JPH0830177B2 - Adhesive for labels - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive for labels. More specifically, the present invention relates to a bottle label adhesive having good cold water resistance and excellent alkaline cleaning properties.

(Prior Art) Label adhesives used for bottles, particularly bottles for filling beverages such as beer, have high adhesive strength and good water-resistant adhesiveness when immersed in cold water (hereinafter, abbreviated as cold water resistance). In addition, it is necessary that the cleaning property with alkaline water when cleaning the bottle (hereinafter, abbreviated as alkaline cleaning property) is excellent. Conventionally, casein-based adhesives, starch-based adhesives, polyvinyl alcohol-based adhesives, and the like are known as such label adhesives. However, since the casein-based adhesive is a natural product, it has a problem that its quality is unstable or it easily decomposes, and its cold water resistance is insufficient. As a starch-based adhesive, a formulation using starch in combination with urea and a styrene-maleic anhydride copolymer (U.S. Pat. No. 3,857,803) is known, but this formulation has poor water resistance, and furthermore has an alkali wash. There was a drawback that sex was bad.

Further, as a polyvinyl alcohol (hereinafter abbreviated as PVA) adhesive, (i) conventional PVA mixed with starch, inorganic sychner, etc. (German Patent Publication No. 2,364,438), (ii) PVA and sychner with urea , Blended with synthetic resin emulsion etc. (JP-A-56-16572)
Etc. are known. However, all of them have the drawbacks of insufficient water resistance and poor alkaline cleaning properties.

(Problems to be Solved by the Invention) An object of the present invention is to satisfy various performances as a label adhesive used for bottle labels, and also to have good adhesiveness, and also to have water resistance and alkali cleaning property. An object of the present invention is to provide an excellent novel label adhesive and a glass substrate having a label coated with the same.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that a polyvinyl alcohol resin (A) having a saponification degree of 90 to 100 mol% and a carboxyl group-containing olefinic monomer. To contain at least one water-insoluble and alkali-soluble and / or alkali-swelling substance (B) selected from a copolymer of a polymer, an acid-type superabsorbent resin and casein as an active ingredient. The present inventors have surprisingly found that the above-mentioned object can be achieved when a characteristic adhesive for labels is used, and completed the present invention. The present invention will be described in detail below.

The PVA-based resin (A) used in the present invention is usually P
In addition to VA, silicon-containing modified PVA, epoxy modified PVA, acetoacetylated PVA, carboxyl group modified PVA, sulfonic acid group modified PVA, phosphoric acid group modified PVA, amino group modified PVA, ammonium group modified PVA, amide modified PVA, methylol Group-modified PV
A or ethylene, vinyl ether having long chain alkyl group, vinyl ester, (meth) acrylamide, α
-Modified PVA copolymerized with olefin and the like can be used.
It is essential that the saponification degree of these is 90 to 100 mol%. More preferably, it is 96 to 100 mol%. If the degree of saponification is less than 90 mol%, the water solubility will decrease, and an adhesive cannot be prepared, or even if it can be prepared, cold water resistance is insufficient. That is, a saponification degree of 90 to 100 mol% is an essential condition for satisfying the requirements of cold water resistance and ease of preparation of an adhesive. The degree of polymerization of these PVA-based resins (A) is not particularly limited, but is usually selected from the range of 100 to 5000 and 300 to 3000 is more preferable in terms of adhesiveness, workability, stability of quality and the like.

The water-insoluble, alkali-soluble and / or alkali-swellable substance (B) (hereinafter sometimes abbreviated as substance (B)) used in the present invention and characterizing the present invention is an aqueous adhesive solution or dispersion. It is necessary to simultaneously have the properties of being able to exist in the form of particles in a liquid, being insoluble in water, and being excellent in alkali solubility or alkali swellability. Further, it is preferable that the compound is dissolved or swelled by an alkali in a short time. The shape of the substance (B) is not particularly limited as long as it does not impair the function as an adhesive as long as it is insoluble in water and can be present in the form of particles in the aqueous adhesive solution or dispersion, but it is not limited to powder, emulsion, suspension dispersion. Such as an aqueous dispersion is preferable. Of these, powder is more preferable. The particle diameter is not particularly limited, but in the case of powder, the average particle diameter is preferably 100 μm or less.

As a copolymer of a carboxyl group-containing olefinic monomer, a carboxyl group-containing monomer such as (meth) acrylic acid, crotonic acid, maleic anhydride, itaconic acid (hereinafter,
It may be abbreviated as a monomer (1). ) And α-olefin, vinyl ester, vinyl ether, (meth) acrylic acid ester, vinyl chloride, acrylonitrile and the like (hereinafter sometimes abbreviated as monomer (2)). α-olefin has 2 to 20 carbon atoms
[Alpha] -olefin, and preferably has 2 to 8 carbon atoms.
Α-olefin is used, specifically, ethylene, propylene, butene-1, butene-2, isobutene, 2-
Methyl-butene-1,3-methyl-butene-1, pentene-1,2-methyl-pentene-1,3-methyl-pentene-1,4-methyl-pentene-1, octene-1,
Examples thereof include diisobutylene, styrene, and α-methylstyrene, and one or more of these are used. Examples of the vinyl ester include vinyl acetate, vinyl propionate, t-butyl vinyl ester, vinyl versatate and the like. Examples of the vinyl ether include ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, lauryl vinyl ether, and stearyl vinyl ether. Examples of the (meth) acrylic acid ester include (meth) acrylic acid methyl, ethyl, butyl, and 2
-Ethylhexyl, lauryl ester and the like can be mentioned.
These can be used alone or as a mixture of two or more kinds. These monomer (1) and monomer (2)
The copolymerization ratio with is not particularly limited as long as it is water-insoluble and alkali-soluble and / or swellable, but when the carboxy group-containing monomer (1) is maleic anhydride, the monomer (2 ) / Monomer (1) molar ratio of 0.
5/1 to 5/1 is preferable, and 1/1 is more preferable. Further, when the caroxyl group-containing monomer (1) is (meth) acrylic acid, crotonic acid or itaconic acid, the monomer (2)
Monomer (2) / monomer (1)
The molar ratio of 5/1 to 50/1 is preferable.

Among the above-mentioned copolymers, for the purpose of the present invention, a copolymer of a carboxyl group-containing monomer and vinyl ester and α
-A copolymer of olefin and maleic anhydride, particularly a copolymer of isobutene and maleic anhydride, or a copolymer of styrene and maleic anhydride, is preferably used in view of insolubility in water and alkali solubility and / or alkali swellability. As the above-mentioned maleic anhydride, maleic acid, maleic acid salt, maleic acid monoester or the like may be mixed and used in a small amount of 10% or less based on maleic anhydride.

It is suitable to use it as a fine powder having the above-mentioned copolymer average particle diameter of 100 μm or less.

Further, the acid-type superabsorbent resin referred to herein can be obtained by subjecting the superabsorbent resin to a treatment for removing alkali (for example, a neutralization treatment with an acid). These include resin powders that are insoluble in water and swell in alkalis. However, the term "super absorbent polymer" as used herein means a crosslinked polyacrylic acid salt, a crosslinked product of a vinyl acetate-methyl acrylate copolymer saponified product, a crosslinked product of a vinyl acetate-monomethyl maleate copolymer saponified product, isobutylene-anhydrous. Maleic acid copolymer Saponified product, starch-acrylic acid graft polymer, polysaccharide-
Examples thereof include acrylic acid graft polymers, starch-acrylonitrile graft copolymer hydrolysates, carboxymethyl cellulose cross-linked products, and cross-linked polyethylene oxides. Among them, it is preferable to use a product obtained by subjecting a crosslinked product of a saponified isobutylene-maleic anhydride copolymer to a dealkalization treatment to be used as a fine powder. Examples of casein include acid casein, rennettocasein, lactic casein and modified compounds thereof,
It is preferable to use these in the form of fine powder.

These substances (B) are insoluble in water, but have the property of dissolving or swelling in a short time when they react with an aqueous alkaline solution. Examples of alkaline include hydroxides and carbonates of sodium, potassium, lithium and the like. salt,
Examples thereof include ammonia, organic amines, inorganic amines, hydroxides and carbonates of calcium, magnesium, aluminum, zinc and the like. As an example, sodium hydroxide which is inexpensive and industrially available as an alkali cleaning liquid in the beer industry. Is used, and it is very practical and useful if the alkaline washing property is effective in an aqueous solution of sodium hydroxide.

Among the above substances (B), α-olefin-maleic anhydride copolymer, crotonic acid-modified polyvinyl acetate, and casein are preferable, and further isobutylene-maleic anhydride copolymer is preferable from the viewpoint of water resistance and alkali detergency. , Styrene-
Maleic anhydride copolymers are especially preferred. These copolymers are preferably used in the form of fine powder.

The mixing weight ratio (solid content ratio) of the PVA-based resin (A) and the substance (B) is not particularly limited, but 100% by weight of the PVA-based resin (A) is added from the viewpoint of the effect of adhesiveness and alkali cleaning property. 2 to 500 parts by weight of the substance (B) is preferable, and the substance (B) is 20 to 300 parts by weight.
More preferably parts by weight. When the amount of the substance (B) is 2 parts by weight or less, the contribution to the alkali cleaning property is small. On the other hand, the substance (B)
If it is more than 500 parts by weight, the water-resistant adhesive strength will decrease and the cold water resistance will deteriorate.

Further, the PVA-based resin (A) and the water-insoluble and alkali-soluble and / or alkali-swellable substance (B) used in the present invention are essential components for the adhesive, but the initial tack is improved, the water resistance is improved, and the fluidity is improved. A filler may also be used in combination with the adhesive for the purpose of improvement. As the filler, clay, talc, silica, calcium carbonate, aluminum hydroxide, aluminum oxide, gypsum, titanium oxide, diatomaceous earth, baurim sulfate, calcium sulfate, mica, inorganic pigments such as glass, plastic pigment, benzoguanamine resin, acrylic resin, It is possible to use one kind or a mixture of two or more kinds selected from organic substances such as styrene resin and urea formalylene resin. Among these, clay is preferable in terms of water resistance and fluidity.

Filler (C) for PVA type resin (A) and substance (B)
When used together, the blending weight ratio (solid content ratio) of the filler (C) is 2 to 500 parts by weight of the filler (C), preferably 20 to 400 parts by weight, based on 100 parts by weight of the PVA resin (A). Is preferably 50 to 300 parts by weight. If the blending ratio of the filler (C) is larger than 500 parts by weight, the fluidity of the adhesive is deteriorated and the adhesive strength is lowered, which is not preferable. If necessary, an aqueous emulsion, a shrinker or the like can be used together for the purpose of improving the initial adhesive force, adjusting the viscosity, improving the fluidity, and preventing the stringing.

As other additives, various antifoaming agents, if necessary,
Preservatives, antifungal agents, viscosity stabilizers, coloring pigments, deodorants, fragrances and the like can also be added. In order to improve the adhesive strength, a water-soluble boron compound such as boric acid, borax, or a boric acid ester of a polyhydric alcohol such as glycerin or ethylene glycol may be added. However, if the amount of addition is large, it has a bad influence on the high-speed coating property.

Although the adhesive of the present invention is water-based, alcohols such as methanol, ethylene glycol and glycerin, and organic solvents such as cellosolves may be added in order to impart flexibility to the antifreezing agent and the adhesive phase.

As an example of the method for preparing the adhesive of the present invention, PVA-based resin (A) and substance (B) are further mixed with a filler and other additives in advance, if necessary, and the mixture is put into water with stirring. To make slurry liquid, or add additive, filler material (B) and PVA type resin (A) into water with continuous stirring to make slurry liquid, then steam this slurry liquid with a jettucker or a preparation tank. Is heated and melted by an optional heating method such as a direct heating method of directly blowing or an indirect heating method using a jacket, and then prepared by cooling, or in the above-mentioned composition except the substance (B) other than the above-mentioned substance (B). It is prepared by adding the substance (B) after heating, melting and cooling. The prepared adhesive of the present invention is used for labeling purposes, and is suitable for glass bottles for beverages, especially beer bottles. Although the viscosity of the adhesive varies depending on each application, when the high-speed coating property is intended, the viscosity at the bonding temperature is preferably 5,000 to 100,000 cps as B type viscosity,
Furthermore, 10,000 to 50,000 cps is a more preferable viscosity range.

Labels for which the adhesive of the present invention is used are paper, processed paper (for example, aluminum vapor-deposited, aluminum laminated, varnished, resin processed, etc.), paper such as synthetic paper, film of organic compound or inorganic compound, metal. Labels attached to films such as compounds are targeted. The other adherend may be anything, and examples thereof include inorganic substances such as glass, metal, and plastics, and organic substances. Among them, a glass bottle for beverage is preferable.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the following, “part” or “%” means “part by weight” or “% by weight” unless otherwise specified.

Example 1 100 parts of PVA resin (PVA-117 made by Kuraray; saponification degree 98.5 mol%, polymerization degree 1750) and crotonic acid-modified polyvinyl acetate fine powder (manufactured by Denki Kagaku Kogyo Co., Ltd.)
ASRCL-09; Alkali-soluble type) 50 parts of powder is put into 500 parts of water and heated at 95 ° C for 1 hour with stirring to produce PVA-1
Only 17 dissolves. This was cooled to obtain an adhesive. The adhesive obtained was a mixture of crotonic acid-modified polyvinyl acetate in the form of fine powder dispersed in an aqueous solution of PVA-117, and had good fluidity. Table 1 shows a summary of the composition and properties of the adhesive, and Table 2 shows the evaluation results (initial adhesive strength, normal adhesive strength, cold water resistance, alkali detergency and odor were evaluated by the following methods). .

(Initial adhesive strength) Glass plate (10cm x 10cm, thickness 2mm) washed and dried in advance
Is preheated to 40 ° C., and the adhesive is applied to the label paper using a bar coater. The coating amount was 10 g / m ² as a solid content. This label paper is adhered to the above glass plate and immediately lightly pressed with a rubber roller to make a test piece, and after 30 seconds, an autograph (DCS-100 manufactured by Shimadzu Corporation) is used to pull at a speed of 500 mm / min. The initial adhesive strength was measured by peeling at 180 °. The results are indicated by the following symbols.

A: There is no interface peeling between the label paper and the glass plate, and only the label paper is broken.

Good: 30% or more and 90% or less of the adhesive area of the label paper is broken.

Δ: 5% or more and less than 30% of the adhesive area of the label paper is broken.

X: The label paper was not broken at all, and only the interface between the label paper and the glass plate was peeled off.

(Normal adhesive strength) After applying and pressure bonding in the same manner as the test piece for measuring the initial adhesive strength described above, the test piece after drying at 40 ° C for 24 hours is autographed after being cured at 20 ° C and 65% RH for 3 days. 180 ° peeling was performed under the same conditions to measure the normal adhesive force. The results are shown by the same symbols as in the case of the above initial adhesive strength.

(Cold water resistance) Soak the test peat prepared in the same manner as the test piece for measuring the normal adhesive strength in cold water at 10 ° C (slowly continue to stir cold water for 30 days). After that, the test piece was taken out from the cold water, and the cold water resistance between the glass plate surface and the label paper was measured by peeling it off with a finger or a fingernail. The results are indicated by the following symbols.

：: When peeled off with a fingernail, there is no interface peeling between the label paper and the glass plate, and only the label paper is broken.

◯: When peeled off strongly with the fingernail, only interface peeling between the label paper and the glass plate occurs.

Δ: Lightly peeled off with the fingernail, and only interface peeling between the label paper and the glass plate occurs.

X: Only the interface peeling between the label paper and the glass plate occurs easily with a finger rubbing lightly.

(Alkali detergency) A test piece prepared by the same method as the above-mentioned test piece for measuring the normal adhesive strength (however, only the drying condition was changed to 40 ° C and 48 hours) was adhered to a 70% 3% NaOH aqueous solution. Was soaked and held that it became vertical. After 4 minutes and 30 minutes thereafter, it was observed whether the label paper peeled off the glass plate and dropped off naturally. The results are indicated by the following symbols.

A: The label paper completely falls off the glass plate.

◯: 30% or more and 90% or less of the adhesive area of the label paper is peeled off from the glass plate.

Δ: 5% or more and less than 30% of the adhesive area of the label paper is peeled off from the glass plate.

X: The label paper does not peel off at all in the state where it adheres to the glass plate.

(Odor) It was evaluated whether or not the adhesive had a bad odor by blowing the nose. The results are indicated by the following symbols.

○: There is no odor.

Δ: Somewhat unpleasant odor.

×: Very unpleasant odor.

Example 2 PVA resin (PVA-CS made by Kuraray; saponification degree 97.5 mol%, degree of polymerization 1750) 100 parts, styrene-maleic anhydride copolymer fine powder (Aco; SMA-100) 50 parts, water 500 parts An adhesive was obtained in the same manner as in Example 1 using. The obtained adhesive is PV
It was a mixture of finely powdered styrene-maleic anhydride in the aqueous solution A, and had good fluidity. Table 1 shows a summary of the composition and properties of the adhesive, and Table 2 shows the evaluation results.

Example 3 (missing number) Example 4 PVA resin (Kuraray product PVA-117; saponification degree 98.5 mol%,
Polymerization degree 1750) 100 parts, 10 parts of the same isobutylene-maleic anhydride copolymer fine powder as used in Example 3, clay
After pouring 150 parts into 550 parts of water, an adhesive was obtained in the same manner as in Example 1. The obtained adhesive was a mixture of clay and fine particles of isobutylene-maleic anhydride copolymer dispersed in a PVA aqueous solution, and had good fluidity. Table 1 shows a summary of the composition and properties of the adhesive, and Table 2 shows the evaluation results.

Example 5 Example 4 was repeated, except that the same styrene-maleic anhydride copolymer fine powder used in Example 4 was used instead of the isobutylene-maleic anhydride copolymer used in Example 4.
Same as above. The resulting adhesive was the same mixture as in Example 4. Table 1 shows a summary of the composition and properties of the adhesive, and Table 2 shows the evaluation results.

Example 6 Example 1 was repeated except that the crotonic acid-modified polyvinyl acetate used in Example 1 was replaced with 50 parts of the same isobutylene-maleic anhydride copolymer fine powder used in Example 4.
An adhesive was obtained in the same manner as in. Table 1 shows a summary of the properties of the blended composition and the adhesive, and Table 2 shows the evaluation results.

Example 7 Instead of the isobutylene-maleic anhydride copolymer used in Example 4, as an acid type superabsorbent resin,
The powder of the crosslinked product of the isobutylene-maleic anhydride copolymerized product was dealkalized in an aqueous hydrochloric acid solution for 4 days, washed with water, washed with methanol, and dried to obtain a powder. The obtained product was insoluble in water, insoluble in an alkaline aqueous solution, and exhibited a particularly large swelling property. This acid-type superabsorbent resin was used and the same procedure as in Example 4 was carried out. Table 1 shows a summary of the composition and properties of the adhesive, and Table 2 shows the evaluation results.

Example 8 The procedure of Example 4 was repeated, except that the isobutylene-maleic anhydride copolymer used in Example 4 was replaced with powder of casein. Table 1 shows a summary of properties and Table 2 shows evaluation results.

Examples 9 to 11 (missing number) Examples 12 to 18 In place of PVA-117 used in Example 4, acetoacetylated PVA (acetoacetyl group content 2.3 mol%, saponification degree 99 mol%, polymerization degree 1700) was used in Example 12. In Example 13, silicon-containing modified PVA (vinyl methoxysilane modification degree 0.2 mol%, saponification degree 98 mol%, polymerization degree 1700)
In Example 14, Poxy-modified PVA (allyl glycidyl ether modification degree 2.5 mol%, saponification degree 98 mol%, polymerization degree 150
0) in Example 15 with carboxyl group-modified PVA (itaconic acid modification degree 1 mol%, saponification degree 98% mol%, polymerization degree 1750).
In Example 16, ammonium group-modified PVA (quaternary ammonium salt modification degree 2 mol%, saponification degree 98 mol%, polymerization degree 17
50) in Example 17, sulfonic acid group-modified PVA (sodium allyl sulfonate modification degree 2 mol%, saponification degree 98 mol%, polymerization degree 1700), and in Example 18 amide-modified PVA (acrylamide modification degree 2 mol%). , Saponification degree 98 mol%, degree of polymerization 170
The same procedure as in Example 5 was carried out except that (0) was used. Table 3 shows a summary of the composition and properties of the adhesive, and Table 4 shows the evaluation results.

Comparative Example 1 PV used in Example 1 and having a saponification degree of 98.5 mol%
PV with a degree of saponification of 79.5 mol% and a degree of polymerization of 1750 instead of A-117
The same procedure as in Example 1 was carried out except that the A-based resin (Kuraray PVA-420) was used.

Table 5 shows a summary of the composition and properties of the adhesive, and Table 6 shows the evaluation results.

Comparative Example 2 The procedure of Example 1 was repeated except that a polyacrylic acid resin (Nippon Pure Chemical Co., Ltd., Diuremer AC-10LP) was used instead of the crotonic acid-modified polyvinyl acetate used in Example 1. Table 5 shows the composition and the properties of the adhesive.
Table 6 shows the evaluation results.

Comparative Example 3 The procedure of Example 1 was repeated, except that a polyvinyl chloride powder was used instead of the crotonic acid-modified polyvinyl acetate used in Example 1. Table 5 shows the composition and the properties of the adhesive.
Table 6 shows the evaluation results.

Comparative Example 4 The procedure of Example 1 was repeated except that the crotonic acid-modified PVA used in Example 1 was not added. Table 5 shows a summary of the composition and properties of the adhesive, and Table 6 shows the evaluation results.

Comparative Example 5 Instead of the crotonic acid-modified polyvinyl acetate used in Example 1, polyacrylic acid soda (manufactured by Nippon Pure Chemical Co., Ltd.
The same procedure as in Example 1 was carried out except that 0H) was used. The obtained product was a mixed aqueous solution of PVA and sodium polyacrylate, and the fine paper-like substance (B) as seen in Examples 1 to 10 was not present. Table 5 shows a summary of the composition and properties of the adhesive, and Table 6 shows the evaluation results.

Comparative Example 6 The procedure of Example 1 was repeated except that urea was used instead of the crotonic acid-modified polyvinyl acetate used in Example 1.
Table 5 shows a summary of the composition and properties of the adhesive, and Table 6 shows the evaluation results.

Comparative Example 7 An adhesive containing casein as a main component, which is currently used as an adhesive for label paper for beer bottles, was tested. Solid content concentration 38.5%, viscosity at 20 ℃ 22,400cps, pH 8.4
It had a bad smell of ammonia. Table 5 summarizes the composition and properties of the adhesive, and Table 6 shows the evaluation results.
Shown in the table.

Comparative Example 8 PVA resin (Kuraray product PVA217; saponification degree 88.0 mol%, polymerization degree 1750) 100 parts, isobutylene-maleic anhydride copolymer (Kuraray Co., Isoban-10) 50 parts, water 500 parts The test was carried out as in Example 1. Table 8 shows a summary of properties and Table 9 shows evaluation results.

(The above Comparative Example is Example 3 described in the specification at the time of filing.) Comparative Example 9 Except that corn starch powder was used instead of the isobutylene-maleic anhydride copolymer used in Example 4. Was performed in the same manner as in Example 4. Table 8 shows a summary of properties and Table 9 shows evaluation results.

(The above Comparative Example is Example 9 described in the specification at the time of filing.) Comparative Examples 10 to 11 In place of the isobutylene-maleic anhydride copolymer used in Example 6, Example 6 except that an alkaline gelatinized starch aqueous solution was used, and in Comparative Example 11, an alkaline gelatinized starch aqueous solution and colloidal silica were used.
I went the same way. Table 8 shows a summary of properties and Table 9 shows evaluation results.

(Effects of the Invention) As is clear from the above examples, the adhesive of the present invention has a high initial adhesive strength and a particularly good balance between cold water resistance and alkali detergency. Therefore, the cold water resistance in the case of cooling the beverage-filled glass bottle with the label coated with the adhesive of the present invention is good, and the peeling of the label by the alkali after collecting the glass bottle is easy. Therefore, it is particularly useful as an adhesive for labels of glass bottles for beverages. In addition, it can be adapted to speed up automation,
It has a very high industrial value such that it can be suitably used as an adhesive for labels such as beverage bottles.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-56-16572 (JP, A) JP-A-55-152770 (JP, A) JP-A-50-6640 (JP, A) JP-A-58- 11573 (JP, A) JP 59-164355 (JP, A) JP 2-84450 (JP, A) JP 40-27188 (JP, B1)

Claims (1)

[Claims] 1. A polyvinyl alcohol-based resin (A) having a saponification degree of 90 to 100 mol%, a copolymer of a carboxyl group-containing olefinic monomer, an acid-type superabsorbent resin and at least casein. An adhesive for labels, comprising a kind of water-insoluble and alkali-soluble and / or alkali-swelling substance (B) as an active ingredient.