JPH093426A - Adhesive - Google Patents

Abstract

PURPOSE: To obtain an adhesive excellent in blocking resistance and the preservability in its aqueous solution state, thus useful as esp. a remoistening adhesive, consisting mainly of a new polyvinyl alcohol-based resin copolymerized with a specific modifying component. CONSTITUTION: This adhesive consists mainly of a new polyvinyl alcohol(PVA)- based resin copolymerized with 0.1-20mol% of an ethylenic unsaturated dicarboxylic acid monoamide having a branched alkylamide component of the formula (R1 is H, an alkyl or aryl group; R2 to R4 are each H, an alkyl or aryl group; where, at least two of them are not H simultaneously, and the number of carbon atoms for R1 to R4 totals >=4) (pref. N-t-octylamaleic acid monoamide). The PVA-based resin is normally obtained by saponification of a copolymer of the above monoamide and a vinyl ester (pref. vinyl acetate). The monoamide is prepared, for example, by reaction between maleic anhydride and t-octylamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive using polyvinyl alcohol (hereinafter abbreviated as PVA), and more specifically, to a blocking resistance when a novel PVA resin is used as a rewetting adhesive. Excellent adhesive.

[0002]

2. Description of the Related Art Conventionally, PVA has been used as a rewetting adhesive for packaging tape, various labels, stamps, stamps, shoji paper,
It is used as a backing paste for wallpaper, fusuma paper, posters, etc., or as an aqueous solution as it is, as an adhesive for various packaging such as cardboard and bag making, and as an office glue. Furthermore, as a hot melt adhesive, bookbinding, bag making, box making, packaging, woodworking, shoe making,
It is used in various adhesives for applications such as fibers.

[0003]

SUMMARY OF THE INVENTION However, PVA
When used for adhesive, in rewetting adhesive,
Blocking of the base material after applying the PVA to the base material, and blocking of the hot melt adhesive during storage in the form of pellets, powders, etc. become a problem, and further rewetting adhesive, pressure sensitive adhesive, etc. In the adhesive used in the form of
There is often a problem also in its storage stability (blocking resistance further decreases when stored for a long time), and a PVA-based resin adhesive excellent in blocking resistance and storage stability has been desired. Of.

[0004]

Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventor has found that an ethylenically unsaturated dicarboxylic acid monoamide (A) containing a branched alkylamide component represented by the following chemical formula 1 is used as a modifying component. It was found that a novel PVA-based resin containing 0.1 to 20 mol% of a copolymer component has excellent blocking resistance and storage stability when it is used for an adhesive, and the present invention has been completed.

Embedded image (However, R ₁ is hydrogen, an alkyl group, or an aryl.
The groups R _{2 to} R ₄ are hydrogen or an alkyl group or aryl (ary
l) groups respectively, and at the same time two or more are not hydrogen but R
The total number of carbon atoms of _{1 to} R ₄ is 4 or more. )

Hereinafter, the present invention will be described in detail. Next, a method for producing the modified PVA-based resin of the present invention will be described. The modified PVA (hereinafter sometimes simply referred to as modified PVA) -based resin of the present invention contains the (A) unit as an essential component as described above, and the (A) unit is a branched alkylamide component represented by the above chemical formula 1. containing ethylenically unsaturated dicarboxylic acid monoamide units are those having the functional group of R ₁ to R _4, stable modifying groups during the saponification is less than the number of carbon atoms of functional groups R ₁ to R ₄ is 4 And storage stability of the aqueous solution when used for rewetting adhesives, etc., and the carbon number is preferably 4 to
Sixteen.

The copolymerizable monomer containing the (A) unit includes N-tert-octyl maleic acid monoamide, N-tert-amyl maleic acid monoamide, and N-tert-amyl maleic acid monoamide.
-1,3-Dimethylbutyl maleic acid monoamide, N-
1,2,2-Trimethylpropyl maleic acid monoamide, N-1-methylhexyl maleic acid monoamide, N
-1-Ethylpentyl maleic acid monoamide, N-1-
Methylheptyl maleic acid monoamide, N-1,5-dimethylhexyl maleic acid monoamide, N, N-ethylisopropyl maleic acid monoamide, N, N-diisopropyl maleic acid monoamide, N, N-methyl-ter
t-Butylmaleic acid monoamide, N, N-isopropyl-tert-butylmaleic acid monoamide, N, N-
Di-sec-butyl maleic acid monoamide, N-1-methylbutyl maleic acid monoamide, N-1-ethylpropyl maleic acid monoamide, N-1,2-dimethylpropyl maleic acid monoamide, N-diphenylmethyl maleic acid monoamide, N -1,2-Diphenylethyl maleic acid monoamide, N-1-methyl-2-phenylethyl maleic acid monoamide, N-1-methyl-3-phenylpropyl maleic acid monoamide, N, N-methyl-1
-Methyl-2-phenylethyl maleic acid monoamide,
N, N-isopropyl-benzyl maleic acid monoamide, N, N-tert-butylbenzyl maleic acid monoamide, N-1,1-dimethyl-2-phenylethyl maleic acid monoamide, N-1-propylbutyl maleic acid monoamide, N -1-Phenylethyl maleic acid monoamide.

N-tert-octyl fumaric acid monoamide, N-tert-amyl fumaric acid monoamide, N-
1,3-dimethylbutyl fumaric acid monoamide, N-1,
2,2-Trimethylpropyl fumaric acid monoamide, N-
1-methylhexyl fumarate monoamide, N-1-ethylpentyl fumarate monoamide, N-1-methylheptyl fumarate monoamide, N-1,5-dimethylhexyl fumarate monoamide, N, N-ethylisopropyl fumarate monoamide, N, N-diisopropyl fumarate monoamide, N, N-methyl-tert-butyl fumarate monoamide, N, N-isopropyl-tert-butyl maleate monoamide, N, N-di-sec-butyl fumarate monoamide, N-1- Methyl butyl fumaric acid monoamide, N-1-ethylpropyl maleic acid monoamide,
N-1,2-dimethylpropyl fumaric acid monoamide, N
-Diphenylmethyl fumaric acid monoamide, N-1,2-
Diphenylethyl fumaric acid monoamide, N-1-methyl-2-phenylethyl fumaric acid monoamide, N-1-methyl-3-phenylpropyl fumaric acid monoamide, N,
N-methyl-1-methyl-2-phenylethyl fumaric acid monoamide, N, N-isopropylbenzyl fumaric acid monoamide, N, N-tert-butylbenzyl fumaric acid monoamide, N-1,1-dimethyl-2-phenylethyl Fumaric acid monoamide, N-1-propylbutyl fumaric acid monoamide, N-1-phenylethyl fumaric acid monoamide.

N-tert-octylitaconic acid monoamide, N-tert-amylitaconic acid monoamide, N
-1,3-Dimethylbutyl itaconic acid monoamide, N-
1,2,2-Trimethylpropyl itaconic acid monoamide, N-1-methylhexyl itaconic acid monoamide, N
-1-Ethylpentylitaconic acid monoamide, N-1-
Methylheptyl itaconic acid monoamide, N-1,5-dimethylhexyl itaconic acid monoamide, N, N-ethylisopropyl itaconic acid monoamide, N, N-diisopropyl itaconic acid monoamide, N, N-methyl-ter
t-Butylitaconic acid monoamide, N, N-isopropyl-tert-butylitaconic acid monoamide, N, N-
Di-sec-butylitaconic acid monoamide, N-1-methylbutylitaconic acid monoamide, N-1-ethylpropylitaconic acid monoamide, N-1,2-dimethylpropylitaconic acid monoamide, N-diphenylmethylitaconic acid monoamide, N -1,2-Diphenylethylitaconic acid monoamide, N-1-methyl-2-phenylethylitaconic acid monoamide, N-1-methyl-3-phenylpropylitaconic acid monoamide, N, N-methyl-1
-Methyl-2-phenylethyl itaconic acid monoamide,
N, N-isopropyl-benzylitaconic acid monoamide, N, N-tert-butylbenzylitaconic acid monoamide, N-1,1-dimethyl-2-phenylethylitaconic acid monoamide, N-1-propylbutylitaconic acid monoamide, N -1-Phenylethyl itaconic acid monoamide.

N-tert-octyl citraconic acid monoamide, N-tert-amyl citraconic acid monoamide, N-1,3-dimethylbutyl citraconic acid monoamide, N-1,2,2-trimethylpropyl citraconic acid monoamide, N-1 -Methylhexyl citraconic acid monoamide, N-1-ethylpentyl citraconic acid monoamide, N-1-methylheptyl citraconic acid monoamide,
N-1,5 dimethylhexyl citraconic acid monoamide,
N, N-ethylisopropyl citraconic acid monoamide,
N, N-diisopropylcitraconic acid monoamide, N,
N-methyl-tert-butyl citraconic acid monoamide, N, N-isopropyl-tert-butyl citraconic acid monoamide, N, N-di-sec-butyl citraconic acid monoamide, N-1-methylbutyl citraconic acid monoamide, N-1 -Ethylpropyl citraconic acid monoamide, N-1,2-dimethylpropyl citraconic acid monoamide, N-diphenylmethyl citraconic acid monoamide, N-1,2-diphenylethyl citraconic acid monoamide, N-1-methyl-2-phenylethyl citracone Acid monoamide, N-1-methyl-3-phenylpropyl citraconic acid monoamide, N, N-methyl-1-methyl-2-phenylethyl citraconic acid monoamide, N, N
-Isopropyl-benzyl citraconic acid monoamide,
N, N-tert-butylbenzyl citraconic acid monoamide, N-1,1-dimethyl-2-phenylethyl citraconic acid monoamide, N-1-propylbutyl citraconic acid monoamide, N-1-phenylethyl citraconic acid monoamide and the like can be mentioned. Preferably N-tert-
Octyl maleic acid monoamide is preferably used.
The carboxylic acid component in the unit (A) of the modified PVA-based resin of the present invention is a free carboxyl group or a salt thereof.

Usually, in order to produce the modified PVA resin of the present invention, the vinyl ester copolymer obtained by copolymerizing (A) and the vinyl ester (B) is saponified. Examples of (B) include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and the like, and vinyl acetate is preferable from the economical viewpoint.

With respect to the proportion of each unit of the modified PVA-based resin, 0.1 to 20 mol% of the ethylenically unsaturated dicarboxylic acid monoamide unit (A) containing the N-branched alkylamide component represented by the above chemical formula 1 is used. , Preferably 0.3-
10 mol%, the vinyl ester unit (B) and the vinyl alcohol unit (C) are suitably in the range of 80 to 99.9 mol% in total. The degree of saponification (the ratio of the vinyl alcohol unit (C) to the total amount of the vinyl ester unit (B) and the vinyl alcohol unit (C)) is not particularly limited, but when the formed film is water-soluble. 70 mol%
It is preferably at least above, and particularly preferably at least 75 mol%.

The degree of polymerization of the modified PVA resin used in the present invention is not particularly limited, but is preferably 10 to 2500, more preferably 300 to 2000, and the degree of polymerization is 10.
If it is less than 0, the adhesiveness will decrease, and if it exceeds 2500, P
Since the viscosity of the VA aqueous solution increases, the workability of the solution adhesive tends to be poor.

Next, a method for producing the modified PVA resin of the present invention will be described. The modified PVA-based resin of the present invention is obtained by saponifying a copolymer of the above-mentioned ethylenically unsaturated dicarboxylic acid monoamide (A) monomer containing a branched alkylamide component represented by Chemical Formula 1 with a vinyl ester. can get.

Such ethylenically unsaturated dicarboxylic acid monoamides (A) include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid,
An ethylenically unsaturated dicarboxylic acid such as citraconic anhydride or an anhydride thereof or an acid halide thereof is used with a primary amine or secondary amine represented by Chemical formula 2 without catalyst or a suitable acid catalyst (sulfuric acid, hydrochloric acid, P- It is obtained by reacting in the presence of (protonic acid such as toluenesulfonic acid). Such amines include tert-octylamine,
tert-amylamine, 1,3-dimethylbutylamine, 2-amino-3,3-dimethylbutane, 2-aminoheptane, 3-aminoheptane, 1-methylheptylamine, 1,5-dimethylhexylamine, N-ethylisopropyl Amine, diisopropylamine, N-methyl-tert-butylamine, N-tert-butylisopropylamine, di-sec-butylamine, 1-methylbutylamine, 1-ethylpropylamine, 1,2-
Dimethylpropylamine, aminodiphenylmethane,
1,2-diphenylethylamine, 1-methyl-2-phenylethylamine, 1-methyl-3-phenylpropylamine, N-methyl-1-methyl-2-phenylethylamine, N-isopropylbenzylamine, N- (t
ert-butyl) benzylamine, α, α-dimethyl-
β-phenylethylamine, 1-propylbutylamine, 1-phenylethylamine and the like can be mentioned.

[0015]

Embedded image (However, R ₁ is hydrogen, an alkyl group, or an aryl.
The groups R _{2 to} R ₄ are hydrogen or an alkyl group or aryl (ary
l) groups respectively, and at the same time not two or more hydrogens, but R
The total number of carbon atoms of _{1 to} R ₄ is 4 or more. )

The copolymerization reaction can be arbitrarily selected from known polymerization methods such as radical polymerization, such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc., but solution polymerization is preferred from the industrial viewpoint. Further, any method such as batch polymerization and continuous polymerization can be adopted. There are no particular restrictions on the method of charging the monomers during the polymerization, and any method such as batch charging, divided charging, continuous charging may be employed. Branched alkyl acrylamide and ethylenically unsaturated carboxylic acid or salts thereof are used as PVA molecules. A divided charging method or a continuous charging method is advantageous in that it can be uniformly introduced into the inside.

As a catalyst for the copolymerization, known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauryl peroxide, and low-temperature catalysts such as azobisdimethylvaleronitrile and azobismethoxydimethylvaleronitrile. An active radical catalyst or the like is used. Further, the reaction temperature is not particularly limited and is appropriately selected from the range well known to those skilled in the art.

In such polymerization, other unsaturated monomers copolymerizable with the monomers other than the above-mentioned two components, such as alkyl vinyl ether, methacrylamide, ethylene, propylene, and α, can be used without impairing the gist of the present invention. −
Olefin such as hexene, α-octene, α-dodecene, α-octadodecene, nitriles such as acrylonitrile and methacrylonitrile, alkyl acrylate, alkyl methacrylate, alkyl crotonic acid, dialkyl maleate, dialkyl itaconate A small amount of ester, citraconic acid dialkyl ester, fumaric acid dialkyl ester and the like may be copolymerized.

The copolymer obtained by such a method is then saponified. As the saponification method, any method such as kneader saponification, continuous saponification, and pearl saponification can be adopted. In the saponification step, the residual monomer is expelled as necessary, and then saponification is performed according to a conventional method. To be done. Examples of the catalyst used for saponification include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate, alkali catalysts such as alcoholate, sulfuric acid, hydrochloric acid and the like. An acid catalyst is used. The saponification reaction temperature is not particularly limited and is usually 10 to 60 ° C, preferably 2
It is selected from the range of 0 to 50 ° C. After the saponification reaction is completed, the target modified PVA-based resin is obtained by neutralizing, washing with alcohol or the like, if necessary, and drying. Next, an adhesive using the obtained modified PVA-based resin will be described. The PVA-based resin can be used for various adhesives such as rewetting adhesives, hot-melt adhesives, pressure-sensitive adhesives, etc., in addition to general adhesives in which the resin is made into an aqueous solution, but it has blocking resistance. Are very useful as rewetting adhesives and hot melt adhesives, and will be described in more detail.

First, when used as a rewetting adhesive,
After the above PVA-based resin is made into an aqueous solution, it is applied to a base material such as gum tape or stamp and dried. At this time, alcohols such as methanol and ethanol and glycols such as ethylene glycol, propylene glycol, polyethylene glycol and glycerin may be added, if necessary. The coating can be performed by a known method such as a gravure coater, a reverse roll coater, an air knife coater, and a spray. It is also possible to form a rewetting adhesive layer by hot-melt coating.

When used as a hot melt adhesive, usually 100 parts by weight of the above PVA resin is used as a plasticizer (glycols such as ethylene glycol, propylene glycol, polyethylene glycol and glycerin, and urea derivatives such as ethylene urea). 5 to 50 parts by weight of hydrophobic resin (ethylene-vinyl acetate copolymer, phenol resin, styrene resin, polyester resin,
5 to 60 parts by weight of a polyamide resin, etc. is blended,
Furthermore, well-known additives for hot-melt adhesives such as hydroxy fatty acids, rosins, rosin esters, pinene-based polymers, hydrogenated petroleum resins, hydrocarbon resins, antioxidants, lubricants, fillers, and colorants. , Fragrance, stabilizer and the like are blended. The coating is carried out by a known hot melt coating machine such as roll, die, nozzle, lip, etc., which can be used for binding bookbinding, packaging, woodworking, adhesion of fibers, etc. In wet adhesive and hot melt adhesive applications, it has excellent blocking resistance after coating, and in rewetting adhesive applications it has excellent storage stability in the aqueous solution state (blocking resistance after long-term storage. There is no decrease in sex), which is very useful. The rewetting adhesive and the hot-melt adhesive have been described above, but the present invention is not limited to these, and a general aqueous solution adhesive, a pressure-sensitive adhesive,
It goes without saying that it can be used for various adhesives such as fast-curing (honeymoon) adhesives.

[0022]

[Operation] Since the adhesive of the present invention uses a specific modified PVA-based resin, it has excellent blocking resistance, and also has excellent storage stability in an adhesive in the form of an aqueous solution. It is very useful in various adhesive applications such as mold adhesives, rewetting adhesives and hot melt adhesives.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “%” and “part” mean on a weight basis unless otherwise specified. (Production of modified PVA-based resin) maleic anhydride 50.0
And 65.9 parts of tert-octylamine were charged into a flask, and the reaction was carried out at 60 ° C. for 2 hours while stirring. After completion of the reaction, the reaction product was recrystallized to obtain the compound represented by Chemical formula 3.

Embedded image The yield was 95%.

A polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 1000 parts of vinyl acetate and 150 parts of methanol, and the temperature was raised under a nitrogen stream while stirring to obtain 0.6 of azobisisobutyronitrile at 62 ° C. A solution prepared by dissolving 1 part in 19.4 parts of methanol was added to initiate polymerization.
Polymerization was performed while continuously adding dropwise 272 parts of a methanol solution containing 27.2 parts of the compound N-tert-octylmaleic acid monoamide obtained above from the polymerization initiation point over 5 hours while the vinyl acetate ester polymerization rate was 50%. The polymerization was terminated when the percentage reached. Then, the unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer. Then, the solution was diluted with methanol to adjust the concentration to 30% and charged in a kneader, and sodium hydroxide was added to neutralize while keeping the solution temperature at 35 ° C. To this, sodium hydroxide was further added in an amount of 30 mmol with respect to the vinyl acetate unit in the polymer and kneaded. As the saponification reaction proceeded, a saponified product was deposited and finally became a particulate form. The resulting modified PVA-based resin was filtered, washed well with methanol, and dried in a hot air drier to obtain the desired product. The obtained modified PVA-based resin was extracted and washed with methanol using a Soxhlet extractor and washed with N
As a result of ¹ H-NMR analysis of the degree of modification with -tert-octyl maleic acid monoamide, the degree of modification was 2.0 mol%. The saponification degree of the modified PVA-based resin was 90 mol% when analyzed by quantifying the amount of alkali consumption required for hydrolysis of the residual vinyl acetate unit. still,
The viscosity of a 4% aqueous solution of this modified PVA-based resin measured by a B-type viscometer was 5.7 cps / 20 ° C., and the degree of polymerization was 500.

Example 1 A 30% aqueous solution of the above-mentioned modified PVA-based resin was prepared, coated on a surface of high-quality paper with a bar coater to a dry thickness of about 10 μm, and dried. Two sheets of the coated paper were prepared and stacked so that the coated surface and the other surface were in contact with each other and 10 g /
A load of cm ² was applied, the mixture was allowed to stand at 20 ° C. and 65% RH for 5 hours, the blocking property (I) was examined, and evaluated as follows. ○ --- There is no blocking at all. (Triangle | delta) -There is some blocking and there is resistance at the time of peeling. × −−− Blocking is remarkable and material destruction occurs during peeling.

Further, after the above PVA aqueous solution was allowed to stand at 40 ° C. for 1 month, the blocking property (II) was similarly examined and evaluated in the same manner. In addition, the above-mentioned modified PVA-based resin 1
00 parts, 25 parts of glycerin, 35 parts of terpene phenolic resin, and 40 parts of 12-oxyoctadecanoic acid were charged into a melting can and melt-mixed at 170 ° C to obtain a hot melt adhesive. The adhesive was heated and melted to prepare a sample having a thickness of 100 μm, two samples were stacked, a load of 100 g / cm ² was applied, and the sample was left at 20 ° C. and 65% RH for 5 hours,
The blocking property (III) was examined and evaluated in the same manner as above.

Examples 2 to 8 and Comparative Examples 1 to 6 Ethylenically unsaturated dicarboxylic acid monoamides were synthesized under the components and conditions shown in Table 1, and obtained various ethylenically unsaturated dicarboxylic acid monoamides and vinyl acetate. The copolymerization of the above-mentioned (modified PV
Various modified PVA-based resins shown in Table 3 were copolymerized with vinyl acetate (in Comparative Example 6, no modifying monomer was added) and saponified by the same procedure as in (Production of A-based resin). The blocking states (I) to (III) were evaluated in the same manner as in Example 1 using the PVA-based resin produced. Table 4 shows the evaluation results of the examples and the comparative examples.

[0028]

[Table 1] Synthetic conditions of ethylenically unsaturated dicarboxylic acid monoamide Synthetic monoamic acid amine Temperature time Yield (parts) (parts) (℃) (hr) (%) Nt-OMMAm Maleic anhydride tert-octylamine 60 2 96 Nt-OIMAm Itaconic anhydride tert-Octylamine 60 2 94 Nt-AMMAm Maleic anhydride tert-Amylamine 60 2 97 N-DMHMMAm Maleic anhydride 1,5-Dimethylhexylamine 60 2 95 N-DMPEMMAn Maleic anhydride α, α -Dimethylhexylamine 60 2 95 Nt-BMMAm Maleic anhydride tert-Butylamine 60 2 96 N-n-OMMAm Maleic anhydride n-octylamine 60 2 90 Note) Abbreviations are as follows. N-t-OMMAm; N-tert-octyl maleic acid monoamide N-t-OIMAm; N-tert-octyl itaconic acid monoamide Nt-AMMAm; N-tert-amyl maleic acid monoamide N-DMHMMAm; N-1, 5-Dimethylhexyl maleic acid monoamide N-DMPEMMAm; N-1,1-dimethylphenylethyl maleic acid monoamide Nt-BMMAm; N-tert-butyl maleic acid monoamide Nn-OMMAm; Nn-octyl maleic acid Monoamide

[0029]

[Table 2] Type of monomer copolymerized with vinyl acetate, charge amount and polymerization rate (A) Monomer Polymerization rate species Charge amount (mol%) (%) Example 1 Nt-OMMAm 2.0 50 〃 2 Nt-OMMAm 0.5 59 〃 3 Nt-OMMAm 8.0 48 〃 4 Nt-OIMAm 2.0 49 〃 5 Nt-AMMAm 2.0 53 〃 6 Nt -MMAm 2.0 50 〃 7 N-DMHMMAm 2.0 50 〃 8 N-DMPEMMMAm 2.0 45 Comparative Example 1 Nt-BMMAm 2.4 51 〃 2 N-n-OMMAm 2.5 52 〃 3 MRM 3.0 55 〃 4 AMPS 2.0 55 〃 5 3M 2.0 60 〃 6 −−− 60

Note) The charged amount represents the charged mole fraction (mol%) of the monomer (A) with respect to the total charged amount of the monomers. Abbreviations are as follows. N-t-OMMAm; N-tert-octyl maleic acid monoamide N-t-OIMAm; N-tert-octyl itaconic acid monoamide Nt-AMMAm; N-tert-amyl maleic acid monoamide N-DMHMMAm; N-1, 5 Dimethylhexyl maleic acid monoamide N-DMPEMMAm; N-1,1-dimethylphenylethyl maleic acid monoamide Nt-BMMAm; N-tert-butyl maleic acid monoamide Nn-OMMAm; Nn-octyl maleic acid monoamide 3M; monomethyl maleate MRM; mono (diisopropylmethyl) malate AMPS; sodium N-sulfoisobutylene acrylamide

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

Since the adhesive of the present invention uses a specific modified PVA-based resin, it has excellent blocking resistance, and further has excellent storage stability in an aqueous adhesive.
It is useful in various adhesive applications such as general aqueous solution adhesives, rewetting adhesives, hot melt adhesives, pressure-sensitive adhesives, and quick-setting (honeymoon) adhesives, especially rewetting adhesives and hot melt adhesives. Very useful for

Claims (1)

[Claims] 1. A polyvinyl alcohol polymer containing 0.1 to 20 mol% of an ethylenically unsaturated dicarboxylic acid monoamide (A) as a copolymerization component, which is an amide of the ethylenically unsaturated dicarboxylic acid monoamide (A). An adhesive comprising a polyvinyl alcohol-based resin represented by the following chemical formula 1 as a main component. Embedded image (However, R ₁ is hydrogen, an alkyl group, or an aryl.
The groups R _{2 to} R ₄ are hydrogen or an alkyl group or aryl (ary
l) groups respectively, and at the same time two or more are not hydrogen but R
The total number of carbon atoms of _{1 to} R ₄ is 4 or more. )