JP2710841B2 - Resin composition and adhesive composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition comprising a vinyl ester-based emulsion and a polyvalent metal compound, and an adhesive composition using the same. More specifically, the present invention relates to a resin composition comprising a vinyl ester-based emulsion having a specific polyvinyl alcohol (hereinafter abbreviated as PVA) -based block copolymer as a protective colloid and a polyvalent metal compound, and an adhesive composition using the same. It is.

B.Prior artVinyl ester emulsions using PAV as a protective colloid are widely used for adhesives, paints, mortar admixtures, etc. due to their good adhesiveness and excellent emulsion stability. Has been awarded. However, in recent years, a higher level of quality has been required for each application, and various modifications and modifications of emulsions have been added to meet the demand.

For example, in the use of adhesives, there is a demand for improvement in water resistance, heat resistance, and even initial adhesiveness, and as one method for achieving this, introduction of crosslinking is performed.

As a method for introducing the crosslinking, a method is known in which a functional group such as a carboxyl group is introduced into the emulsion and a polyvalent metal compound is combined. However, when a carboxyl group is introduced into a vinyl ester emulsion using PVA as a protective colloid, it is difficult to ensure the stability of the emulsion, and particularly the storage stability is poor, and there is a practical problem.

C. Means for Solving the Problems To solve the above problems, the present inventors have proposed a method for introducing a functional group such as a carboxyl group or an amide group into an emulsion without impairing the characteristics of the PVA protective colloid-based emulsion. As a result of intensive studies, the polymer of the vinyl compound represented by the general formula (I) and the polyvinyl alcohol-based polymer
In the presence of a PVA-based block copolymer, a vinyl ester-based emulsion characterized by being emulsified (co) polymerized with a monomer mainly composed of a vinyl ester is excellent in storage stability, etc. They also found that the reactivity was good, and completed the present invention.

Provided that R ¹ is hydrogen or a methyl group.

X is hydrogen, -COOM or -COOR ² (R ² is an alkyl group having 1 to 12 carbon atoms).

Y is -COOM (M is hydrogen, metal ion or N
^{_{H 4 +), - CONH 2}} , -CONHCH 2 OH, -CON (CH 3) 2, -SO 3
_{N, -C 6 H 5 SO 3} M (M is hydrogen, a metal ion or NH ₄ ^+).

 Hereinafter, the present invention will be described in detail.

PVA used as a protective colloid in the present invention
The block copolymer is a PVA block copolymer of a polymer of a vinyl compound represented by the general formula (I) and a PVA polymer.

As the vinyl compound of the general formula (I), it is preferable to use a vinyl compound having an amide group and a carboxyl group, and acrylamide, acrylic acid, and methacrylic acid are more preferable in terms of easiness of polymerization and economy.

There are no particular restrictions on the PVA polymer, but those having a degree of polymerization of 50 to 5,000, preferably 100 to 3,000, and a degree of saponification of 60 to 99.9 mol% are suitably used.

Further, among the PVA-based polymers, a PVA-based polymer having a mercapto group is particularly preferable.

As the PVA-based polymer having a mercapto group, a polymer having a mercapto group on the side chain of PVA may be used, but a polymer having a mercapto group at the terminal of PVA is particularly preferable. The PVA-based polymer is obtained by saponifying a polyvinyl ester-based polymer obtained by polymerizing a vinyl monomer mainly containing a vinyl ester monomer such as vinyl acetate in the presence of thiolic acid by a conventional method.

The PVA-based block copolymer of the present invention needs to be obtained by radical polymerization of a vinyl compound of the general formula (I) in a medium in which a PVA-based polymer having a mercapto group is dissolved.
Suitable media include water and dimethyl sulfoxide, but in consideration of the subsequent emulsion (co) polymerization step, an aqueous medium which eliminates the step of removing the solvent and isolating is most preferable.

The selection of the ratio of the PVA-based polymer having a mercapto group to the vinyl compound of the general formula (I) is important because the structure of the PVA-based block copolymer is directly related to the original design. If the ratio of the PVA-based polymer having a mercapto group to the vinyl compound of the general formula (I) is too low, the characteristics of the PVA-protected colloid emulsion in the resulting emulsion will be impaired. On the other hand, if the proportion of the vinyl compound of the general formula (I) is too low, it becomes difficult to use the functional groups. Further, the structure of the block copolymer greatly depends on the emulsion (co) polymerization formulation of a monomer mainly composed of a vinyl ester in the presence of the block copolymer, but has a great influence on the stability of the emulsion.

Therefore, it is necessary to select the ratio of the PVA-based polymer to the vinyl compound of the general formula (I) in accordance with the monomer composition in the emulsion (co) polymerization and the purpose of the final emulsion. [PVA polymer / vinyl compound of general formula (I)] = 20/80 to 95/5, preferably 30/80
It is necessary to select from the range of 70 to 90/10.

The vinyl compound of the general formula (I) may be a single vinyl compound or a combination of one or two kinds of vinyl compounds. Further, other vinyl compounds copolymerizable with the vinyl compound of the general formula (I) may be used in a small amount as long as the object of the present invention is not impaired.

Other copolymerizable vinyl monomers include, for example, acrylonitrile, methacrylonitrile, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, acrylic acid Examples include alkyl (meth) acrylates such as methyl, ethyl acrylate and methyl methacrylate, and vinyl esters such as vinyl acetate.

As the radical polymerization initiator for obtaining the PVA-based block copolymer of the present invention, for example, 2,2'-azobisbutyronitrile, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate,
Any of potassium persulfate, ammonium persulfate and hydrogen peroxide that is suitable for the polymerization system may be used, but polymerization in an aqueous system is preferred as described.In this case, the mercapto group at the terminal of the PVA polymer and the bromate are used. Potassium, potassium persulfate,
Redox initiation with an oxidizing agent such as ammonium persulfate or hydrogen peroxide is also possible, and among these, potassium bromate does not generate radicals alone under ordinary polymerization conditions, and redox with the mercapto group at the terminal of the PVA polymer. It is a particularly preferred initiator for synthesizing the block copolymer of the present invention because it decomposes and generates radicals only by the reaction.

In conducting the polymerization for obtaining the PVA-based block copolymer of the present invention, it is important and desirable that the polymerization system is acidic. This is because, when the mercapto group is basic, the rate of ionic addition and disappearance to the double bond of the vinyl compound is large, and the polymerization efficiency is significantly reduced. Is preferably carried out at pH 4 or less. The vinyl ester emulsion of the present invention is obtained by emulsifying (co) a monomer mainly composed of a vinyl ester in the presence of the PVA block copolymer obtained by the above method.
It is obtained by polymerization. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl versatate, with vinyl acetate being preferred.

As monomers other than vinyl esters, one or two kinds of monomers copolymerizable with vinyl esters may be used in combination. Examples of such monomers include olefins such as ethylene, propylene and isobutylene, vinyl chloride, vinyl fluoride, and vinylidene. Halogenated olefins such as chloride and vinylidene fluoride, acrylic acid, methyl acrylate which is an ester of methacrylic acid, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, methacrylic Methyl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and These quaternized, acrylamido-2-methylpropanesulfonic acid and acrylamide monomer of its sodium salt, styrene, alpha-
Examples include styrene-based monomers such as methylstyrene, p-styrenesulfonic acid and its sodium and potassium salts, and N-vinylpyrrolidone.

In the present invention, the selection of the ratio of the PVA-based block copolymer to the monomer mainly composed of vinyl ester is particularly important from the viewpoint of obtaining a stable emulsion and utilizing the functional groups of the emulsion.

First, in order to obtain a stable emulsion, the amount of the block polymer varies somewhat depending on the structure of the PVA-based block copolymer.
More than 0.5, preferably more than 2 parts should be used per 0 parts. If the amount of the PVA-based block copolymer is less than 0.5 part, it is difficult to stably obtain a practically high-emulsion emulsion having a high solid content.

On the other hand, from the viewpoint of utilizing the functional groups in the emulsion, it is preferable to use a large amount of the PVA-based block copolymer, but if the amount is too large, the water resistance will be increased even if a curing agent that reacts with the functional groups is added later. The problem of lowering occurs.

From the above, the amount of the PVA-based block copolymer used is 0.5 to 100 parts of the monomer mainly composed of vinyl ester.
Parts to 300 parts, preferably 2 parts to 200 parts.

The emulsion (co) polymerization reaction is carried out in an aqueous medium in the presence of a radical polymerization initiator. As a polymerization initiator, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutylnitrile, persulfate, hydrogen peroxide water or the like alone or sodium sulfite, triethanolamine, Rongalit, L-ascorbic acid It is used by forming a redox system with tartaric acid and the like.

The polymerization method is a method in which water, a PVA-based block copolymer, a monomer mainly composed of vinyl ester are charged at a time, and a part of the monomer mainly composed of vinyl ester is charged, polymerization is started, and then the remainder is polymerized. Or a method in which water, a PVA-based block copolymer, and a monomer mainly composed of a vinyl ester are mixed in advance, a part of this is charged, polymerization is started, and the rest is sequentially added to the polymerization system. Is also possible.

The vinyl ester emulsion obtained as described above has good standing stability, excellent mechanical stability, retains the characteristics of PVA protective colloid emulsion such as a large wet tack, and has a functional group. I have. Emulsions having functional groups such as amide groups, carboxyl groups and sulfonic acid groups have good adhesiveness to other substrates, and are useful alone for applications such as adhesives. By adding a compound having a polyvalent metal capable of reacting with the functional group, a so-called cross-linking agent, it is possible to form a cross-linked body.
Heat resistance and initial adhesion can be improved.

An object of the present invention is to provide a vinyl ester emulsion having a PVA-based block copolymer of a PVA-based polymer and the vinyl compound of the general formula (I) as a protective colloid, and a functional group of the vinyl compound of the general formula (I). It is an object of the present invention to provide an adhesive composition obtained by adding a polyvalent metal compound having a polyvalent metal capable of reacting with a polyvalent metal.

Examples of the polyvalent metal compound capable of reacting with the functional group of the vinyl compound of the general formula (I) include a zirconium compound, a zinc compound, a calcium compound, a barium compound, a strontium compound, a magnesium compound, and an aluminum compound. Zirconium compounds having a crosslinking effect are particularly preferred.

Examples of zirconium compounds include zirconyl hydrochloride, zirconyl sulfate, zirconyl nitrate, zirconyl carbonate, zirconyl hydroxide, zirconyl acetate, and zirconyl ammonium carbonate.

The mixing ratio of the vinyl ester emulsion and the polyvalent metal compound is 100% of the vinyl ester emulsion in terms of solid content.
The polyvalent metal compound is preferably 0.02 to 100 parts by weight, more preferably 0.2 to 50 parts by weight, based on parts by weight.

In addition, the resin composition of the present invention includes clay, calcium carbonate, talc, pigments such as aluminum hydroxide, additives such as an antifoaming agent, an antifungal agent, and PVA as long as the effects of the present invention are not impaired. It can also be used in combination with known adhesives such as starch and starch.

The adhesive composition of the present invention is useful as various adhesives such as various plastics such as vinyl chloride and celluloses such as wood and paper.

The adhesive compositions of the invention 2~500dry · g / m ^2, and more preferably about as used 10~300dry · g / m ² approximately coating amounts.

Further, the adhesive composition of the present invention can obtain good results by air drying or heat drying.

D. Examples The present invention will be described specifically with reference to the following examples.
The present invention is not limited by these.
In the examples, parts and% mean weight basis.

[Synthesis of PVA Polymer Having Mercapto Group at Terminal] Synthesis Example 1 2400 parts of vinyl acetate (hereinafter abbreviated as VAc), methanol 580
Part and thiolacetic acid 0.93 part in a reaction vessel, and after sufficiently purging the inside with nitrogen, raise the external temperature to 65 ° C and raise the internal temperature to 60 ° C.
At which point 20 parts of methanol containing 0.868 parts of 2,2'-azobisisoisobutyronitrile were added. Immediately, 60 parts of a methanol solution containing 17.4 parts of thiolacetic acid was uniformly added over 5 hours. The polymerization rate after 5 hours was 50.4%. After 5 hours the vessel is cooled and the remaining Vac under reduced pressure
Was removed from the system together with the menota, while removing methanol, to obtain a methanol solution of polyvinyl acetate (hereinafter abbreviated as PVAc) (concentration: 64.5%). Take a part of this methanol solution, PVAc concentration 50%, [NaOH] /
A methanol solution of NaOH was added so that [VAc] = 0.05 (molar ratio), and the mixture was saponified at 40 ° C. to obtain a PVA-based polymer.
After purifying the PVA-based polymer by Soxhlet's washing with methanol, [η] was measured at 30 ° C. in water, and [η] was measured.
= 7.51 × 10 ^-3 () ^0.64 where the degree of polymerization was calculated 130
When the degree of saponification was measured, it was 98.6%.

Next, using this purified PVA-based polymer, when the amount of mercapto groups contained in the PVA-based polymer was determined by a method using iodine oxidation, 1.87 × 10 ⁻⁴ equivalents / g-mercapto group of the PVA-based polymer was determined. Existence confirmed.

Synthesis Examples 2 and 3 Polymerization was performed in the same manner as in Synthesis Example 1 except that the amount of thiolacetic acid was changed, and saponification was performed to obtain a PVA-based polymer having a mercapto group at a terminal. The results are summarized in Table 1.

[Production of emulsion using PVA-based block copolymer as protective colloid] Production Example 1 To 10 parts of PVA-based polymer of Synthesis Example 1, 110 parts of distilled water was added, and
The PVA polymer was dissolved at ℃, cooled to 30 ℃ under a nitrogen stream, and 10 parts of acrylic acid which had been replaced with nitrogen in advance was added.
Next, an aqueous solution obtained by dissolving 0.32 part of potassium bromate in 10 parts of distilled water in which nitrogen was replaced was added, and polymerization was started at 30 ° C. Polymerization was completed in 2 hours, and a PVA-based polymer-polyacrylic acid-based PVA-based block copolymer (A) aqueous solution having a polymerization rate of 100.1% and a solid content of 14.4% was obtained.

Next, an aqueous solution of the block copolymer (A) is placed in another reactor.
Transfer 62.5 parts, add 45 parts of water and 100 parts of vinyl acetate,
After the replacement with nitrogen, an aqueous solution in which 0.5 part of ammonium persulfate was dissolved in 6 parts of water was added, and polymerization was started at 70 ° C. The polymerization was completed in 2 hours, and a stable emulsion having a residual vinyl acetate concentration of 0.2%, a solid content of 50.8%, and a viscosity of 4,500 cps was obtained.

The obtained emulsion was allowed to stand at 60 ° C., and the presence or absence of a change after 7 days was examined. As a result, there was no change in appearance and the viscosity was 4300 cp, which was stable with almost no change.

Production Example 2 To 10 parts of the PVA-based polymer of Synthesis Example 2, 108 parts of distilled water was added, and 95 parts of
The PVA-based polymer was dissolved at ℃ and cooled to room temperature. N / 2−H ₂
SO ₄ was added to adjust the pH to 3, and 10 parts of acrylamide was added and dissolved, followed by nitrogen replacement and the temperature was raised to 60 ° C. Then, the addition of an aqueous solution of 0.217 g of potassium bromate dissolved in distilled water purged with nitrogen was started to start polymerization. The aqueous potassium bromate solution was added uniformly at a rate of 2 ml / 5 minutes for 30 minutes. The polymerization was completed in 90 minutes, and a PVA-based polymer-polyacrylamide-based PVA-based block copolymer (B) aqueous solution having a polymerization rate of 101.7% and a solid content of 14.5% was obtained.

Next, 34.5 parts of the aqueous solution of the block copolymer (B), 60 parts of water and 82 parts of vinyl acetate were added to a pressure-resistant autoclave, and after purging with nitrogen, ethylene was injected to 40 kg / cm ² . Then, the internal temperature was raised to 50 ° C., and 4 parts of a 5% Rongalite aqueous solution and 1 part
% Hydrogen peroxide was added sequentially to carry out polymerization. The polymerization was completed in 3 hours, the residual vinyl acetate concentration was 0.4%, and the solid concentration was 5%.
A stable emulsion having 0.7%, ethylene content of 17.9% and viscosity of 3200 cp was obtained. The viscosity of this emulsion after standing at 60 ° C. for 7 days was 3,400 cp, indicating that the emulsion had good standing stability.

Production Example 3 Distilled water (110 parts) was added to the PVA-based polymer (10 parts) of Synthesis Example 3 to give 95 parts.
The PVA-based polymer was dissolved at ℃ and cooled to room temperature. After 9 parts of acrylic acid and 1 part of acrylamide were added and dissolved, the temperature was raised to 60 ° C. by purging with nitrogen. Then potassium persulfate 0.
The whole amount of an aqueous solution obtained by dissolving 05 parts in distilled water was added to initiate polymerization. The polymerization was completed in 2 hours, and an aqueous solution of a PVA-based block copolymer (C) of PVA-based polymer-poly (acrylic acid-allylamide) having a weight ratio of 99.7% and a solid content of 14.3% was obtained. 49 parts of the aqueous solution of the block copolymer (C) was transferred to another reactor, and 56 parts of water, 17 parts of vinyl acetate and 3 parts of n-butyl acrylate were added. After purging with nitrogen, the temperature was raised to 70 ° C., and the temperature was increased by 5%. Two parts of ammonium sulfate were added to initiate polymerization. Next, 68 parts of vinyl acetate and n-butyl acrylate were added over 3 hours.
12 parts of the mixture was added sequentially, and after the addition was completed, the internal temperature was raised to 75 ° C for 30 minutes.
Hold for minutes.

The resulting emulsion had a solid content of 51.3% and a viscosity of 6800
It has a stable cp and a viscosity of 6700 after standing at 60 ° C for 7 days.
cp almost changed.

Production Example 4 Distilled water (110 parts) was added to the PVA-based polymer (10 parts) of Synthesis Example 2 to give 95 parts.
After dissolving the PVA-based polymer at ℃, it was cooled to room temperature. After adding and dissolving 7.5 parts of acrylic acid and 1.5 parts of N-methylolacrylamide, the temperature was raised to 60 ° C after replacement with nitrogen. Next, an entire aqueous solution in which 0.05 part of potassium persulfate was dissolved in 1 part of distilled water was added, and polymerization was started. The polymerization was completed in 2 hours and the conversion was 9
9.8%, 14.6% solids concentration PVA-based polymer as one component
A PVA-based block copolymer (D) aqueous solution was obtained.

Next, 55 parts of the block copolymer (D) aqueous solution was transferred to another reactor, 63 parts of water and 10 parts of vinyl acetate were added, and after purging with nitrogen, the temperature was raised to 70 ° C., and 2 parts of a 5% aqueous solution of potassium persulfate was added. Was added to initiate polymerization. Then take the vinyl acetate over 3 hours.
After the addition was completed, the internal temperature was kept at 75 ° C. for 30 minutes.

The obtained emulsion has a solid content of 49.8% and a viscosity of 7500
It was a stable cp. 60 ℃ of this emulsion, 7
The viscosity after standing for a day was 7,600 cp, and was stable without any change in appearance.

Production Example 5 To 55.9 parts of the aqueous solution of the PVA-based block copolymer (C) obtained in Production Example 3, 62 parts of water and 10 parts of vinyl acetate were added, and after purging with nitrogen, 3 parts of a 3% potassium persulfate solution at 65 ° C was added. It was added to initiate polymerization. Next, after continuously adding 90 parts of vinyl acetate over 3 hours, the internal temperature was maintained at 75 ° C. 48.7% solid content,
It was a stable emulsion with a viscosity of 8600 cp and was stable after standing at 60 ° C for 7 days.

Examples 1 to 3 The following adhesion test was carried out in a system in which the zirconium compound was combined with the emulsions obtained in Production Examples 1, 4 and 5. Table 2 shows the results.

1. Synthetic adhesion test 50 parts of talc were mixed with 100 parts of emulsion and plywood was prepared under the following conditions.

Single board construction; Face and pack …… Red Rawan 1.2mm core …… Red Rawan 2.5mm 3 ply Adhesion condition; Adhesive application amount (both sides)… 260g / m ² Cold pressure (room temperature)… 10kg / cm ² , 20 minutes Heat pressure (115 ° C.) 10 kg / cm ² , 1.5 minutes Example 4 The same adhesion test as in Example 1 was carried out in a system in which a calcium compound was added to the emulsion obtained in Production Example 5.
Table 2 shows the results.

Comparative Example 1 8 parts of PVA having an average degree of polymerization of 1300 and a degree of saponification of 88 mol% was added to water 109
After dissolution in parts, 10 parts of vinyl acetate are added. After the replacement with nitrogen, the internal temperature was raised to 70 ° C., and an aqueous solution obtained by dissolving 0.10 part of potassium persulfate in 2 parts of distilled water was added to initiate polymerization. Next, 90 parts of vinyl acetate was added over 3 hours, and after the addition was completed, the internal temperature was maintained at 75 ° C. for 30 minutes.

The resulting emulsion had a solids concentration of 49.7% and a viscosity of 1100
It was 0cp.

The same adhesion test as in Example 1 was carried out in a system in which a zirconium compound was added to the emulsion. Table 2 shows the results.

Examples 5 and 6 The adhesion test of the vinyl chloride decorative board described below was performed on the system of the combination of the emulsion and the zirconium compound obtained in Production Examples 2 and 3. The results are shown in Table-3.

2. Adhesion test of vinyl chloride decorative board One part of zirconium compound was added to 100 parts of emulsion and a vinyl chloride decorative board was prepared under the following conditions.

Test piece Vinyl chloride sheet: 0.2 mm thick semi-rigid sheet Backing paper: 5.5 mm thick, 3 plies, Type I Rawan plywood Adhesion condition Adhesive application amount: 120 g / m ² Pressing: 20 ° C, 0.5 kg / cm ² , 16Hr Curing: 7 days Test method Water resistance Strength: After immersion in water at 20 ° C for 24 hours, determine the peel strength in a wet state. (180 degree peeling) Heat resistance creep: 90 degree peeling of 500g / 25mm width at 60 ° C.

Example 7 Evaluation by creep length after one hour by applying a static load Example 7 A vinyl chloride cosmetic similar to Example 5 in a system obtained by adding a calcium compound (1 part to 100 parts of emulsion) to the emulsion obtained in Production Example 2. A board adhesion test was performed.
The results are shown in Table-3.

Comparative Example 2 In a pressure-resistant autoclave, the degree of polymerization was 1300 and the degree of saponification was 87 mol%.
5 parts of PVA was dissolved in 96 parts of water, 82 parts of vinyl acetate was added, and the mixture was purged with nitrogen and then pressurized to 40 kg / cm ^{2 of} ethylene. Then internal temperature
The temperature was raised to 50 ° C., and 4 parts of a 5% aqueous solution of Rongalite and 3 parts of a 1% aqueous hydrogen peroxide solution were successively added to polymerize.
An emulsion having an ethylene content of 18.0% was obtained. Example 5 with the combination of this emulsion and zirconium compound
In the same manner as in the above, an adhesion test of a vinyl chloride decorative board was performed. The results are shown in Table-3.

Comparative Example 3 An adhesion test of a vinyl chloride decorative plate was performed using the emulsion alone obtained in Production Example 2 in the same manner as in Example 5. The crystals are shown in Table-3.

E. Effects of the Invention As is clear from the above examples, the adhesive composition comprising the resin composition of the present invention has a large adhesive strength, good water resistance, good heat resistance, and is one component of the resin composition. Certain emulsions also have good storage stability and are of extremely high industrial value.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C09J 151/00 C09J 151/00 153/00 153/00

Claims (5)

(57) [Claims] 1. A monomer mainly composed of a vinyl ester is emulsified (co) in the presence of a polyvinyl alcohol-based block copolymer of a polymer of a vinyl compound represented by the general formula (I) and a polyvinyl alcohol-based polymer. A resin composition comprising a polymerized emulsion and a polyvalent metal compound as main components. Provided that R ¹ is hydrogen or a methyl group. X is hydrogen, -COOM or -COOR ² (R ² is an alkyl group having 1 to 12 carbon atoms). Y is -COOM (M is hydrogen, a metal ion or NH ₄ ^+), - CO
_{NH 2, -CONHCH 2 OH, -CON} (CH 3) 2, -SO 3 M, -C 6 H 5 SO
₃ M (M is hydrogen, metal ion or NH ₄ ⁺ ). 2. The resin composition according to claim 1, wherein the polyvinyl alcohol-based polymer is a polyvinyl alcohol-based polymer having a mercapto group. 3. The resin composition according to claim 1, wherein the vinyl ester is vinyl acetate. 4. The resin composition according to claim 1, wherein the polyvalent metal compound is a zirconium compound. 5. An adhesive composition comprising the resin composition according to claim 1.