JPH0786188B2 - Pressure sensitive adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a pressure-sensitive adhesive composition, more specifically, an acrylic emulsion pressure-sensitive adhesive composition, which is made of glass, pottery and plastic. The present invention relates to a pressure-sensitive adhesive composition which is useful for sticking to the outer surface of a container and for sealing and labeling used for sealing various cases in the distribution industry.

(Prior Art) In recent years, acrylic pressure-sensitive adhesives have been widely used in place of conventional natural rubber-based and synthetic rubber-based pressure-sensitive adhesives because of their excellent adhesive properties and durability. Also, water-based pressure-sensitive adhesives have been researched and developed in consideration of resource saving, environmental hygiene, and product cost.

Natural rubber-based and synthetic rubber-based pressure-sensitive adhesives have poor durability at low temperature, lack of cohesive strength at high temperature, etc. Excellent shearing force.

For this reason, a pressure-sensitive adhesive is applied to a base material such as paper to resist the restoring force of the base material such as when used as a label, a seal, etc. on a curved surface of a container or a bent part, or for sealing various cases. Natural rubber-based and synthetic rubber-based pressure-sensitive adhesives are still predominant in applications requiring repulsion resistance.

Conventional acrylic pressure sensitive adhesives are not satisfactory when applied to applications where high shear forces are desired. Therefore, in order to further improve the shearing force of this type of pressure-sensitive adhesive, it has been attempted to add a cross-linking agent such as an aziridine compound, a melamine compound, an epoxy compound, a metal salt to an acrylic emulsion obtained by emulsion polymerization. Came. However, with such a means, only the cohesive force becomes large, and the adhesive force and the tackiness are reduced accordingly, so that the pressure sensitive adhesive having high adhesive force, high tackiness and high shearing force is eventually obtained. It was difficult to obtain an agent composition.

(Problems to be Solved by the Invention) The present invention provides a pressure-sensitive adhesive having both durability and high shearing force. Furthermore, the present invention provides a water-based pressure-sensitive adhesive having high adhesive strength and high tackiness.

[Structure of Invention]

(Means for Solving the Problems) In the present invention, 50 to 99.9% by weight of an alkyl acrylate having an alkyl group with 4 to 12 carbon atoms, 0.1 to 15% by weight of an α, β-unsaturated carboxylic acid, and others 100 parts by weight of an acrylic copolymer consisting of 0 to 49.9% by weight of vinyl monomer of dialkyldiallylammonium halide
The pressure-sensitive adhesive composition is characterized by containing 0.01 to 50 parts by weight.

The alkyl acrylates having 4 to 12 carbon atoms in the alkyl group of the present invention include straight chain or branched aliphatic alcohols such as butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. The acrylic acid ester of Particularly preferred is 2-ethylhexyl acrylate. In order to obtain basic physical properties as a pressure-sensitive adhesive, the amount of these alkyl acrylates used is preferably 50 to 99.9% by weight of the acrylic copolymer.

Examples of the α, β-unsaturated carboxylic acid of the present invention include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid and fumaric acid. These α,
β-unsaturated carboxylic acid is 0.1 ~ 15 of acrylic copolymer
The adhesiveness and cohesive force of the pressure-sensitive adhesive can be balanced by mixing and copolymerizing the weight% of the alkyl acrylate and other necessary vinyl monomers and copolymerizing them.

Examples of vinyl monomers other than the above that can be used in the acrylic copolymer of the present invention include alkyl acrylates having an alkyl group with 3 or less carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, and the like. There is a methacrylic acid ester having 1 to 12 carbon atoms, such as methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate group, and in addition, vinyl acetate, styrene, vinyltoluene, acrylonitrile and the like.

The acrylic copolymer of the present invention is preferably obtained by emulsion polymerization. For example, emulsion polymerization may be carried out in an aqueous system in the presence of an emulsifier and a polymerization initiator as the monomer mixture.

The pressure-sensitive adhesive composition of the present invention is a dialkyldiyl ammonium halide in the emulsion of the acrylic copolymer obtained as described above, It is a mixture of. In the above formula, R is a lower alkyl group such as methyl group, ethyl group, propyl group or butyl group, X
Is a halogen atom such as chlorine or bromine. These dialkyl diallyl ammonium halides can be obtained as an aqueous solution.

The dialkyl diallyl ammonium halide is 0.01 to 50 parts by weight with respect to 100 parts by weight of the solid content of the acrylic copolymer.
Weight parts are preferable, and in applications where adhesive strength is important,
0.1 to 5 parts by weight is preferable. The upper limit of the above numerical value is limited by a decrease in adhesive strength, and the lower limit of the above numerical value is limited by a decrease in cohesive strength.

Example 1 Pure water 65 parts Sodium diphosphate 0.6 parts Dodecylbenzene sulfonate 1 part Polyoxyethylene octylphenol ether 1 part Weigh and heat to 80 ° C. under stirring at 150 RPM Then, A mixture of 2-ethylhexyl acrylate 74.5 parts Vinyl acetate 22 parts Acrylic acid 3.5 parts and 6 parts of a 5% potassium persulfate aqueous solution was uniformly added dropwise to the reaction system kept at 80 ° C. for 3 hours for polymerization. After all the monomers have been added dropwise, the reaction is continued at 80 ° C. for 2 hours to complete the polymerization.

0.5 part of dimethyldiallylammonium chloride was added to 100 parts of the solid content of this composition to obtain a pressure-sensitive adhesive composition.

This pressure-sensitive adhesive composition was applied to crystal-coated paper (manufactured by Nippon Kakoh Paper Co., Ltd.) and dried by heating at 100 ° C. for 2 minutes (coating amount dry 30 to 40 g / m ² ) to obtain a sample piece.

Next, the above sample was pasted on a stainless steel plate, roll-pressed according to JIS method, 180 degree peel strength, ball tack and shear force were measured by a Shopper type peel tester, stuck to various containers with curved surfaces and marketed It was used to seal the cardboard case.

The results are shown in Table 1.

Example 2 Pure water 68. parts Sodium acetate 0.6 parts Polyoxyethylene sorbitan monolaurate 1 part Polyoxyethylene nonylphenol ether 1 part Weigh and heat to 80 ° C. under stirring at 15 RPM. Then, a mixture of 2 ethylhexyl acrylate 59.5 parts butyl acrylate 30.0 parts vinyl acetate 6.5 parts acrylic acid 4.0 parts and 6 parts of 10% ammonium persulfate aqueous solution was added dropwise uniformly over 3 hours into the reaction system kept at 80 ° C to carry out polymerization. Let After all the monomers were dropped, the reaction was continued at 80 ° C. for 2 hours to complete the polymerization. The solid content of this composition
1.5 parts of dibutyldiallylammonium chloride was added to 100 parts, and a sample piece was prepared in the same manner as in Example 1 below, and the same test was conducted. The results are shown in Table 1.

Comparative Example 1 A sample piece was prepared in the same manner as in Example 1, except that the composition obtained in Example 1 was not blended with dialkyldiallylammonium chloride, and a comparison was made with each pressure-sensitive adhesive composition. . The measurement results are shown in Table 1.

Example 3 Pure water 65 parts Sodium diphosphate 0.6 parts Dodecylbenzene sulfonate 1 part Polyoxyethylene octylphenol ether 1 part Weigh and heat to 80 ° C. under stirring at 100 RPM Next, 29.5 ethyl hexyl acrylate 89.5 parts A mixture of 4.6 parts of vinyl acetate and 6.0 parts of acrylic acid and 6 parts of a 5% aqueous solution of potassium persulfate were uniformly added dropwise to the reaction system kept at 80 ° C. for 3 hours for polymerization. After all the monomers have been added dropwise, the reaction is continued at 80 ° C. for 2 hours to complete the polymerization.

5 parts of dimethyldiallylammonium chloride was added to 100 parts of the solid content of this composition to obtain a pressure-sensitive adhesive composition.

Apply this pressure-sensitive adhesive composition to high-quality paper (45 kg),
A sample piece was obtained by heating and drying at 0 ° C. for 2 minutes (coating amount dry 20 g / m ² ).

Next, the above-mentioned sample piece was attached to a stainless plate, roll-bonded according to JIS method, and 180 degree peel strength was measured by a Shopper type peel tester to examine the contamination property to various adherends. The results are shown in the table below.

Example 4 Pure water 68 parts Sodium acetate 0.6 parts Polyoxyethylene sorbitan monolaurate 1 part Polyoxyethylene nonylphenol ether 1 part Weigh and heat to 80 ° C. under stirring at 100 RPM. Then, a mixture of 2-ethylhexyl acrylate 59.5 parts butyl acrylate 30.0 parts vinyl acetate 6.5 parts acrylic acid 4.0 parts and 6 parts of 10% ammonium persulfate aqueous solution were added dropwise uniformly over 3 hours into the reaction system kept at 80 ° C. , Polymerize. After all the monomers were dropped, the reaction was continued at 80 ° C. for 2 hours to complete the polymerization.

10 parts of dibutyldiallylammonium chloride was added to 100 parts of the solid content of this composition, and a sample piece was prepared in the same manner as in Example 1 below. Similarly, adhesive strength and contamination of various adherends were obtained. The results of examining the sex are shown in Table 2.

Comparative Example 2 A sample piece was prepared in the same manner as in Example 3, except that the composition obtained in Example 3 was not blended with dialkyldiallylammonium chloride, and a comparison was made with each pressure-sensitive adhesive composition. . The measurement results are shown in Table 2.

EFFECTS OF THE INVENTION The pressure-sensitive adhesive composition of the present invention has high adhesive strength, high tackiness, and high shearing force, and therefore metal, glass, pottery, PVC,
It can be applied by selecting the kind of adherend such as polyethylene. In particular, even if it is attached to a curved surface of the container, a bent part, a label for sealing the case, a part such as a seal where the restoring force of the base material works, the label and the seal partly peel off with time. There is no such thing.

In addition, the pressure-sensitive adhesive composition of the present invention can be designed in a wide range from removable pressure-sensitive adhesives to applications in which adhesive strength is important, depending on the amount of the dialkyldiallylammonium halide compounded.

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Claims (1)

[Claims] 1. An acrylic acid alkyl ester having an alkyl group with 4 to 12 carbon atoms in an amount of 50 to 99.9% by weight, an α, β-unsaturated carboxylic acid in an amount of 0.1 to 15% by weight, and other vinyl monomers in an amount of 0 to 49.9% by weight. % Acrylic copolymer 100%
A pressure-sensitive adhesive composition, characterized in that 0.01 to 50 parts by weight of a dialkyl diallyl ammonium halide is blended with respect to parts by weight.