JPH0130954B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a spray-type adhesive composition with good sprayability. [Prior art and its problems] There are three types of glues used at home: powder, liquid, and spray (aerosol or pump type), and products that take advantage of the characteristics of each type are commercially available. Among these, spray-type adhesives are particularly convenient because they allow for easy local pasting. In spray-type adhesives, in addition to imparting tensile strength,
It is necessary to have good ironing slipperiness and to have little adhesion of glue to the iron. Further, since spray-type glues have a relatively long shelf life, the spray button may become clogged during home use, resulting in uneven spray patterns or even inability to spray. Therefore, it is necessary to maintain good sprayability over a long period of time. Additionally, since it takes a long time for the aerosol to reach the consumer from the manufacturer, it is important to prevent corrosion of the aerosol can. Now, as a spray type adhesive, JP-A-52-
As shown in Japanese Patent No. 18992 and No. 53-49190, modified starch is generally used as the main base. Modified starch is an optimal base for imparting tensile strength, but when used for a long period of time, the spray pattern may become uneven or it may become impossible to spray. Therefore, one possible method for improving the spraying problem is, for example, increasing the inner diameter of the nozzle of the spray button. However, in this case, even if the poor spraying is improved, a preferable spray pattern or fine mist cannot be obtained. Another possible method for improving the spraying problem is to use modified starch with low viscosity. However, in this case, the tensile strength decreases and a satisfactory result cannot be obtained. In order to satisfy tensile strength, it is necessary to use modified starch with an appropriate viscosity. [Means for Solving the Problems] The present inventors have developed a nozzle that uses a polymer material with excellent tensile strength as the main base and has a small inner diameter (for example, 0.4 mm).
As a result of intensive study to create a spray-type adhesive that can provide a stable spray condition over a long period of time even when using
Unexpectedly, by limiting the ratio of sodium ions and ammonium ions blended in the glue composition to a specific range,
The present inventors have discovered that it is possible to obtain a glue composition that can achieve the above objectives, has an excellent aroma, and can be comfortably used as a spray-type glue, and has completed the present invention. That is, the present invention provides a spray-type adhesive composition mainly based on a polymeric substance, which contains sodium ions and ammonium ions as essential components,
The present invention provides a spray type adhesive composition characterized in that the mixing molar ratio thereof is 1/1 to 100/1. The best polymeric substance to be used as the main base of the glue composition of the present invention is modified starch, but other starch derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, or their oxidized decomposition products, as well as polyvinyl alcohol and polyvinyl alcohol, are also suitable. Any material can be used, such as acrylic acid or a salt thereof, a copolymer of maleic anhydride with ethylene, vinyl acetate, etc., or a synthetic polymer such as polyacrylamide. The modified starch used in the present invention has a viscosity of 5% aqueous solution, 20 centipoise or less at 20°C,
It is preferably 10 centipoise or less, and the blending amount is preferably 0.5 to 10% by weight, more preferably 2 to 7% by weight. The modified starch used in the present invention preferably includes hydroxyalkylated starch and carboxyalkylated starch, with hydroxypropylated starch and hydroxyethylated starch being particularly preferred. The degree of substitution is preferably 0.01 to 0.6, more preferably 0.03 to 0.4. The degree of substitution is
If it is less than 0.01, precipitates will be formed during long-term storage due to denaturation of the modified starch, and the whitening phenomenon will become noticeable when used in colored products. Also, the degree of substitution is 0.6
A larger one may be used, but this is not preferable since it tends to lower the tensile strength. The main base polymer material is usually 0.1% in the composition.
Contains ~10% by weight. Sodium ions and ammonium ions can be supplied to the paste composition of the present invention by adding a sodium compound and an ammonium compound. Examples of the sodium compound include sodium hydroxide, sodium sulfate, sodium chloride, sodium nitrate, sodium nitrite, and sodium benzoate, with sodium hydroxide, sodium nitrite, and sodium benzoate being particularly preferred. Examples of ammonium compounds include ammonium hydroxide, ammonium chloride, ammonium benzoate, aqueous ammonia, and the like. Since benzoate is also a rust inhibitor, it is most advantageously supplied as the sodium or ammonium salt. The molar ratio of the content of sodium ions and ammonium ions in the composition of the present invention is 1/1 to 100/
1, preferably 5/1 to 30/1. Outside this range, a composition with excellent spray stability and aroma cannot be obtained. In the present invention, the sodium compound and ammonium compound are usually added in a total amount of 0.05 to 5% by weight, preferably 0.3 to 2% by weight. The most preferred method for using the spray-type glue composition of the present invention is an aerosol-type spray, in which liquefied petroleum gas such as propane or butane, or fluorocarbon gas is preferably used as the propellant. The composition of the present invention may further include other additives as necessary, such as benzoic acid, a rust inhibitor such as potassium benzoate, a silicone activator, urea, ethylene glycol, propylene glycol, dipropylene glycol, fragrance, and a bactericidal agent. , alcohol, etc. can also be added. The PH of the glue according to the invention is 5-11, preferably 7
~9.5 is good. [Examples] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. In addition, "%" and "part" in the examples are based on weight. Examples 1 to 6 and Comparative Examples 1 to 2 Hydroxypropylated starch gelatinized at 70°C (degree of substitution 0.25; viscosity of 5% aqueous solution at 20°C is 10 cp) was used as the polymer base. The mixing ratio of sodium benzoate and ammonium benzoate was changed as shown in Table 1, and the amount added was 0.5% in total. 80 parts of this liquid and LPG (pressure 3.5Kg/at 20℃)
cm ² ) was filled into an aerosol can. Using this filled aerosol can, spray stability and aroma were examined by the method shown below. The results are shown in Table-1. (a) Spray stability: The above aerosol spray type glue was stored indoors at 20°C and 50% relative humidity, and a test was conducted for 6 months in which it was sprayed for about 10 seconds once every two weeks. ○...Spray pattern is uniform and spraying is possible ○～△...Spray pattern is almost uniform and spraying is possible △...Spray pattern is uneven but spraying is possible ×...Spray pattern is uneven and spraying is poor or spraying is possible Impossible (a) Fragrance: After filling the above aerosol spray type glue,
The test was conducted by spraying at room temperature. ○...Good ○～△...Slightly good △...Slightly bad ×...Poor

[Table] As is clear from Table 1, the ratio of sodium ions to ammonium ions is within a specific range [Na ⁺ /
NH ₄ ⁺ (molar ratio); 1/1 to 100/1, preferably 5/1 to 30/1],
Excellent sprayability and scent.

Claims (1)

[Claims] 1. A spray-type adhesive composition containing a polymeric substance as a main base, containing sodium ions and ammonium ions as essential components, with a mixing molar ratio of 1/1 to 100/1. A spray-type glue composition characterized by: 2. The spray type adhesive composition according to claim 1, wherein the mixed molar ratio of sodium ions and ammonium ions is 5/1 to 30/1. 3. The spray-type glue composition according to claim 1 or 2, wherein the polymeric substance as the main base is a modified starch. 4. The spray-type adhesive composition according to any one of claims 1 to 3, wherein the sodium ion or ammonium ion source is sodium benzoate or ammonium benzoate.