JPS6054993B2 - adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The main component of the present invention is a vinyl acetate resin emulsion (hereinafter referred to as vinyl acetate emulsion).

This invention relates to adhesives for paper tubes and paper processing that have excellent initial adhesive strength, workability, and film strength. Conventionally, glue or vinyl acetate emulsion has been used as an adhesive for paper tubes. Vinegar emulsion has a longer adhesion time and better workability than glue, but its initial adhesive strength and paper tube pressure resistance are poor. On the other hand, glue has excellent initial adhesion and pressure resistance, but it has to be used in the form of a heated aqueous solution and has poor workability.

Especially when working in winter, the adhesive speed of vinyl vinegar emulsion had to be reduced because the initial adhesive strength was poor, and it took about half a day to adjust the glue.

An object of the present invention is to provide an adhesive for paper tubes that has only the advantages of the above-mentioned glue or vinyl acetic acid emulsion, solves the disadvantages, and is also excellent in economical efficiency.

In the present invention, a basic substance is added to a copolymer of an α-olefin and an unsaturated carboxylic acid or a derivative thereof to make it water-soluble, and an unsaturated carboxylic acid and a peroxide are added to the copolymer and a derivative thereof to cause a reaction. Acetic acid emulsion obtained by emulsion polymerization using the reaction product as a protective colloid, benzyl alcohols which may be further substituted with an alkyl group, with the addition of an inorganic filler,
Or an adhesive composition characterized in that an alkyl carbitol acetate or a glycol monophenyl ether is added.

In the present invention, the α-olefin is a linear or branched one having 2 to 6 carbon atoms, such as polyethylene, propylene, n-butene, isobutylene, n-pentene,
Examples include isoprene and n-hexane.

Among these, isobutylene is suitable. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride, among which maleic anhydride is suitable. That is, isobutylene-maleic anhydride is suitable, and more preferably, isobutylene-maleic anhydride is neutralized with aqueous ammonia to a degree of neutralization of 0.3 to 0.8, and then heat-treated, and the most suitable is a partial imidized product of isobutylene-maleic anhydride. . That is, the copolymer of α-olefin and unsaturated carboxylic acid or its derivative in the present invention is expressed as follows.

Examples of the basic substance include caustic soda, soda carbonate, ammonia, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, organic amines, etc. alone or in combination, and preferably caustic soda, ammonia,
It is calcium carbonate, and the amount added is such that the degree of neutralization is 0.
Add so that it becomes 2 to 0.8.

Examples of unsaturated carboxylic acids include maleic acid, fumaric acid,
There are itaconic acid, acrylic acid, methacrylic acid, etc. Among these, acrylic acid, itaconic acid, and methacrylic acid are good, and the amount added is 0.0% based on the carboxylic acid polymer.
5 to 5% by weight is good. Peroxides include ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. Among these, hydrogen peroxide is the most suitable, and the amount added is 0.05 to 5 ml per carboxylic acid polymer. % is good. Examples of inorganic substances added to the emulsion include chalk and carbonic acid. There are calcium, silica powder, talc, clay, etc. Among these, calcium carbonate is suitable, and the amount added is 0.1 to 10% by weight based on the emulsion. Examples of benzyl alcohols which may be substituted with an alkyl group and which are added to increase wet tack include benzyl alcohol, methylbenzyl alcohol, ethylbenzyl alcohol, propylbenzyl alcohol, etc. is optimal.

Alkyl carbitol acetates R-0 (CH2-C
H2-0) 2C0CH3R: As the alkyl group having 1 to 4 carbon atoms, methyl carbitol acetate, ethyl carbitol acetate, propyl carbitol acetate,
There are butyl carbitol acetate, among which butyl carbitol acetate is the most suitable.

Glycol monophenyl ethers include monoethylene glycol, monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, and tetraethylene glycol monophenyl ether, among which monoethylene glycol monophenyl ether is suitable. .

These additives may be used alone or in combination, and the amount added is 0.5 to 1 weight percent, preferably 1 to 5 percent, based on the total weight of the emulsion. Furthermore, it is also possible to carry out emulsion polymerization using polyvinyl alcohol as a protective colloid in combination with the above reaction product. The adhesive composition of the present invention has the following characteristics.

(1) Excellent initial adhesive strength. The reason for this is thought to be that the protective colloid has a strong wet tack, and the addition of the wet tack imparting agent swells the particle surface of the vinyl acetate emulsion, increasing its tackiness.

(2) Wide working width.

The reason for this is thought to be that firstly, the protective colloid has strong wet tack and increases water retention, and the effects of additives promote adhesiveness and water retention.

(3) The film is hard.

The reason for this is firstly that the carboxy group-containing polymer forms a hard film.

Second, inorganic substances are used as fillers. Thirdly, the additive for improving wet tack is also effective as a plasticizer.
Normal DBP. ．． Compared to plasticizers such as DOP, the film-forming temperature is lower when added in small amounts, and at the same film-forming temperature, a film is formed with a smaller amount than the usual amount of plasticizer added, so the plasticization rate of the resin is small and a hard film is produced. This can increase the pressure resistance of paper tubes as an adhesive for paper tubes. (4) The cost of adhesive can be reduced.

The reason for this is that, compared to conventional products, the adhesive of the present invention exhibits less decrease in adhesive strength even when the amount of inexpensive inorganic filler added is increased. (5) The cost of paper tubes can be reduced.

The reason for this is that, as explained in (3), the adhesive of the present invention increases the pressure strength of the paper tube, so even if paper tube base paper of inferior quality is used, the same strength as the conventional paper tube can be obtained. I can do it. This is a big advantage, especially since base paper accounts for a high proportion of the cost of paper tubes. As described above, the adhesive composition of the present invention is particularly suitable as an adhesive for paper tubes, but by utilizing the above characteristics (1), (2), and (4), It is also effective as

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Isobutylene-maleic anhydride (molar ratio 1:1) copolymer 25V was dispersed in 65f1 of water, 7y of 50% caustic soda was added and stirred with heating to make it water-soluble, and methacrylic acid 1
Add f1 ammonium persulfate 1y and heat at 80°C for 3
Vinyl acetate monomer was emulsion polymerized as follows, using the product reacted for a period of time as a protective colloid.

The above reaction product 140y was mixed with 480y of water, heated and stirred, and vinyl acetate monomer 380f was added dropwise in a conventional manner using 1.5fI of ammonium persulfate as an initiator for emulsion polymerization to form an emulsion. Calcium carbonate 2 and 6f were added to 100y of the emulsion, and further 35f of butyl carbitol acetate was added to obtain an adhesive composition having a solid content of M% and a viscosity of 10,0001) PS/30C. Example 2 Isobutylene-maleic anhydride (molar ratio 1:
1) Imidized copolymer (imidization rate 50%) 25f
was dispersed in 70y of water, 14f of 25% ammonia water was added, heated and stirred to make an aqueous solution, 2f itaconic acid, 1.0y of hydrogen peroxide were added, and the reaction product was reacted at 80°C for 3 hours. A protective colloid was added to 200 f of a 10% aqueous solution of partially saponified polyvinyl alcohol (degree of polymerization 1,700), and emulsion polymerization was carried out in the same manner as in Example 1 to obtain an emulsion.

Calcium carbonate 25% for 100f of the emulsion
y and further added 3.5 f of benzyl alcohol to obtain an adhesive composition having a solid content percentage and a viscosity of 25,00 [Ps/30'C. Example 3 In the same manner as in Example 2, except that 3.5 f of phenyl glycol was added instead of benzyl alcohol,
An adhesive composition having a solid content of 53% and a viscosity of 23,000 CpS/30°C was obtained.

Comparative Example 1 10y of completely saponified polyvinyl alcohol is added to 90f of water and dissolved at 80C for 2 hours.

Using this solution as a protective colloid, 80y of vinyl acetate monomer was emulsion polymerized using a conventional method, and DBP7f and 0.19% of carbonic acid/soda were added as plasticizers to form a coating with a solid content of 52% and a viscosity of 22,000CpS/3C). A drug composition was obtained.
Table 1 shows the results of measuring the initial adhesive strength, working width, film hardness, and compressive strength of Examples 1 to 3 and Comparative Example 1 using the following test methods. Gate test method (4) Initial adhesive strength formulation: Adhesive/water = 10V20 (parts by weight) Adherent: Liner paper x liner paper (K-280) Application amount: 60g/W
t) Open time (coating deposition time): 10T+,
3@press; 0.
04k9/C7l! , 1 (8,2CfC adhesive strength; paper tear rate was measured by forcibly peeling off the paper at predetermined set time intervals.

(B) Film hardness (pencil hardness) A dry film was created on a glass plate, and 20C65RH%
The pencil hardness was measured after curing for one day.

(C) Pressure strength of paper tube Adherent: 0.77TL/TrL, thickness, 360f/Wt base paper composition for paper tube; Adhesive/water = 10V20 (parts by weight) Application amount: 30-40y/I open time; 5 to 10 seconds paper tube; 0.7 WL, / m x 4 fly spiral paper tube adhesion speed; 8 to 12 wL, / min Adhesion temperature: 2 (generations) Compressive strength: When compressed at a compression speed of 20 WL/TrL/min maximum strength under normal conditions.

Claims (1)

[Claims] 1 Add a basic substance to a copolymer of α-olefin and unsaturated carboxylic acid or its derivative to form an aqueous solution, and react the unsaturated carboxylic acid with peroxide to emulsify the reaction product as a protective colloid. An adhesive characterized in that an inorganic substance is added to a polymerized vinyl acetate resin emulsion, and benzene alcohols that may be substituted with an alkyl group, alkyl carbitols, or glycol monophenyl ethers are added to the polymerized vinyl acetate resin emulsion. agent composition.