JP2001139751A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-resistant composition having good water resistance not only to cold water, but also to warm water, without problems such as viscosity stability and without problems about safely when dried or heat-treated at <=70 deg.C, particularly at nearly room temperature to 50 deg.C, further at a relatively low temperature such as about room temperature after forming a film or applying to a substrate. SOLUTION: This water-resistant composition comprises (A) a vinyl alcohol- based polymer having 0.01-1 mol% silyl group and (B) an organic titanium compound at (99.99/0.01) to (60/40) weight ratio of the component A to the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having good water resistance comprising a vinyl alcohol polymer having a silyl group and an organic titanium compound.

[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 studied. For example, PVA is glyoxal,
A method of crosslinking with glutaraldehyde or dialdehyde starch, a water-soluble epoxy compound, a methylol compound, or the like is known. However, in order to make PVA sufficiently water-resistant by this method, it is necessary to perform heat treatment at a high temperature of 100 ° C. or more, particularly 120 ° 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. In addition, there is a problem that the use of such severe conditions causes the PVA to be colored, thereby impairing the appearance of the film. Further, a method of crosslinking carboxyl group-containing PVA with a polyamide epichlorohydrin resin and a method of crosslinking acetoacetyl group-containing PVA with a polyhydric aldehyde compound such as glyoxal are also known. Requires a large amount of polyamide epichlorohydrin,
The latter has high water resistance but has problems such as extremely poor viscosity stability of the PVA aqueous solution. Use of polyamide epichlorohydrin or polyhydric aldehyde is not preferable from the viewpoint of safety. Also, PVA
There is also known a method of imparting water resistance by blending titanium lactate with an aqueous composition containing (Japanese Patent Laid-Open No. 49-947).
No. 68), when the composition is molded or coated on a substrate and then treated at a relatively low temperature around room temperature, as described in Comparative Example 1 described later, sufficient water resistance such as collapse of the sheet in boiling water is obtained. However, there is a problem that the PVA aqueous solution containing titanium lactate also has poor stability at low temperature storage.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to dry or heat-treat at a relatively low temperature of 70 ° C. or less, particularly around room temperature to 50 ° C., and further around room temperature, after film formation or coating on a substrate. Even in the case of providing a water-resistant composition having good water resistance not only to cold water but also to warm water, having no problems such as viscosity stability, and having no problem in terms of safety. is there.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a silyl group has a content of 0.01%.
(A) and an organotitanium compound (B) having a mole ratio of (A) / (B) of 99.99 / 0. 0
It has been found that a composition having a ratio of 1 to 60/40 solves the above-mentioned problems, and has completed the present invention.

The present inventors have also found that when the vinyl alcohol polymer (A) has a silyl group having the structure shown in the following chemical formula 2, the effect of the present invention is remarkably improved.

[0006]

Embedded image

Wherein R 1 represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms which may have a substituent;
R2 represents an alkoxyl group or an acyloxyl group having 1 to 40 carbon atoms (where the alkoxyl group and the acyloxyl group may have a substituent containing oxygen), and n + m
Is 3 or less, n is an integer of 0 to 2, m is an integer of 0 to 3, and X represents a monovalent metal. Monovalent metals include sodium and potassium, which are mainly introduced during saponification.

[0008] The silyl group represented by the formula (2) is present on the side chain or terminal of PVA (A), and the silyl group and PVA (A)
A linking group that is not cleaved at the time of saponification may be interposed between the side chains or terminals.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A vinyl alcohol polymer having a silyl group is used for synthesizing the vinyl alcohol polymer described above, and for polymerizing a vinyl ester monomer at the time of the polymerization to form a silyl group represented by the above formula (2). Is carried out in the presence of an olefinically unsaturated monomer having a group capable of forming a silyl group represented by the above-mentioned formula after polymerization or saponification, and the obtained silyl group-containing vinyl ester copolymer is obtained. Obtained by saponification.

Specific examples of the olefinically unsaturated monomer having a silyl group having the structure shown in Chemical Formula 2 above or having a group capable of forming a silyl group having the structure shown in Chemical Formula 2 after polymerization or saponification are shown below. Is, for example, vinyltrimethoxysilane, vinyltris- (β-methoxyethoxy) silane,
Allyltrimethoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxy Silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl trihexyloxy silane, vinyl methoxy dihexyloxy silane, vinyl dimethoxy octyloxy silane, vinyl methoxy dioctyloxy silane,
Vinyltrioctyloxysilane, vinylmethoxydilauroxysilane, vinyldimethoxylauryloxysilane, vinylmethoxydioleyloxysilane, vinyldimethoxyoleyloxysilane, 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide -Propyltriethoxysilane, 3- (meth)
Acrylamido-propyltri (β-methoxyethoxy) silane, 2- (meth) acrylamido-2-methylpropyltrimethoxysilane, 2- (meth) acrylamido-2-methylethyltrimethoxysilane, N- (2
-(Meth) acrylamido-ethyl) -aminopropyltrimethoxysilane, 3- (meth) acrylamido-propyltriacetoxysilane, 2- (meth) acrylamido-ethyltrimethoxysilane, 1- (meth) acrylamido-methyltrimethoxysilane , 3- (meth) acrylamido-propylmethyldimethoxysilane, 3-
(Meth) acrylamide-propyldimethylmethoxysilane, 3- (N-methyl- (meth) acrylamide)-
Propyltrimethoxysilane, 3-((meth) acrylamido-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth) acrylamido-methoxy) -propyltrimethoxysilane, dimethyl-3-
(Meth) acrylamido-propyl-3- (trimethoxysilyl) -propylammonium chloride, dimethyl-2- (meth) acrylamido-2-methylpropyl-3- (trimethoxysilyl) -propylammonium chloride, and the like, It is not limited to these.

As another method for obtaining the vinyl alcohol polymer (A) having a silyl group in the water-resistant composition of the present invention, for example, in the synthesis of the vinyl alcohol polymer described above, the polymerization of a vinyl ester is carried out. The reaction was carried out in the presence of a comonomer having an epoxy group such as allyl glycidyl ether or butadiene monoxide, and a compound having a mercapto group and a silane group in the same molecule was reacted with the obtained vinyl ester copolymer having an epoxy group. Post-saponification is performed to obtain a vinyl alcohol-based polymer. In the synthesis of a vinyl alcohol polymer, a compound having a mercapto group and a silyl group in the same molecule is polymerized as a chain transfer agent, and the obtained vinyl ester polymer is saponified to form a silyl group. (In this case, a terminal modified product) may be used as a vinyl alcohol-based polymer,
It is not limited to these.

It is important that the content of the silyl group is from 0.01 to 1 mol%, more preferably from 0.1 to 1 mol%. When the content of the silyl group is less than 0.01 mol%, the effect of the modification of the silyl group is small, and when the content is more than 1 mol%, the composition of the present invention cannot be obtained.

The degree of polymerization of the vinyl alcohol polymer (A) is not particularly limited, but is usually 50 to 10,000, more preferably 100 to 7000, and more preferably 15 to 10,000.
More preferably, it is 0 to 5000, and 200 to 400.
Particularly preferred is 0. Here, the degree of polymerization refers to JIS
It is measured according to K6726, and is determined from the intrinsic viscosity measured in water at 30 ° C. using a re-saponified and purified vinyl alcohol-based polymer. If the degree of polymerization is less than 50, the strength of the film when formed into a film may be significantly reduced. Those having a degree of polymerization exceeding 10,000 are difficult to synthesize.

The degree of saponification of the vinyl alcohol-based polymer (A) in the water-resistant composition of the present invention is not particularly limited, but is usually 75 to 99.99 mol%, and is preferably 80 to 9 mol%.
More preferably, it is 9.98 mol%, and 90 to 99.
More preferably, it is 97 mol%. If the saponification degree is lower than 65 mol%, the water solubility of the vinyl alcohol polymer (A) may be reduced. Saponification degree 9
If it is higher than 9.99 mol%, it is difficult to synthesize.

The vinyl alcohol polymer (A) contains 16
It has a melting point of 5C to 228C, preferably 180C to 227C, more preferably 190C to 225C. The melting point referred to here is 10 ° C./min. Represents the temperature at the peak top position of the endothermic curve obtained by performing the DSC measurement at the temperature rising rate. Factors that determine the melting point of PVA include the degree of saponification, the introduction of various modifications, and the polymerization temperature.

The vinyl alcohol-based polymer (A) can be obtained by various methods. Typically, as described above, a vinyl ester-based monomer and an olefinic unsaturated monomer having a silyl group are copolymerized. Later, it is obtained by saponification. Here, examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caproate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. However, vinyl acetate is usually preferably used. Known polymerization methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method are used as a polymerization method of the vinyl ester monomer, but a solution polymerization method using an alcohol such as methanol as a solvent is usually used. Used. The polymerization temperature is not particularly limited, but is usually arbitrarily selected between 0 ° C and 150 ° C. As a method for saponifying a vinyl ester polymer, various known methods can be used. Usually, sodium alcoholate, sodium hydroxide, potassium hydroxide, or the like is used in an alcohol solvent (which may contain a small amount of water). A saponification method using an alkali is used.

The vinyl alcohol-based polymer (A) in the water-resistant composition of the present invention has one or more other monomer units as long as the purpose of the present invention is not impaired. But it doesn't matter. Examples of such a unit include unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, (anhydride) maleic acid, and itaconic acid and salts thereof, or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide , Carbon number 1-18
Acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid and salts thereof, acrylamidopropyldimethylamine or salts thereof or quaternary salts thereof; methacrylamide, having 1 to 18 carbon atoms; Methacrylamides such as N-alkyl methacrylamide, N, N-dimethyl methacrylamide, 2-methacrylamidopropanesulfonic acid and salts thereof, methacrylamidopropyldimethylamine or acid salts or quaternary salts thereof; N-vinylpyrrolidone; N-vinylformamide,
N-vinylamides such as N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers; polyethylene glycol allyl ether, methoxy Allyl ethers having a poly (oxyalkylene) group, such as polyethylene glycol allyl ether, polypropylene glycol allyl ether, and polyethylene glycol-polypropylene glycol allyl ether; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, etc. Vinyl halides; allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, etc .; The present invention is not limited. The content of these monomer units is not particularly limited, as long as the resulting polymer is water-soluble, but the content of these components is usually preferably 10 mol% or less.

The vinyl alcohol-based polymer (A) in the water-resistant composition of the present invention can be reacted with a vinyl ester-based monomer in the presence of a thiol compound such as thiolacetic acid, mercaptopropionic acid, or alkylmercaptan having 18 or less carbon atoms. A modified product having a mercapto group or a carboxyl group at the terminal obtained by copolymerization with an olefinic unsaturated monomer having a silyl group and saponifying the copolymer may be used. In dissolving the PVA used in the present invention in water, a uniform aqueous solution is usually obtained by dispersing the PVA in water, optionally adding an alkali such as sodium hydroxide, and heating while stirring. Can be.

As the organotitanium compound (B) constituting the water-resistant composition of the present invention, a titanium compound having a chelate type ligand is suitable. Specifically, titanium lactate, its partial or complete neutralization (For example, titanium lactate monoammonium salt, titanium lactate diammonium salt, titanium lactate monosodium salt, titanium lactate disodium salt, titanium lactate monopotassium salt, titanium lactate dipotassium salt), ammonium salt diisopropoxytitanium bis (triethanol Aminate), di-n-butoxycytitanium bis (triethanol aminate), diisopropoxy titanium bis (acetylacetonate), titanium tetrakis (acetylacetonate), and polytitanium bis (acetylacetonate) are preferred. It is but tetraisopropoxytitanium, tetra -n- butoxy, also titanium tetra stearyl rate can be used. Among these organic titanium compounds, water-soluble ones are preferable. Specifically, titanium lactate, titanium lactate ammonium salt, diisopropoxytitanium bis (triethanol aminate),
Di-n-butoxytitanium bis (triethanol aminate). These organic titanium compounds do not necessarily have to be used alone, and may be used as a mixture of two or more as necessary. Here, the chelate-type ligand means a ligand capable of coordinating one titanium atom in a bidentate or more polydentate by a covalent bond or a hydrogen bond, As the ligand, hydroxycarboxylic acid or a salt thereof (lactic acid, malic acid, tartaric acid,
Typical examples include salicylic acid or salts thereof), β-diketone (eg, acetylacetone), and amino alcohol (eg, triethanolamine).
It is not limited to these.

In the water-resistant composition of the present invention, PVA
The weight ratio [(A) / (B)] of (A) and the organic titanium compound (B) is 99.99 / 0.01 to 60/4.
0, preferably 99.99 / 0.01 to 80/2
0, more preferably 99.97 to 85/15, and most preferably 99.95 / 0.05 to 90/10. When (A) / (B) is more than 99.99 / 0.01, the water-proofing effect is low, and when it is less than 60/40, the aqueous solution viscosity stability and strength of the water-resistant composition are reduced, which is preferable. Absent.

As described above, in the present invention, PVA (A) having a silyl group in an amount of 0.01 to 1 mol% and an organic titanium compound, preferably an organic titanium compound (B) having a chelate type ligand are used. The specific PVA (A) and the organotitanium compound (B) are mixed uniformly, and the specific weight ratio, that is, [(A) / (B)] is 99.99 /
By using at a ratio of 0.01 to 60/40,
After coating the composition comprising (A) and (B) on a substrate,
Alternatively, even if the film is treated at a relatively low temperature after film formation, that is, at 70 ° C. or lower, particularly around room temperature to 50 ° C., and even around room temperature, it exhibits excellent water resistance, especially boiling water resistance, and (A)
It is surprising that the aqueous solution obtained by homogeneously mixing C and B shows excellent low temperature storage viscosity stability.

As described above, the water-resistant composition of the present invention comprises the vinyl alcohol polymer (A) and the organotitanium compound (B), and the weight ratio of (A) to (B) is (A) / ( It is an essential condition that B) = 99.99 / 0.01 to 60/40, but a solvent, various additives, another water-soluble resin, a polymer aqueous dispersion, or the like is contained depending on the application. be able to. 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 dispersants, nonionic or anionic surfactants, silane coupling agents, pH regulators, and fillers such as calcium carbonate, clay, talc, and flour. As the water-soluble resin, carboxymethyl cellulose,
Cellulose derivatives such as hydroxyethylcellulose, poly (meth) acrylic acid, polyhydroxy (meth) acrylate or copolymer thereof, (meth) acrylic polymers such as polyacrylamide, polyvinylpyrrolidone or copolymer thereof, carboxyl group-containing modification PVA, modified PVA containing sulfate group, modified PVA containing sulfonic acid group, modified PVA containing phosphate group, modified P containing quaternary ammonium base
Examples thereof include PVA derivatives such as VA, 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.

In the present invention, it is important that the component (A) and the component (B) are a homogeneously mixed composition. As a method of mixing uniformly, the component (A) and the component (B) are used. Are dissolved or dispersed in a solvent, preferably water, or a method of mixing an aqueous solution of the component (A) with an aqueous solution of the component (B). Modified PVA (A)
When the molded product of (1), for example, a film is immersed in an aqueous solution of an organotitanium compound (B) having a chelate type ligand, the components (A) and (B) do not mix uniformly. A molded article having excellent water resistance cannot be obtained.

By drying or heat-treating the composition of the present invention at a low temperature such as around room temperature, a sufficient water resistance effect can be obtained not only for cold water but also for warm water or hot water. Although it does not require processing at high temperatures,
There is no problem to perform drying or heat treatment at a high temperature in order to obtain a higher water resistance effect. However, in this case,
It is not preferable to perform the treatment at an extremely high temperature because, in rare cases, the coating of the composition or the like may cause coloring,
Usually, a heat treatment at about 70 ° C. is sufficient. The composition of the present invention makes use of film forming properties at low temperatures, film strength or water resistance, and uses an adhesive or binder for inorganic or organic substances, a vehicle for coating, a treating agent for inorganic or organic materials, for example, a surface coating agent, especially Effectively used for thermal paper overcoating agents that cannot be heat treated at high temperatures. In addition, dispersants such as pigment dispersions, polymerization stabilizers for crosslinkable emulsions, image forming materials such as gelatin blends or photosensitive resins, base materials for hydrogels such as cell-fixed gels or enzyme-fixed gels, It can be widely used in applications where the conductive resin was used. 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 dissolved or dispersed in water or water containing the aforementioned organic solvent, and is preferably used as an aqueous dispersion. The composition of the present invention may be used as a mixture of the component (A) and the component (B), or a method of subsequently allowing the component (B) to act on the component (A) may be used.

[0026]

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.

Swelling degree and dissolution rate of sheet material The swelling degree and dissolution rate of the sheet material in the following examples were calculated as follows. Swelling degree (fold) = b / (axe / d) Elution rate (%) = [{(axe / d) -c} / (ax)
e / d)] × 100 a: Weight (g) of sheet before immersion b: Weight (g) of sheet pulled up after immersion in water at 20 ° C. for 24 hours c: 24 hours in water at 20 ° C. Pull up after immersion, 105 ℃
(G) after drying for 24 hours at d: Weight (g) of sheet cut separately d: Weight (g) after drying the sheet cut at d at 105 ° C. for 24 hours

Synthesis Example of Modified PVA Having Silane Group In a 5 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet and a thermometer, 1050 g of vinyl acetate monomer was added.
4.5 g of vinyltrimethoxysilane and methanol 1
950 g was charged, and nitrogen gas was bubbled for 30 minutes to degas. When the temperature of the reactor was raised and the internal temperature reached 60 ° C., 2,2′-azobis (isobutyronitrile)
0.3 g was added to initiate polymerization. After polymerization at 60 ° C. for 5 hours, the polymerization was terminated by cooling, followed by removal of unreacted vinyl acetate monomer while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution of a polyvinyl acetate copolymer. I got Next, to a methanol solution of PVAc adjusted to 25%, a NaOH methanol solution (10% concentration) having a molar ratio of {number of moles of NaOH / number of moles of polyvinyl acetate (PVAc)} 0.01 was added and saponified. The saponification degree of the obtained modified PVA (PVA-2) was 94.2 mol%. An aqueous solution in which a part of the obtained PVA was dissolved in a small amount of water was cast to form a PVA thin film. After washing this thin film with methanol soxhlet for 3 days, it was dried at 65 ° C. overnight in a hot air drier, and subjected to DSC measurement (heating rate 10 ° C./min.).
The melting point of A-1 was 202 ° C.

A methanol solution of PVAc obtained by polymerization and removal of unreacted vinyl acetate monomer is precipitated in n-hexane, and reprecipitated and purified by dissolving in acetone three times.
It dried under reduced pressure at ° C, and obtained purified PVAc. 1 of the PVAc
The amount of vinyltrimethoxysilane modification determined by 1 H NMR measurement was 0.55 mol%. After saponifying the above methanol solution of PVAc at an alkali molar ratio of 0.2, methanol Soxhlet was performed for 3 days, and then dried to obtain purified PVA. The average degree of polymerization of the PVA was determined by a conventional method of JI.
It was 500 when measured according to SK6726.

Example 1 PVA-1 was dissolved in water to prepare a 5% aqueous solution. To 100 parts of this aqueous PVA solution, 2 parts of TC-310 (a 45% solution of titanium lactate manufactured by Matsumoto Pharmaceutical Co., Ltd.) (0.9 parts as pure titanium lactate) was added to prepare a 5% aqueous solution of a water-resistant composition. did. This solution was cast, and 20
Drying at 0 ° C. gave a colorless and transparent sheet. When the degree of swelling and the dissolution rate after immersing the obtained sheet in hot water at 50 ° C. for 24 hours were measured, the swelling degree was 18 times and the dissolution rate was 50%. Further, when the sheet was immersed in hot water in a boiling water bath for 1 hour and then pulled up, the sheet-like material maintained a firm shape and had no sliminess on the surface. Further, an aqueous solution of the composition prepared above was added at room temperature (about 20 ° C.) for 1 hour.
After standing for a week, the aqueous solution maintained fluidity and no gelation was observed.

Comparative Example 1 The degree of polymerization was 175 in place of PVA-1 used in Example 1.
0, PVA-5 having a saponification degree of 99.5 mol% (melting point: 23
1 ° C.) to obtain a sheet material in the same manner as in Example 1. This sheet was evaluated in the same manner as in Example 1. The sheet was disintegrated in warm water at 50 ° C., and when the aqueous solution of the composition was allowed to stand at room temperature, the solution gelled within one week.

Examples 2 to 4 and Comparative Examples 2 and 3 Examples 1 and 2 were the same as those of Example 1 except that the PVA-1 and TC-310 used in Example 1 and the amounts thereof were changed as shown in Tables 1 and 2. Performed similarly. Table 2 shows the results.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

As is evident from the above examples, the water-resistant composition of the present invention, after film formation or after coating on a substrate, has a temperature of 70 ° C. or less, especially around room temperature to 50 ° C., and furthermore, at room temperature. Even in the case of drying or heat treatment at a relatively low temperature such as near, it has good water resistance not only to cold water but also to hot water, there is no problem such as viscosity stability, and it is also excellent in safety. .

Claims (3)

[Claims] 1. A composition comprising a vinyl alcohol polymer (A) having a silyl group in an amount of 0.01 to 1 mol% and an organotitanium compound (B), and a weight ratio (A) of the components (A) and (B). / (B) is 99.99 / 0.01 to 60/40
A water-resistant composition. 2. The water-resistant composition according to claim 1, wherein the organic titanium compound is an organic titanium having a chelate type ligand. 3. The water-resistant composition according to claim 1, wherein the vinyl alcohol-based polymer (A) has a silyl group having a structure represented by the following chemical formula 1. Embedded image Here, R1 represents a hydrogen atom or an optionally substituted hydrocarbon group having 8 or less carbon atoms, and R2 represents an alkoxyl group or an acyloxyl group having 1 to 40 carbon atoms (here, an alkoxyl group, an acyloxyl group) The group may have a substituent containing oxygen), and n + m is 3 or less;
n represents an integer of 0 to 2, m represents an integer of 0 to 3, and X represents a monovalent metal. ｝