, triglycidyl isocyanurate, triglycidylaminophenol; epoxy Linear aliphatic epoxy resins such as hydrogenated polybutadiene and epoxidized soybean oil; 3,4 epoxy-6 methylcyclohexylmethyl Tyl-3,4 epoxy-6 methylcyclohexanecarboxylate, 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, Dicyclopentadiene oxide,
Examples include alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether and limonenedioxide, and polyamide epichlorohydrin.

Examples of the aldehyde compound include monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde and benzaldehyde, and dialdehydes such as glyoxal, malonaldehyde, glutaraldehyde, pimerin dialdehyde, suberin dialdehyde and dialdehyde starch. Is mentioned.

Examples of the polyvalent isocyanate compound include tolylene diisocyanate (TDI); hydrogenated TDI; trimethylolpropane-TDI adduct (eg, Desmour L, manufactured by Bayer); triphenylmethane triisocyanate; methylenebisdiphenyl isocyanate (MDI); hydrogenated MDI; polymerized MDI; hexamethylene diisocyanate; xylylene diisocyanate; 4,4-dicyclohexylmethane diisocyanate; isophorone diisocyanate. Further, an isocyanate dispersed in water using an emulsifier can also be used.

The amino resin is obtained by a condensation reaction between an amino compound and an aldehyde. Examples of the amino compound subjected to the condensation reaction include melamine, urea, thiourea, dicyandiamide, benzoguanamine, acetoguanamine and the like. These can be used alone or in combination of two or more. As the aldehyde, formaldehyde is used in the form of an aqueous solution or alcohol solution, and a compound capable of generating formaldehyde under condensation reaction conditions, for example, paraformaldehyde is also used.

The phenol resin is obtained by a condensation reaction between a phenol compound and an aldehyde. Examples of the phenol compound to be subjected to the condensation reaction include phenol, m-cresol, O-cresol, p-cresol, 3,5-xylenol, 2,5-xylenol, 2,4-xylenol, 3,4-xylenol, saligenin , 2,3,5
-Trimethylphenol and the like. These can be used alone or in combination of two or more. As the aldehyde, formaldehyde is used in the form of an aqueous solution or alcohol solution, and a compound capable of generating formaldehyde under condensation reaction conditions, for example, paraformaldehyde, hexamethylenetetramine and the like are also used.

As di (meth) acrylamide, N,
N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-propylenebisacrylamide.

In the resin composition of the present invention, the weight ratio (A) / (B) of the amino group-containing PVA (A) to the waterproofing agent (B) is 99.99 / 0.01 to 10/90, preferably 99.9 / 0.1 to 70/30. (A) / (B) is 99.99 / 0.0
When it exceeds 1, the water resistance effect is low, and when it is less than 10/90, the viscosity stability of the aqueous solution of the composition decreases.

The resin composition of the present invention comprises an amino group-containing PV
It is an essential condition to contain A (A) and a water-proofing agent (B), but other than that, depending on the application, a solvent, various additives, another water-soluble resin or a polymer aqueous dispersion. Etc. can be contained. As a solvent, water is preferably used, and a solvent such as various alcohols, ketones, dimethylformamide, and dimethylsulfoxide can be used in combination. Examples of the additives include various antifoaming agents, various dispersing agents, nonionic or anionic surfactants, silane coupling agents, pH regulators, and fillers such as calcium carbide, clay, talc, and flour. Examples of the water-soluble resin include cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, poly (meth) acrylic acid, polyhydroxy (meth) acrylate or a copolymer thereof, (meth) acrylic polymers such as polyacrylamide, polyvinylpyrrolidone or The copolymer, carboxyl group-containing modified PV
A Modified PVA containing a sulfate group, modified PV containing a sulfonic acid group
A, a PVA derivative such as a modified PVA containing a phosphoric acid group, a modified PVA containing a quaternary ammonium base, and a general PVA. Examples of the aqueous polymer dispersion include aqueous dispersions of acrylic polymers and copolymers, ethylene-vinyl acetate copolymers, vinyl ester polymers and copolymers, and styrene-butadiene copolymers.

The resin composition of the present invention has a film-forming property at a low temperature,
Utilizing film strength or water resistance, it is used as an overcoat agent for paper, especially an overcoat agent for thermal paper which cannot be heat-treated at high temperatures. In addition, inorganic or organic adhesives such as plywood secondary processing adhesives, ceramic binders, dispersants such as pigment dispersions, polymerization stabilizers for crosslinkable emulsions, image forming materials such as gelatin blends or photosensitive resins, and bacteria It is effectively used as a base material for hydrogels such as a body-fixed gel or an enzyme-fixed gel, a vehicle for a paint, a treatment agent for an inorganic material or an organic material, for example, a surface coating agent. Furthermore, it can be widely used in applications where a water-soluble resin has been conventionally used. Further, it can be used for molded products such as films, sheets, and fibers.

The resin composition of the present invention is usually used by dissolving or dispersing it in water or water containing the above-mentioned organic solvent. For example, when used as an overcoat agent for paper, the amino group-containing PVA (A) and the water-proofing agent (B) may be mixed and applied, or the component (B) may be applied to the paper in advance, and Component (A) may be applied. When used in an adhesive, the component (A) and the component (B) may be mixed and applied to the surface to be bonded, or the component (B) may be applied to one of the surfaces in advance. Alternatively, the component (A) may be used after being applied to the other surface. As described above, the water-resistant composition of the present invention may be used by mixing the component (A) and the component (B), or by using a method in which the component (B) is allowed to act on the component (A) later. Is also good.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the following examples, “parts” and “%” are “parts by weight” unless otherwise specified.
And "% by weight".

Synthesis Example of Vinyl Ester Polymer Having Epoxy Group Synthesis Example 1 405 parts of vinyl acetate monomer, 11 parts of allyl glycidyl ether and methanol were placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer. Charge 30 parts,
Degas by bubbling nitrogen gas for 15 minutes. Separately, an initiator solution was prepared by dissolving 4.5 parts of 2,2′-azoisobutyronitrile in 15 parts of methanol, and the mixture was purged with nitrogen by bubbling nitrogen gas. Start raising the temperature of the reactor until the internal temperature reaches 6
When the temperature reached 0 ° C., a separately prepared initiator solution was added to initiate polymerization. Polymerization was carried out at 60 ° C. for 4 hours, and the polymerization was stopped by cooling. At this time, the solid content concentration was 54.8%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure, and a methanol solution of polyvinyl acetate copolymer (concentration: 44.5%)
I got A part of this methanol solution was put into ether to recover the polymer, which was purified by reprecipitation twice with acetone-ether, and then dried at 40 ° C. under reduced pressure. Proton NMR (GSX-270, manufactured by JEOL Ltd.) and intrinsic viscosity measurement in acetone (JIS) were performed on this purified polymer and the viscosity average molecular weight was calculated using CDCl ₃ as a solvent. As a result, allyl glycidyl ether units (epoxy Is a polyvinyl acetate copolymer having a viscosity average molecular weight of 80 × 10 ³ containing 2.1 mol% of

Synthesis Examples 2 to 6 In the same manner as in Synthesis Example 1 except that the type and amount of vinyl ester monomer, the amount of methanol, the type and amount of initiator, and the removal of unreacted vinyl ester monomer were partly n-butanol , Etc.) to obtain a vinyl ester polymer having an epoxy group shown in Table 1.

[0037]

[Table 1]

Example 1 100 parts of a methanol solution (concentration: 44.5%) of the polymer having an epoxy group obtained in Synthesis Example 1 was placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer. After weighing and bubbling nitrogen gas for 15 minutes, 2-amino-5-
A solution prepared by dissolving 8.5 parts of mercapto-1,3,4-thiadiazole and 0.03 part of sodium hydroxide in 48 parts of methanol was charged. After reacting at 50 ° C. for 2 hours with stirring, the mixture was cooled to 40 ° C., and saponification was performed by adding 40 parts of a 10% strength solution of sodium hydroxide in methanol.
After standing at 40 ° C. for 5 hours, the mixture was ground and neutralized by adding 8 parts of acetic acid. Using a Soxhlet extractor, add 48
After washing for more than an hour, amino group-containing PVA was obtained by drying at 60 ° C. for 20 hours. Was measured for IR and proton NMR (d ₆ -DMSO) of the polymer, epoxy groups completely disappeared, the introduction of 2.1 mol% of aniline group is confirmed, the vinyl alcohol content 97.0 Mole%. The concentration of the polymer is 4%.
Was prepared and its viscosity was measured at 20 ° C. to find that it was 61.2 cp.

Examples 2 to 6 An amino group-containing PVA was obtained in the same manner as in Example 1 except that the conditions shown in Table 2 were changed. In each case, the desired denatured product was obtained. Table 2 shows the results.

Example 7 2-amino-5-mercapto-1, used in Example 1,
Except that 3,4-thiadiazole was changed to 5-amino-3-mercapto-1,2,4-triazole,
In the same manner as in Example 1, an amino group-containing PVA was obtained. Table 2 shows the results.

[0041]

[Table 2]

Example 8 A 10% aqueous solution of the amino group-containing PVA obtained in Example 1 was used.
To 3 parts, 3 parts of ethylene glycol diglycidyl ether was added to prepare a water-resistant composition. Cast this solution,
Drying at 20 ° C. gave a sheet. After immersing the obtained sheet in water at 20 ° C. for 24 hours, the degree of swelling (weight after immersion in water / absolute dry weight) was measured. The degree of swelling of the sheet was twice, and a firm film state was maintained. The obtained sheet was heat-treated at 60 ° C. for 10 minutes, and the degree of swelling was measured in the same manner as above. The degree of swelling was twice as much, and the water resistance was completed at 20 ° C. Table 3 shows the results.

Example 9 A sheet was obtained in the same manner as in Example 8, except that the water-resistant agent used in Example 8, ethylene glycol diglycidyl ether, was changed to glyoxal. The results are shown in Table 3.

Example 10 Same as Example 8 except that the water-resistant agent, ethylene glycol diglycidyl ether, used in Example 8 was changed to a water-dispersible isocyanate (Coronate C-3053, manufactured by Nippon Polyurethane Industry Co., Ltd.). To obtain a sheet. The results are shown in Table 3.

Example 11 The procedure of Example 8 was repeated except that the water-resistant agent, ethylene glycol diglycidyl ether, was changed to an amino resin.
A sheet was obtained in the same manner as in Example 8. The results are shown in Table 3.

Example 12 A sheet was obtained in the same manner as in Example 8, except that the water-resistant agent, ethylene glycol diglycidyl ether, used in Example 8 was changed to a phenol resin. The results are shown in Table 3.

Example 13 A sheet was obtained in the same manner as in Example 8, except that ethylene glycol diglycidyl ether as the water-proofing agent used in Example 8 was changed to methylenebisacrylamide. The results are shown in Table 3.

Example 14 Example 8 was repeated except that the amino group-containing PVA used in Example 8 was changed to the amino group-containing PVA obtained in Example 7.
A sheet was obtained in the same manner as described above.

Comparative Example 1 The amino group-containing PVA used in Example 8 was unmodified PVA
(Polymerization degree: 1000, saponification degree: 98.5 mol%) A sheet was obtained in the same manner as in Example 8, except that the degree of polymerization was changed to 1000. The results are shown in Table 3.

Comparative Example 2 The amino group-containing PVA obtained by saponifying a copolymer of N-vinylformamide and vinyl acetate with the amino group-containing PVA used in Example 8 (a saponification degree of 98.5 mol% and a polymerization degree of 10
Example 8, except that the modification amount was changed to 2 mol%).
A sheet was obtained in the same manner as described above. The results are shown in Table 3.

Comparative Example 3 The amino group-containing PVA used in Example 8 was carboxylic acid-modified PVA obtained by saponifying a copolymer of itaconic acid and vinyl acetate (a saponification degree of 98.0 mol%, a polymerization degree of 1,000, Amount was obtained in the same manner as in Example 8 except that the amount was changed to 2 mol%). The results are shown in Table 3.

Comparative Example 4 To 100 parts of a 10% aqueous solution of acetoacetyl group-modified PVA having a degree of saponification of 98.0 mol%, a degree of polymerization of 1000 and a modification amount of 5 mol% was added 5 g of glyoxal and dissolved. To form a sheet, and the degree of swelling was measured. The results are shown in Table 3.

[0053]

[Table 3]

[0054]

The vinyl alcohol polymer containing an amino group bonded to a heterocyclic ring according to the present invention has excellent reactivity with a water-proofing agent, and therefore has remarkably excellent water resistance even at room temperature. A water resistant composition is obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/20 C08K 5/20 5/29 5/29 C08L 29/04 C08L 29/04 A // (C08F 216/06 224: 00) ( C08L 29/04 61:00)

Claims (4)

[Claims] 1. A vinyl alcohol-based polymer containing 0.01 to 30 mol% of a unit containing an amino group bonded to a heterocyclic ring. 2. The vinyl alcohol-based polymer according to claim 1, wherein the unit having an amino group bonded to the heterocyclic ring is a unit represented by the following chemical formula 1. Embedded image (Where R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, A represents a divalent hydrocarbon group, and S represents a sulfur atom. And X represents a monovalent group containing an amino group bonded to the heterocyclic ring.) 3. The vinyl alcohol polymer according to claim 1, wherein the monovalent group containing an amino group bonded to the heterocyclic ring is a group represented by the following chemical formula 2. Embedded image (Where Z represents S, O, NH or CH ₂ ) 4. The vinyl alcohol-based polymer (A) according to claim 1, and a polyvalent epoxy compound, an aldehyde compound, a polyvalent isocyanate compound,
A resin composition comprising at least one water-resistant agent (B) selected from an amino resin, a phenol resin and di (meth) acrylamide.