JPH1149913A - Water-resistant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in resistance to both cold water and hot water and not problematic in viscosity stability, etc., by mixing a vinyl alcohol polymer having phenyl-bonded amino groups with a water-soluble oxidizing agent. SOLUTION: The vinyl alcohol polymer (A) used is represented by formula I or II (wherein R<1> to R<5> are each H, an 8C or lower hydrocarbon group; A is a divalent hydrocarbon group or a divalent hydrocarbon group having at least one kind of N, O or S atoms; and X is a monovalent group having a phenyl-bonded amino group). The content of structural units X is 0.01-30 mol.%. Further, the viscosity-average degree of polymerization is 50-10,000. The water- soluble oxidizing agent (B) is exemplified by ammonium persulfate. The mixing ratio component A/component B is 99.99/0.01 to 10/90. If necessary, this composition may contain a polyepoxy compound (e.g. bisphenol a diglycidyl ether), a formaldehyde compound (e.g. formaldehyde) or a polyisocyanate compound (e.g. TDI).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising a specific polyvinyl alcohol resin and having excellent water resistance.

[0002]

2. Description of the Related Art Conventionally, vinyl alcohol-based polymers (hereinafter, vinyl alcohol-based polymers may be abbreviated as PVA) have been widely used as various kinds of binders, adhesives or surface treatment agents. Is known to have excellent performance unmatched by other water-soluble resins. However, because PVA is water-soluble,
There is a disadvantage that the water resistance, particularly when dried at a low temperature, is low, and various methods for improving this defect have been conventionally studied. 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 this way P
In order to make VA sufficiently water resistant, the temperature should be 100 ° C. or higher, especially 12 ° C.
It is necessary to heat-treat at a high temperature of 0 ° C. or more for a long time.
It is also known to use strongly acidic conditions such as pH 2 or less in order to make water resistant by drying at low temperature, but in this case, the viscosity stability of the PVA aqueous solution is poor and gelation occurs during use. In addition to having problems, it has a drawback that water resistance is insufficient. Further, a method of crosslinking a carboxylic acid-containing PVA with a polyamide epichlorohydrin resin, a method of crosslinking an acetoacetyl group-containing PVA with a polyhydric aldehyde compound such as glyoxal, and the like are also known. However, even with these methods, water resistance is insufficient. This has problems such as poor viscosity stability of the PVA aqueous solution.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for drying or heat-treating from room temperature to a low temperature of about 50.degree. Another object of the present invention is to provide a water-resistant composition free from problems such as the above.

[0004]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a vinyl alcohol-based polymer having an amino group (hereinafter abbreviated as an aromatic amino group) bonded to a phenyl group. It has been found that a composition comprising the coalesced (A) and the water-soluble oxidizing agent (B) is a composition that solves the above problems. Furthermore, the present invention has found that when such a composition further contains at least one compound (C) selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound, the water resistance is further improved, The present invention has been completed based on those findings.

That is, the present invention is a composition mainly comprising a vinyl alcohol polymer having an amino group bonded to a phenyl group and a water-soluble oxidizing agent.

Further, the present invention provides a polyepoxy compound,
The above-mentioned water-resistant composition further containing at least one compound selected from aldehyde compounds and polyvalent isocyanate compounds is included in the scope of the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The structure of the PVA having an aromatic amino group constituting the composition of the present invention is not particularly limited as long as it is a vinyl alcohol polymer having an amino group bonded to a phenyl group. Specific examples thereof include PVA having a structural unit represented by Chemical Formula 3 or 4 below, PVA having an amino group bonded to a phenyl group obtained by acetalizing PVA with an aldehyde having an aromatic amino group,
Examples include PVA having a vinyl aminobenzoate unit, and among them, PVA having a structural unit represented by the following chemical formula 3 or 4 is most suitable.

[0008]

Embedded image

[0009]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms, and A is a divalent At least one hydrocarbon group or at least one nitrogen, oxygen or sulfur atom
Represents a divalent hydrocarbon group containing species, S represents a sulfur atom,
X represents a monovalent group containing an amino group bonded to a phenyl group. )

R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the structural unit represented by Chemical Formula 3 or Chemical Formula 4 may have a hydrogen atom or a substituent having 8 or less carbon atoms. There is no particular limitation as long as it is a hydrocarbon group, but R ¹ is a hydrogen atom,
² is a hydrogen atom or a methyl group, and R ³ , R ⁴ and R ⁵ are preferably 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. A in the structural unit represented by Chemical Formula 4 is a divalent hydrocarbon group or a nitrogen atom,
The structure is not particularly limited as long as it is a divalent hydrocarbon group containing at least one oxygen atom or sulfur atom. For example,-(CH2) n- (n = 1 to 10, preferably 1 to 8),- C
H2OCH2-, -OCH2-, -CONH-ph
-OCH2-, -CONHCH2-, -CONHCH
2 OCH2-, -CONHCH2 OCH2 CH2
-, -CONHCH2 OCH2 CH2 CH2-,-
CONHCH2 OCH2 CH2 CH2 CH2-,
—CONHCH 2 —ph (CH 3) 2 —CH 2 — and the like. (Note that ph represents a phenyl group.) X in the structural unit represented by Chemical Formula 3 or Chemical Formula 4 is not particularly limited as long as it is a monovalent group containing an amino group bonded to the phenyl group. But, for example, -ph-NH2
(1,2-), -ph-NH2 (1,3-), -ph-
NH2 (1,4-), -CH2-ph-NH2 (1,
2-), -CH2-ph-NH2 (1,3-), -C
H2-ph-NH2 (1,4-), -CH2 CH2
-Ph-NH2 (1,2-), -CH2CH2-ph
-NH2 (1,3-), -CH2CH2-ph-NH
2 (1,4-), -ph (CH3) -NH2 (1,
2,3-), -ph (CH3) -NH2 (1,2,4
-, -Ph (CH3) -NH2 (1,2,5-),-
ph (CH3) -NH2 (1,2,6-), -nph
-NH2 (1,2-), -nph-NH2 (1,4
-), -Nph-NH2 (1,8-) and the like.
(In addition, ph means a phenyl group, and nph means a naphthalene group.)

The content of the structural unit containing an amino group bonded to a phenyl group is 0.01 to 30 mol%, and the distribution of the structural unit in the polymer is not particularly limited. When the content of the structural unit is O. If the amount is less than 1 mol%, the effect of introduction is not sufficiently exhibited, and if it exceeds 30 mol%, a problem (eg, gelation) occurs in the storage stability of the water-resistant composition. A more preferred range for the content of the structural unit is 0.1.
02 to 20 mol%, and a particularly preferable range is 0.05 to 20 mol%.
１５15 mol%.

The viscosity-average degree of polymerization of PVA (hereinafter abbreviated as degree of polymerization) and the degree of saponification are appropriately selected according to the purpose.
There is no particular limitation. The degree of polymerization is usually 50 to 1000
0, preferably 100-7000, more preferably 10
0 to 5000. The degree of saponification is at least 50 mol%, preferably at least 70 mol%. Saponification degree 50
If it is lower than mol%, the water solubility will decrease.

The water-soluble oxidizing agent (B) constituting the composition of the present invention includes persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, and the like. Cumene hydroperoxide, t-butyl hydroperoxide, potassium bromate, t-butyl peracetate, t-butyl benzoate, and the like. One or more of these water-soluble oxidizing agents may be used. Can be.

Further, in the water-resistant composition of the present invention,
If necessary, at least one compound (C) selected from a polyepoxy compound, an aldehyde compound and an isocyanate compound may be contained. When the water-resistant composition of the present invention contains at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and an isocyanate compound, it is possible to further increase the water resistance of the composition. In this case, the polyhydric epoxy compound, aldehyde compound and isocyanate compound may be any compound which can be easily mixed with the water-resistant composition of the present invention in the form of a solution and / or an emulsion and does not significantly inhibit the storage stability of the composition. Any of them can be used. Such polyepoxy compounds 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, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, epoxy Glycidyl ether type such as urethane resin; glycidyl ether / ester type such as P-oxybenzoic acid glycidyl ether / ester; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahexaphthalate, diglycidyl acrylate Glycidyl ester type such as glycidyl ester and dimer acid diglycidyl ester; glycidyl aniline, Glycidylamine type such as laglycidyl diaminodiphenylmethane, triglycidyl isocyanurate and triglycidylaminophenol; linear aliphatic epoxy resin such as epoxidized polybutadiene and epoxidized soybean oil; 3,4 epoxy-6-methylcyclohexylmethyl-3,4 Epoxy-6 methylcyclohexanecarboxylate, 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, Screw (2, 3
-Epoxycyclopentyl) ethers, alicyclic epoxy resins such as limonene dioxide, polyamide epichlorohydrin and the like.

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 polyvalent isocyanate compounds include tolylene diisocyanate (TDI); hydrogenated TDI; MDI); hydrogenated MDI; polymerized MDI; hexamethylene diisocyanate; xylylene diisocyanate; 4,4-dicyclohexylmethane diisocyanate;
And isophorone diisocyanate. Isocyanates dispersed in water using emulsifiers can also be used.

At least one compound selected from polyhydric epoxy compounds, aldehyde compounds and isocyanate compounds may be used alone or in combination of two or more.

In the composition of the present invention, the weight ratio (A) / (B) of the PVA (A) having an aromatic amino group and the waterproofing agent (B) is 99.99 / 0.01 to 10 /. 90
And preferably 99.9 / 0.1 to 70/30. When (A) / (B) is more than 99.99 / 0.01, the water-resistant effect is low, and when it is less than 10/90, the viscosity stability of the water-resistant composition is reduced.

The amount of at least one compound (C) selected from a polyepoxy compound, an aldehyde compound and an isocyanate compound depends on the use of the water-resistant composition and the type and amount of other components used in the water-resistant composition. When at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and an isocyanate compound is added, the aromatic amino group-containing PVA 10
With respect to 0 parts by weight, it is preferable to set the amount to 1 to 200 parts by weight from the viewpoint of water resistance and storage stability of the composition,
More preferably, the content is 3 to 100 parts by weight.

The PVA having an aromatic amino group having a structural unit represented by Chemical formula 3 or Chemical formula 4 used in the present invention.
Is obtained by reacting a polymer obtained by copolymerizing a monomer having an epoxy group and a vinyl ester-based monomer with a mercaptan having an aromatic amino group, followed by saponification.

As a method for copolymerizing a monomer having an epoxy group and a vinyl ester-based monomer, known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. Above all, a bulk polymerization method or a solution polymerization method in which polymerization is carried out without a solvent or in a solvent such as an alcohol is usually employed, and when a polymer having a high degree of polymerization is obtained, an emulsion polymerization method is employed. Examples of the alcohol used as a solvent during the solution polymerization include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol.
Examples of the initiator used for the copolymerization include, for example, α, α ′
-Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, n- Known initiators such as azo initiators such as propyl peroxycarbonate and peroxide initiators are exemplified. The polymerization temperature is not particularly limited, but is preferably in the range of -30 to 150 ° C.

The reaction between the epoxy group of the polymer composed of the monomer having an epoxy group and the vinyl ester monomer and the mercaptan having an aromatic amino group is carried out without solvent or in a solvent such as an alcohol in the presence of triethylamine, The reaction is performed using an alkali such as diethanolamine and sodium hydroxide as a catalyst. The reaction temperature is not particularly limited,
A range of 30 to 150C is suitable. Examples of the vinyl ester monomer used in the above method include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like. In general, vinyl acetate is used.

The modified polyvinyl ester-based polymer obtained by the above method may be composed of only a monomer having an epoxy group and a vinyl ester-based monomer, or may impair the effects of the present invention. A copolymerizable ethylenically unsaturated monomer may be copolymerized within a range not present. Ethylenically unsaturated monomers include ethylene, propylene,
Olefins such as butene and isobutene; acrylic acid, methacrylic acid, crotonic acid, (phthalic anhydride) phthalic acid,
Unsaturated acids such as (anhydride) maleic acid and (anhydride) itaconic acid or salts thereof or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, 1 to 1 carbon atoms
18 acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; methacrylamide, having 1 to 18 carbon atoms N-
Methacrylamides such as alkyl methacrylamide, N, N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; N-vinylpyrrolidone, N- N-vinyl amides such as vinyl formamide and N-vinyl acetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl ethers such as alkyl vinyl ether having 1 to 18 carbon atoms, hydroxyalkyl vinyl ether and alkoxyalkyl vinyl ether; vinyl chloride; Vinyl halides such as vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxy vinyl silane; allyl acetate;
Allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonate and the like can be mentioned.

Examples of the monomer having an epoxy group include allyl glycidyl ether, methacryl glycidyl ether, butadiene monoepoxide, 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) propylmethacrylamide, 4-acrylamidophenylglycidyl ether, 3-acrylamidophenylglycidylether , 4-methacrylamidophenyl glycidyl ether, 3-methacrylamidophenyl glycidyl ether, N-glycidoxymethyl acrylamide, N-glycidoxymethyl methacrylamide, N-glycidoxyethyl acrylamide, N-glycidoxyethyl methacrylamide , N-glycidoxypropylacrylamide,
N-glycidoxypropyl methacrylamide, N-glycidoxybutyl acrylamide, N-glycidoxybutyl methacrylamide, 4-acrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, 4-methacrylamidomethyl-2,5 -Dimethyl-phenylglycidyl ether, acrylamidopropyldimethyl (2,3-epoxy)
Propyl ammonium chloride, methacrylamidopropyl dimethyl (2,3-epoxy) propyl ammonium chloride, glycidyl methacrylate and the like are used.

The mercaptan having an aromatic amino group to be added to the epoxy group of the modified polyvinyl ester polymer is a compound having a mercapto group and an amino group bonded to an aromatic ring. For example, 2-aminothiophenol, 3
-Aminothiophenol, 4-aminothiophenol,
2- (N-methyl) aminothiophenol, 3- (N-
Methyl) aminothiophenol, 4- (N-methyl) aminothiophenol, 2- (NN-dimethyl) aminothiophenol, 3- (NN-dimethyl) aminothiophenol, 4- (NN- Dimethyl) aminothiophenol and the like, and esters thereof such as acetic acid ester and benzoic acid ester can also be used.

It is essential that the composition of the present invention contains PVA (A) having an aromatic amino group and a water-soluble oxidizing agent (B). And other water-soluble resins or aqueous polymer dispersions. As a solvent, water is preferably used, and a solvent such as various alcohols, ketones, dimethylformamide, and dimethylsulfoxide can be used in combination. As additives, various antifoaming agents, various dispersants, nonionic or anionic surfactants,
Examples include 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 carboxymethyl cellulose and hydroxyethyl cellulose, poly (meth) acrylic acid, polyhydroxy (meth)
Acrylate or copolymer thereof, (meth) acrylic polymer such as polyacrylamide, polyvinylpyrrolidone or copolymer thereof, carboxyl group-containing modified PVA sulfate group-containing modified PVA, sulfonic acid group-containing modified PVA, phosphate group-containing modified Examples include PVA derivatives such as PVA and quaternary ammonium base-containing modified PVA, and 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 composition of the present invention is suitably used as an overcoat agent for paper, especially a thermal paper overcoat agent which cannot be heat-treated at high temperature, by taking advantage of film forming properties, film strength and water resistance at low 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 paint, and a treatment agent (for example, a surface coating agent) for an inorganic material or an organic material. Furthermore, it can be used for molded products such as films, sheets, and fibers. Furthermore, it can be widely used in applications where a water-soluble resin has been conventionally used.

The composition of the present invention is usually used by dissolving or dispersing in water or water containing the above-mentioned organic solvent.
For example, when used as a paper overcoat agent, PVA (A) having an aromatic amino group and a water-soluble oxidizing agent (B) may be mixed and applied, or the component (B) may be applied to the paper surface in advance. Then, the component (A) may be applied thereafter. When used for an adhesive, component (A) and component (B)
May be mixed and applied to the surface to be adhered, or the component (B) may be applied in advance to one of the surfaces to be applied, and the component (A) applied to the other surface in advance. May be used. 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 of subsequently reacting the component (B) with the component (A). Good.

[0030]

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 examples, unless otherwise noted.
“%” And “parts” mean “% by weight” and “parts by weight”, respectively.

<< Synthesis Example 1 >> (PVA containing aromatic amino group)
(1) A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 405 parts of vinyl acetate monomer, 11 parts of allyl glycidyl ether and 30 parts of methanol, and nitrogen gas was bubbled for 15 minutes. And degassed. Separately, an initiator solution prepared by dissolving 4.5 parts of 2,2-azoisobutyronitrile in 15 parts of methanol was prepared, and nitrogen was replaced by bubbling with nitrogen gas. Start heating the reactor,
When the internal temperature reached 60 ° C., a separately adjusted initiator solution was added to initiate polymerization. After polymerization at 60 ° C. for 4 hours, the polymerization was stopped by cooling. The solid concentration at this time is 5
It was 4.8%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution of polyvinyl acetate copolymer (concentration: 44.5%). A portion 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. The purified polymer was subjected to proton NMR (model GSX-27, manufactured by JEOL Ltd.) using CDCl3 as a solvent.
0) The measurement and intrinsic viscosity measurement in acetone (JIS) were performed to calculate the viscosity average molecular weight. The viscosity average molecular weight containing 2.1 mol% of allyl glycidyl ether units (epoxy group-containing units) was 80 × 10 ^3. Was a polyvinyl acetate copolymer.

(2) In a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, a methanol solution of the polymer having an epoxy group obtained in Synthesis Example 1 (concentration: 44.5%)
After 100 parts were weighed and nitrogen gas was bubbled for 15 minutes, a solution prepared by dissolving 8.0 parts of 2-aminothiophenol and 0.03 part of sodium hydroxide in 48 parts of methanol was charged. After reacting at 50 ° C. for 2 hours with stirring, 40
After cooling to 0 ° C., 40 parts of a 10% methanol solution of sodium hydroxide was added to perform saponification. After leaving at 40 ° C. for 5 hours, pulverized, neutralized by adding 8 parts of acetic acid, washed with methanol using a Soxhlet extractor for 48 hours or more, and dried at 60 ° C. for 20 hours or more.
A modified PVA was obtained. When the modified PVA was measured by IR and proton NMR (d6-DMSO), the epoxy group had completely disappeared, the introduction of 2.1 mol% aniline group was confirmed, and the vinyl alcohol content was 97.0 mol. %Met. Further, a 4% DMSO solution of the PVA was prepared, and the viscosity was measured at 20 ° C., and it was 61.2 cp.

Example 1 Ammonium persulfate was added to and dissolved in 100 parts of a 10% aqueous solution of an aromatic amino group-containing PVA obtained in Synthesis Example 1 to prepare a 10% aqueous solution of a water-resistant composition. This solution was cast and dried at 20 ° C. to obtain a sheet. After immersing the obtained sheet in water (20 ° C.) for 24 hours, the degree of swelling (weight after immersion in water / absolute dry weight) was measured. The degree of swelling in water of the sheet material was twice, and a firm film state was maintained. The obtained sheet was heat-treated at 60 ° C. and 120 ° C. for 10 minutes, and the degree of swelling was measured in the same manner as described above. The degree of swelling is twice as high as 20 ° C
It was found that the waterproofing was completed. Table 1 shows the results.

Example 2 The procedure of Example 1 was repeated, except that the oxidizing agent ammonium persulfate used in Example 1 was replaced with hydrogen peroxide. The results are shown in Table 1.

Example 3 To 100 parts (solid content) of the water-resistant composition prepared in Example 1, 5 parts of ethylene glycol diglycidyl ether was further added and dissolved. This solution was cast, and the degree of swelling in water of the sheet was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The procedure of Example 3 was repeated, except that the ethylene glycol diglycidyl ether used in Example 3 was replaced with a 40% aqueous glyoxal solution. The results are shown in Table 1.

Example 5 The procedure of Example 3 was repeated, except that the ethylene glycol diglycidyl ether used in Example 3 was replaced with a water-dispersible polyvalent isocyanate compound (manufactured by Nippon Polyurethane Industry, trade name: Coronate C-3053). Was. The results are shown in Table 1.

Comparative Example 1 In place of the aromatic amino group-containing PVA used in Example 1,
The procedure was performed in the same manner as in Example 1 except that unmodified PVA (manufactured by Kuraray, trade name: PVA-110; polymerization degree: 1000, saponification degree: 98.5 mol%) was used. The results are shown in Table 1.

Comparative Example 2 In place of the aromatic amino group-containing PVA used in Example 1,
The procedure was performed in the same manner as in Example 2 except that unmodified PVA (manufactured by Kuraray, trade name: PVA-110; degree of polymerization: 1000, degree of saponification: 98.5 mol%) was used. The results are shown in Table 1.

Comparative Example 3 A saponification degree of 9 obtained by saponifying a copolymer of itaconic acid and vinyl acetate in place of the modified PVA used in Example 1.
A carboxylic acid-modified PVA having a molar ratio of 8.0 mol%, a degree of polymerization of 1000 and a modification amount of 2 mol% was used, and instead of ammonium persulfate used in Example 1, polyamide epichlorohydrin (manufactured by Nippon PMC) was added at the compounding ratio shown in Table 1. Except using, it carried out similarly to Example 1. The results are shown in Table 1.

Comparative Example 4 10% aqueous solution of acetoacetyl group-modified PVA having a saponification degree of 98.0 mol%, a polymerization degree of 1000 and a modification amount of 5 mol%
The procedure was performed in the same manner as in Example 1 except that 5 parts of glyoxal was added to 0 parts. Table 1 with the results
Shown in

[0042]

[Table 1]

[0043]

As is clear from the above examples, the composition of the present invention is remarkably excellent in water resistance even when treated at room temperature.

Claims (3)

[Claims] 1. A composition comprising a vinyl alcohol polymer having an amino group bonded to a phenyl group (A) and a water-soluble oxidizing agent (B). 2. The composition according to claim 1, wherein the vinyl alcohol polymer having an amino group bonded to a phenyl group is a vinyl alcohol polymer having the following structural unit. Embedded image Embedded image (Where R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms, and A is a divalent hydrocarbon group Or a nitrogen atom,
It represents a divalent hydrocarbon group containing at least one oxygen atom or sulfur atom, S represents a sulfur atom, and X represents a monovalent group containing an amino group bonded to a phenyl group. ) 3. The composition according to claim 1, further comprising at least one compound (C) selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound.
A composition as described.