JPH08134419A - Aerosol adhesive composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition which leaves no mark on a porous material adherend and does not cause the denaturation and discoloration of an organic material adherend by dissolving or dispersing an adhesive component containing a pressure-sensitive adhesive in a volatile component comprising a liquefied propellant gas.

CONSTITUTION: There is provided an aerosol adhesive composition prepared by dissolving or dispersing an adhesive component containing a pressure-sensitive adhesive (e.g. one containing a base polymer such as an acrylic polymer or a silicone polymer) in a volatile component comprising a liquefied propellant gas (e.g. one based on n-butane, isobutane, dimethyl ether, or the like). This composition is free from an organic solvent and water and therefore it has very rapid driability and requires no open time. Further, when it is applied to a porous adherend such as paper, it does not penetrate into its inside and leaves no mark on the part to which it has been applied. Furthermore, when it is applied to an organic material adherend such as a plastic, the discoloration and denaturation of the surface of the adherend are prevented.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aerosol type adhesive composition. More specifically, it contains a specific adhesive component having adhesiveness at room temperature and a liquefied gas for injection as main components.
The present invention relates to an aerosol-type adhesive composition that does not require an organic solvent or water as a solvent. The adhesive composition of the present invention can be filled into a pressure resistant container such as an aerosol can to form an aerosol type adhesive product, and the adhesive composition can form a uniform and stable solution in the aerosol can. Has a uniform particle or lace-like spray pattern when it is sprayed from a can, and can exhibit good adhesiveness in bonding paper or film.

[0002]

2. Description of the Related Art Sprayable adhesives (aerosol adhesives) have been developed and provided for convenience of handling. Such an adhesive is usually an organic solvent type adhesive containing a base polymer (also referred to as a base polymer) as an adhesive component, a propellant, an organic solvent as a solvent of the base polymer, and other additives. It is an agent. In such organic solvent-based adhesives, environmental damage of chlorine-based organic solvents and harmfulness of petroleum-based solvents such as toluene and hexane to humans have recently become a problem. These environmental destruction,
The problems such as harmfulness to the human body are largely caused by the organic solvent mainly used as a solvent for the adhesive, and it is desired to reduce the amount of the organic solvent used in the adhesive.

A conventional aerosol-based adhesive has a rubber-like elastomer such as styrene-butadiene rubber (SBR) as a base polymer and is prepared by using propane and dioxide as disclosed in Japanese Patent Publication No. 45-22239. It is used by being uniformly dispersed in an organic solvent such as hexane, methyl ethyl ketone, methyl isobutyl ketone and various alcohols together with a propellant such as carbon and fluorohydrocarbon.
This adhesive is characterized in particular by a high solids content and therefore can be stored for a long time and also
At the time of spraying, it is possible to avoid inconveniences such as pulling a string and forming a spider web.

Japanese Patent Publication No. 46-12640 also discloses a sprayable adhesive containing an organic solvent as an essential component, similarly to the above. This adhesive is characterized in particular in that it contains, as base polymer, a particular cross-linked acrylic acid ester polymer or copolymer in a relatively high concentration. Using this adhesive, it is possible to perform atomization without the stringing and spider web formation that were the drawbacks of the prior art.

However, conventional organic solvent type adhesives have the following problems. (1) Since the adherend contains an organic solvent, when the adherend is a porous material such as paper or cloth, it penetrates into the adherend during spraying and leaves a trace of application of the adhesive. (2) When the adherend is plastic or a similar material, the plastic or the processed substance on the surface is dissolved by the organic solvent, and the surface of the adherend is discolored or deteriorated. Specific examples include thermal paper such as vinyl chloride film and facsimile paper.

Although such a problem can be substantially solved by avoiding the use of an organic solvent,
Since it is essential to use the above-mentioned base polymer and the like, an organic solvent is indispensable, and therefore, it has not been solved. In order to solve the above problems, it has been proposed to use water instead of the organic solvent. That is, it is an emulsion type adhesive agent using water, which is solvent-free, as a medium. Emulsion type adhesives are disclosed, for example, in JP-A-61-60769.
It consists of a base polymer emulsion and a pressurized gas. However, this adhesive tends to cause nozzle clogging during spraying due to lack of mechanical stability of polymer particles,
Not practical. In addition, Japanese Patent Publication No. 2-42397 discloses
We have proposed a water-dispersible adhesive consisting of a water-dispersed hiddle sol of an acrylic copolymer. However, since this adhesive uses water as the medium, it swells paper and remains wrinkles after drying in applications where paper is adhered, and the adhesive component soaks into the paper to ensure sufficient adhesion. There is a problem that you cannot obtain strength. Even in applications other than paper, there are disadvantages unique to water-dispersed adhesives, such as slow drying.

On the other hand, as solvent-free adhesives that do not use organic solvents or water, there are hot-melt adhesives and many reactive adhesives including epoxy resin-based and urethane-based adhesives. However, these adhesives also have some problems. For example, a hot-melt type adhesive has to be applied using a special melting tool, is complicated to handle, and is very difficult to apply thinly and evenly to paper or the like. Although the reactive adhesive does not contain an organic solvent, the monomer component contained has a negative effect on the human body in terms of hygiene.

[0008]

SUMMARY OF THE INVENTION The first object of the present invention is to:
In addition, when the adherend is a porous material such as paper or cloth,
It is an object of the present invention to provide an improved aerosol-type adhesive composition in which the adhesive component does not soak into the inside thereof to leave a trace of application. Secondly, the object of the present invention is such that when the adherend is made of an organic material such as plastic or the surface of the adherend is surface-treated with such an organic material, it is possible to do so when the adhesive is sprayed. Another object of the present invention is to provide an improved aerosol-type adhesive composition in which various materials are dissolved and the surface of an adherend is not discolored or deteriorated.

Thirdly, an object of the present invention is to provide an aerosol-type adhesive composition which can cope with environmental problems and solvent regulation, which essentially eliminates the use of a volatile organic solvent harmful to the human body. To provide. Fourthly, the object of the present invention is not to cause clogging of the spray nozzle, and when the adherend is paper, does not swell the paper or leave wrinkles, and the adhesive strength and the drying property. Another object is to provide an excellent aerosol-type adhesive composition.

Other objects of the present invention will be readily understood from the following detailed description.

[0011]

According to the present invention, the above-mentioned object is to dissolve or disperse an adhesive component containing a pressure-sensitive adhesive in a volatile component essentially consisting of a liquefied gas for injection. It can be achieved by an aerosol type adhesive composition characterized in that In the aerosol type adhesive composition according to the present invention, the pressure-sensitive adhesive is preferably one or more selected from the group consisting of acrylic polymers, silicone polymers, ethylene-vinyl acetate copolymers and styrene polymers. And the liquefied gas for injection preferably contains one or more liquefied gases selected from the group consisting of n-butane, isobutane and dimethyl ether.

The aerosol type adhesive composition of the present invention can preferably have the following composition. 1. The adhesive contains an acrylic polymer as a base polymer, and the liquefied gas for injection is isobutane, n
-Aerosol type adhesive composition containing butane or dimethyl ether as a main component.

2. The adhesive contains a silicon-based polymer as a base polymer, and the liquefied gas for injection is n
An aerosol-type adhesive composition containing butane or isobutane as a main component. 3. An aerosol-type adhesive composition in which the pressure-sensitive adhesive contains an ethylene-vinyl acetate copolymer as a base polymer, and the liquefied gas for injection contains dimethyl ether as a main component.

4. An aerosol-type adhesive composition in which the pressure-sensitive adhesive contains a styrene-based polymer as a base polymer, and the liquefied gas for injection contains dimethyl ether as a main component. In the aerosol-type adhesive composition according to the present invention, each of the components to be contained therein will be described in detail below. However, in order to fully understand the present invention, the terms used in the present specification are first explained. To do.

The term "adhesive agent" as used herein means a substance (base polymer) or a mixture thereof (base polymer) which is adhesive at room temperature and can be adhered to an adherend with a light pressure. Polymer and tackifier). That is, the definition of this term is "JIS K" in the JIS standard.
6800, adhesive / adhesive term ”.

To explain further, in the pressure-sensitive adhesive composed of the base polymer, the base polymer has self-adhesiveness, in other words, has the property of being a pressure-sensitive adhesive itself. Even if it is applied in the absence of solvent, excellent adhesiveness can be achieved. Also, when a mixture of a base polymer and a tackifier serves as a pressure-sensitive adhesive, the same effect is obtained. By the way, generally speaking, an organic solvent-based adhesive can exhibit its adhesive strength only after the organic solvent of its component is well wetted with the material to which it is adhered, in the absence of an organic solvent. It can't be an adhesive. In addition, such adhesives
It can be easily dissolved or uniformly dispersed in the liquefied gas for injection used in combination with it.

The term "adhesive component" means a non-volatile component capable of exerting adhesiveness after the adhesive composition of the present invention is applied to an adherend by spraying and then the volatile components are evaporated. means. “Liquefied gas for injection” means a volatile component that is liquid at room temperature and high pressure, and has three functions as follows when used in the adhesive composition of the present invention: (1) The function of dissolving or dispersing in the liquefied gas, (2) the function as a propellant of injecting the adhesive composition from a closed container such as an aerosol can, and (3) the adherent composition to an adherend by injection. After applying
The adhesive composition has a function of rapidly drying, and as the function of the drying function (3), (a) when an adherend made of a porous material such as paper or cloth is used as an adherend, The effect of preventing the adhesive component from penetrating inside and leaving a coating mark, and (b) when the adherend or its surface is made of an organic material such as plastic, such a material is dissolved and the adherend is adhered. The effect of preventing discoloration and deterioration of the surface of the can be introduced.

"Dissolved or dispersed" means that
It means that the adhesive component is contained in the volatile component in a liquid state of either a solution or a dispersion. Such liquids should be placed in a container such as an aerosol can and stirred without stirring. Otherwise, after gently stirring such as shaking the aerosol can by hand several times, a uniform solution or dispersion liquid should be obtained. become. By making the solution or dispersion into a uniform state, when spraying the aerosol-type adhesive composition from a can or the like, the spray pattern can be laced or particulate, and therefore,
The adhesive composition can be applied to the adherend uniformly and easily without causing unevenness in application. The adhesive composition is particularly preferably in a solution state.

In the aerosol type adhesive composition according to the present invention, the pressure-sensitive adhesive used as the adhesive component is, as described above, an acrylic polymer, a silicone polymer,
Advantageously, it comprises one or more base polymers selected from the group consisting of ethylene-vinyl acetate copolymers and styrenic polymers. Such base polymers preferably have a glass transition temperature of about -80 to about 80 ° C, more preferably about -50 to about 25 ° C. Also, when the adhesive is composed of a base polymer, such base polymer is preferably about -80 to about 25.
C., more preferably about -50 to about 15 [deg.] C. glass transition temperature. Furthermore, such base polymers preferably have a weight average molecular weight of about 3 × 10 ³ to about 1 × 10 ⁶ , more preferably about 1 × 10 ⁴ to about 5 × 10 ⁵ .

A preferred example of a base polymer which can be advantageously used in the practice of the present invention is as follows:

Acrylic Polymer The acrylic polymer is preferably a monomer composed of an acrylic acid alkyl ester or a methacrylic acid alkyl ester, in which the side chain alkyl group has 1 to 14 carbon atoms. It is a polymer or a copolymer. Since this acrylic polymer dissolves or disperses particularly easily in the liquefied gas for injection used in the aerosol-type adhesive composition of the present invention, the adhesive composition should be sprayed in the form of particles or flakes. To facilitate. Further, since such a polymer itself can serve as a pressure-sensitive adhesive, even if it is sprayed and coated in the absence of a solvent, it can exhibit excellent adhesiveness. Such polymers are particularly preferably homopolymers or copolymers of alkyl acrylates. Specific examples are: "Aroset 8101" available from Nippon Shokubai Co., Ltd. "Acronal available from Toagosei Kagaku Co., Ltd."
(Acronal) 8501D ”and the like.

Silicon-Based Polymer The silicon-based polymer is preferably a homopolymer or copolymer of a monomer composed of alkylsiloxane.
Since this silicone polymer is particularly easily dissolved or dispersed in the liquefied gas for injection used in the aerosol-type adhesive composition of the present invention, the adhesive composition should be sprayed in the form of particles or flakes. To facilitate. Further, since such a polymer itself can serve as a pressure-sensitive adhesive, even if it is sprayed and coated in the absence of a solvent, it can exhibit excellent adhesiveness. Such polymers are particularly preferably polydimethylsiloxane or methylsilicone varnish. Specific examples include: "SD 4560" available from Toray Dow Co., Ltd.
(Polydimethylsiloxane) "TSR129 available from Toshiba Silicone Co., Ltd.
1 ”(methyl silicone varnish).

Ethylene-Vinyl Acetate Copolymer (EVA) The ethylene-vinyl acetate copolymer is preferably an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25 to 60 mol%. Since this EVA copolymer is particularly easily dissolved or dispersed in the liquefied gas for injection used in the aerosol-type adhesive composition of the present invention, the adhesive composition is sprayed in the form of particles or flakes. Make it easy. Further, since such a copolymer itself can serve as a pressure-sensitive adhesive, it can exhibit excellent adhesiveness even if it is sprayed and applied in the absence of a solvent. Such a copolymer is particularly preferably an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30 to 45 mol%. Specific examples are, for example, all available from DuPont: "EVA 40Y" (vinyl acetate content 40 mol%) and "EVA 150" (vinyl acetate content 33 mol%).

Styrenic Polymer The styrenic polymer is preferably a copolymer of styrene and one or more monomers selected from the group consisting of butadiene, isoprene, ethylene, butylene and the like, particularly preferably a block copolymer thereof. It is a polymer. Since such a copolymer is particularly easily dissolved or dispersed in the liquefied gas for injection used in the aerosol-type adhesive composition of the present invention, the adhesive composition is sprayed in the form of particles or flakes. Easy to do. Further, since such a copolymer itself can serve as a pressure-sensitive adhesive, it can exhibit excellent adhesiveness even if it is sprayed and applied in the absence of a solvent. Specific examples of such copolymers are available, for example, from Shell Chemical Company: "Kraton 1107" (styrene-
Isoprene-styrene block copolymer) "Kraton 1101" (styrene-
Butadiene-styrene block copolymer) "Kraton (Clayton) G1657" (styrene-ethylene, butylene-styrene block copolymer) and the like.

In the aerosol type adhesive composition of the present invention, the liquefied gas for injection used to function as a propellant or the like is a liquefied gas which can be liquid at room temperature and high pressure as described in the definition of terms above. It is gas. By using such a liquefied gas, the adhesive component containing the above-mentioned pressure-sensitive adhesive can be dissolved or stably and uniformly dispersed in the volatile component essentially consisting of the liquefied gas. Is. The liquefied gas for injection that can be used in the practice of the present invention is preferably liquefied petroleum gas such as propane, isobutane, n-butane, dimethyl ether, Freon 134a (CH ₂ FCF ₃ ), Freon 1
52a (CH ₃ CHF ₂ ) and other fluorinated hydrocarbons, and part 2
It is a mixture of types or more. Compressed gases such as nitrogen gas and carbon dioxide gas cannot be used in the practice of the present invention because they do not become liquid even at room temperature and high pressure.

It was mentioned above that the liquefied gas for injection constitutes an essential part of the volatile constituents. This is especially intended to obtain two effects (a) and (b) which are derived as the action of the drying function (3) among the three functions of the liquefied gas for injection. Therefore, if a large amount of a volatile component other than the liquefied gas, for example, an organic solvent such as toluene, xylene, or ethyl acetate is mixed in the volatile component, the above effects (a) and (b) cannot be obtained. . According to the knowledge of the present inventors, the proportion of the liquefied gas for injection in the volatile component is preferably 90 to 100% by weight, more preferably 95 to 100% by weight.

The aerosol type adhesive composition of the present invention preferably contains a tackifier in the adhesive. The tackifier, in the adhesive composition of the present invention, has the function of improving the wettability of the entire adhesive to the adherend and increasing the cohesive force of the entire adhesive, and as a result, the adhesive strength as an adhesive. Improve the quality. As the tackifier, a base polymer which is also used in the adhesive and a material which is well compatible with the liquefied gas for injection can be advantageously used.
Such tackifiers preferably include, for example, naturally occurring resins such as rosin and its derivatives (rosin ester) and terpene-based resins (polyterpene resins), and synthetic resins such as petroleum-based resins, Preferably, rosin, rosin ester, and polyterpene resin are included.

Rosin is a refined resin acid contained in pine, contains abietic acid as a main component, and has a softening point of about 70 to 80 ° C. Rosin is available as "rosin" from Arakawa Chemical Industries, Ltd., for example. The rosin ester is obtained by esterifying rosin with alcohol, glycerin or the like, preferably 70 to 10
It has a softening point of 0 ° C. Rosin ester is commercially available from Arakawa Chemical Industry Co., Ltd. under the trade name of "Super Ester A1".
00 ”and the product name“ Stevelite Ester 10 ”from Rika Hercules Co., Ltd., respectively. The terpene resin includes a terpene polymer such as pinene and limonene, preferably 55 to 13
It has a softening point of 5 ° C. This type of resin is, for example,
Product name “Picolite (Pic
colyte) A115 ”,“ Picolite A125 ”and“ Picolite A135 ”(α-pinene resin),
Product name "YS Resin PX10" from Yasuhara Chemical Co., Ltd.
00 ”(β-pinene-based resin). The petroleum-based resin is typically a hydrocarbon resin having 5 to 9 carbon atoms, and preferably has a softening point of 80 to 145 ° C. The "softening point" described above is a ball-and-ring softening point (according to JIS K2207). This type of hydrocarbon resin is commercially available, for example, from Arakawa Chemical Industry Co., Ltd. under the trade name "ALCON P-90".
(Alicyclic saturated hydrocarbon resin) and from Tonex Co., Ltd. under the trade name “Escorez 130
5 ”, respectively.

In the aerosol type adhesive composition of the present invention, a base polymer, a liquefied gas for injection and, if necessary,
The tackifiers may be mixed in various combinations and in various ratios depending on the intended use of the adhesive composition, desired effect, adhesion conditions, material of the adherend, and other factors. it can. In the aerosol adhesive composition of the present invention, according to the first preferred embodiment of the present invention, the adhesive contains an acrylic polymer as a base polymer, and the liquefied gas for injection is isobutane, n-butane or dimethyl ether. Contains as a main component. In such an adhesive, the acrylic polymer is preferably contained in an amount of more than 50% by weight, particularly preferably in the range of 60 to 90% by weight, based on the total weight of the adhesive. The content of such a polymer is 50% by weight
When it is below, there is a possibility that sufficient wettability to the adherend may not be secured when the adhesive composition of the present invention is applied by spraying. Also, here, "include as main component"
The term, when used herein to describe the composition of a liquefied gas for injection, has the following meaning. That is, with respect to the total weight of the liquefied gas for injection, a specific liquefied gas for injection, that is, isobutane here,
It means that n-butane or dimethyl ether is contained in an amount of more than 50% by weight, preferably 60% by weight or more. The content of such a specific liquefied gas for injection is 5
When it is 0% by weight or less, it becomes difficult to form a stable and uniform solution or dispersion of the adhesive composition of the present invention, and it may not be possible to spray the particles in the form of particles or lace. In the first aspect, the liquefied gas for injection is particularly preferably isobutane or dimethyl ether.

According to a second preferred embodiment of the present invention, the adhesive contains a silicon polymer as a base polymer, and the liquefied gas for injection contains n-butane or isobutane as a main component. Here, the silicone polymer is contained in an amount of preferably more than 50% by weight, particularly preferably 60 to 90% by weight, based on the total weight of the pressure-sensitive adhesive. The content of such a polymer is 5
When the content is 0% by weight or less, it may not be possible to secure sufficient wettability with respect to an adherend when the adhesive composition of the present invention is applied by spraying. Further, n-butane or isobutane is 50% by weight based on the total weight of the liquefied gas for injection.
More than 60 wt%.
The content of such a specific liquefied gas for injection is 50% by weight
When the content is below, it becomes difficult to form a stable and uniform solution or dispersion of the adhesive composition of the present invention, and there is a possibility that it cannot be sprayed in the form of particles or lace. In the second aspect, isobutane is particularly preferable as the liquefied gas for injection.

Furthermore, according to a third preferred embodiment of the present invention, said adhesive contains ethylene-vinyl acetate copolymer as a base polymer and said liquefied gas for injection contains dimethyl ether as a main component. Here, the ethylene-vinyl acetate copolymer is contained in an amount of preferably more than 50% by weight, particularly preferably 60 to 90% by weight, based on the total weight of the pressure-sensitive adhesive. When the content of such a copolymer is 50% by weight or less, sufficient wettability with respect to an adherend may not be secured when the adhesive composition of the present invention is applied by spraying. Also,
Dimethyl ether is contained in an amount of more than 50% by weight, preferably 60% by weight or more, based on the total weight of the liquefied gas for injection. When the content of such a specific liquefied gas for injection is 50% by weight or less, it becomes difficult to form a stable and uniform solution or dispersion of the adhesive composition of the present invention, and it becomes particulate or lace. May not be able to spray like

Furthermore, according to a fourth preferred embodiment of the present invention, the adhesive contains a styrene polymer as a base polymer, and the liquefied gas for injection contains dimethyl ether as a main component. Here, the styrene-based polymer is contained in an amount of preferably more than 50% by weight, particularly preferably 60 to 90% by weight, based on the total weight of the pressure-sensitive adhesive.
It is included in the range of. The content of such a polymer is 50
When it is at most% by weight, it may not be possible to secure sufficient wettability with respect to the adherend when the adhesive composition of the present invention is applied by spraying. Further, dimethyl ether is contained in an amount of more than 50% by weight, preferably 60% by weight or more, based on the total weight of the liquefied gas for injection. When the content of such a specific liquefied gas for injection is 50% by weight or less, it becomes difficult to form a stable and uniform solution or dispersion of the adhesive composition of the present invention, and it becomes particulate or lace. May not be able to spray like

In any of the above-mentioned first to fourth aspects, since it is easy to form a stable and uniform solution or dispersion of the adhesive composition of the present invention, it is sprayed in the form of particles or lace. It is possible to spray, and it is easy to secure sufficient wettability to the adherend when applied by spraying. Further, the blending ratio of the pressure-sensitive adhesive and the liquefied gas for injection can be widely and arbitrarily changed within the preferable range as described above. According to the knowledge of the present inventors, the blending amount of the liquefied gas for injection with respect to 100 parts by weight of the pressure-sensitive adhesive is preferably in the range of 200 to 10000 parts by weight, more preferably 500 to 3300 parts by weight. If the amount of the liquefied gas for injection is less than 200 parts by weight, the viscosity of the solution or dispersion of the adhesive composition is too high, and there is a tendency that it does not spread well as a spray. On the contrary, if it is more than 10,000 parts by weight. Since the concentration of the adhesive becomes thin, it is necessary to increase the number of sprays in order to obtain high adhesive strength.

The tackifier, which can be advantageously used in combination with the above-mentioned pressure-sensitive adhesive as required, can be arbitrarily changed depending on the kind of the pressure-sensitive adhesive used. For example, in the aspect in which the pressure-sensitive adhesive contains an acrylic polymer as a base polymer, it is preferable to use rosin, a rosin ester, or a polyterpene resin as a tackifier,
It is particularly preferred to use rosin esters. Further, in the embodiment in which the pressure-sensitive adhesive contains a silicon-based polymer as a base polymer, it is preferable to use rosin, rosin ester or petroleum-based resin as the tackifier, and it is particularly preferable to use petroleum-based resin. Further, in the aspect in which the pressure-sensitive adhesive contains an ethylene-vinyl acetate copolymer as a base polymer, it is preferable to use rosin, a rosin ester or a petroleum-based resin as a tackifier, and it is particularly preferable to use a petroleum-based resin. preferable. Furthermore, in the embodiment in which the pressure-sensitive adhesive contains a styrene-based polymer as a base polymer, it is preferable to use rosin, a rosin ester, a polyterpene resin or a petroleum-based resin as a tackifier, and it is particularly preferable to use a polyterpene resin. . In any of the above-mentioned aspects in which the pressure-sensitive adhesive contains a specific base polymer and a specific tackifier, the wettability of the whole pressure-sensitive adhesive to the adherend is particularly improved, and the cohesive force of the whole pressure-sensitive adhesive is particularly improved. Since it is increased, the adhesive strength as an adhesive is particularly improved.

The tackifier can be arbitrarily mixed with the pressure-sensitive adhesive in a wide range. The tackifier is adhesive 1
It is preferable to mix it in the range of 0 to 200 parts by weight with respect to 00 parts by weight. That is, the tackifier is preferably not more than 200 parts by weight in order to obtain the desired adhesive strength if it is not added or if it is added. The tackifier is 50 to 100 parts by weight of the adhesive.
It is particularly preferable to blend in the range of 100 parts by weight.

The aerosol-type adhesive composition of the present invention is used by filling it into a pressure container such as a metal aerosol can made of steel or a glass bottle. Such a pressure vessel can have any shape and size, and
If necessary, in order to prevent undesired reactions and the like from occurring between the inner wall of the container and the adhesive composition, the inner wall of the container may be coated with a suitable material.
Suitable coating materials can include, for example, epoxy resins.

[0037]

In the aerosol type adhesive composition of the present invention, a base polymer which has the property of itself being a pressure sensitive adhesive and can be easily dissolved or dispersed in a liquefied gas for injection, or a base polymer and a tackifier. Since the mixture consisting of and is contained in the adhesive component as a pressure-sensitive adhesive, it is possible to secure sufficient wettability to the adherend without the need for water and an organic solvent, and it is satisfactory after coating. The adhesiveness to be obtained can be obtained. Also, such an adhesive is
By mixing with a liquefied gas for injection, a stable and uniform solution or dispersion can be provided, and therefore, it can be uniformly spray-injected into particles or lace on paper or cloth. In fact, when these adhesive compositions are filled into aerosol cans and the like, they can be sprayed with just a few shakings, and the contents of the aerosol cans remain stable over time. Further, since the adhesive composition of the present invention does not contain water and an organic solvent as a solvent, it not only dries very quickly, but also does not soak when applied to paper, cloth, etc., and the human body caused by the organic solvent. It also avoids adverse effects on the environment.

[0038]

EXAMPLES Next, the present invention will be described in detail with reference to the following examples and comparative examples. In the following, the amounts of the constituent components of the composition are shown in parts, but this means “parts by weight” unless otherwise specified.

Example 1 Compatibility of Base Polymer with Liquefied Gas for Injection In this example, the following base polymer was used to evaluate the compatibility of the base polymer used in the present invention with the liquefied gas for injection. Prepared. Since Polymers 1 and 2 were obtained in the form of a solution containing a solvent, the solvent was evaporated in a hot-air thermostat and the remaining non-volatile components were used as the base polymer.

Polymer 1 Acrylic polymer "Aroset 8101" Polymer 2 Silicon polymer "SD 456
0 ”Polymer 3 Ethylene-vinyl acetate copolymer“ EV
A 40Y ”Polymer 4 Styrene-based polymer“ Clayton 11
07 ”Each base polymer was put in a glass pressure resistant bottle, and the bottle valve was crimped and sealed. Then, one of the following liquefied gases in the same amount as the base polymer: Liquefied gas 1 Freon 134a (CH ₂ FCF ₃ ) Liquefied gas 2 Propane gas Liquefied gas 3 Isobutane gas Liquefied gas 4 Dimethyl ether (DME) Liquefied gas 5 n- After the butane was filled in a pressure bottle and shaken sufficiently by hand, the dissolved state of the base polymer and the liquefied gas was visually observed. The results are summarized in the table below.

Then, for comparison, the above procedure was repeated using a base polymer outside the scope of the present invention. The base polymers prepared for comparison here are the following two types of polymers that are not tacky at room temperature. Polymer 5 Acrylonitrile-Butadiene Rubber "Hycar 1551" Polymer 6 Chloroprene Rubber "Neoprene"
(Neoprene) AC ”These base polymers did not dissolve as lumps, and the results summarized in the following table were obtained.

[0042]

[Table 1]

In the above table, "soluble" means that the mixture of the base polymer and the liquefied gas is easy to form a uniform solution, and "partially soluble" means that the mixture is compared. "Swelling" means that the mixture becomes a solution at a relatively low concentration, or that it becomes a uniform and stable dispersion easily by a dispersing means such as stirring, but the mixture does not become a solution.
A uniform and stable dispersion liquid is obtained by the dispersing means, and further, "insoluble" means that the mixture does not become a solution literally and the stable dispersion liquid is not formed even by the dispersing means. .

As can be seen from the results set forth in the table above, the use of a base polymer outside the scope of the present invention did not allow it to be dissolved in the liquefied gas for injection and also When using a base polymer within the range, solubility (compatibility) of the polymer in the liquefied gas for injection
Is variable depending on the liquefied gas.

Example 2 Preparation of a sample of an aerosol-type adhesive composition Preparation of sample 1: An aerosol-type adhesive composition containing the following components in the indicated amounts was prepared. Base polymer Silicon-based polymer "SD 4560" 5 parts (as non-volatile content after solvent evaporation) Liquefied gas for injection Isobutane 95 parts Base polymer was put into an aerosol can, and the valve of the aerosol was crimped to close the can. Then, isobutane was filled in an aerosol can and shaken by hand sufficiently to obtain a target sample 1. Preparation of Samples 2 to 11: Samples 2 to 11 were prepared by repeating the procedure for preparing Sample 1 above. The components and blending amounts (parts by weight) used are as described in the following table. For reference, Sample 1 is also shown.

[0046]

[Table 2]

Preparation of Comparative Samples 1-6: Comparative Samples 1-6 were prepared by repeating the procedure of Sample 1 above. The components and blending amounts (parts by weight) used are as described in the following table. In this example, "SD 4560"
And “Aloset 8101” used the non-volatile component obtained in the same manner as in Example 1 above as the base polymer,
"Acronal 8501D" was used as it was as an aqueous emulsion.

[0048]

[Table 3]

Example 3 Evaluation of Physical Properties of Samples 1 to 7 Each sample was evaluated by the following items: Evaluation item 1 Condition in aerosol can Evaluation item 2 Spray pattern evaluation item 3 Penetration into paper Evaluation item 4 Initial adhesive strength Evaluation item 5 Peeling adhesive strength [g / 25 mm] and paper / paper (coated twice on one side) were evaluated. The following describes each item. Evaluation item 1: In order to evaluate the state (dissolution-dispersion) of each sample in the can, a glass pressure resistant bottle was used in place of the aerosol can to repeat the above sample preparation method. In each sample, it was possible to visually confirm that the composition was completely dissolved in the pressure bottle. Evaluation item 2: Each sample was spray-coated on paper, and the obtained spray pattern was visually observed.
In this evaluation, A4 size fine paper is used as the paper,
The adhesive composition was applied once to the paper by moving the aerosol can at a distance of 20 cm from the paper and spraying at a moving speed of about 20 cm / sec. In all the samples, the spray pattern obtained was lace-like, and no scattering to the periphery was observed. Evaluation item 3: In the same manner as in the evaluation item 2, the part of the paper coated with the adhesive composition was visually observed. Even when each sample was spray-coated on paper, it could be adhered cleanly without leaving any stain. Evaluation item 4: Each sample was spray-applied once at a distance of 20 cm to the short side of 100 × 150 mm wood free paper. Then, within 5 seconds after application, the applied portion and the short side on the opposite side were attached to each other to form a loop. At that time, it was observed whether or not the adhesive portion was peeled off due to the repulsive force of the paper.
The case where there was no peeling was defined as "good", but all samples showed good initial adhesive strength. Evaluation item 5: Each sample was spray-coated twice on one side of 100 × 150 mm high-quality paper with a distance of 20 cm. Next, 5 to 10 seconds after application, another fine paper of the same size was attached to the sample-coated surface of the preceding fine paper. The bonded part was rolled with a rubber roller (2 kg) twice. After being left at room temperature for 24 hours, a peel test was conducted with a tensile tester at a tensile speed of 300 mm / min. All samples showed satisfactory peel adhesion strength.

The evaluation results of the evaluation items 1 to 5 are shown below.

[0051]

[Table 4]

Example 4 (Comparative Example) Evaluation of Physical Properties of Comparative Samples 1 to 4 For comparison, the procedure of Example 3 was repeated using Comparative Samples 1 to 4. However, in this example, evaluation item 5 was omitted. In the case of this example, in contrast to the case of Example 3, satisfactory results could not be obtained. For example, Comparative Samples 1, 2 and 3 were prepared by dissolving the base polymer in an organic solvent,
Furthermore, although it was filled in an aerosol can together with the liquefied gas for injection, in the aerosol can it evenly melted and showed a lace-like spray pattern, but when it was applied to paper, it did not penetrate into the inside of the paper. It was remarkable, and the trace of the bonded portion remained even after drying, impairing the appearance. Moreover, even if the papers were pasted together immediately after spray coating, the adhesive strength (initial adhesive strength) could not be obtained immediately because the solvent still remained. Furthermore, comparative sample 4
Is an example of an emulsion type aerosol adhesive,
Since it uses water as the medium, it soaked strongly when applied to paper, leaving marks and wrinkles of the adhesive. The drying speed was also very slow.

The respective evaluation results of evaluation items 1 to 4 are shown below.

[0054]

[Table 5]

Example 5 Influence of ratio of base polymer to liquefied gas for injection on adhesion performance (1) To examine influence of ratio of base polymer to liquefied gas for injection on adhesion performance, Samples 8 to 11 and comparison The procedure of Example 3 above was repeated using Samples 5 and 6. However, in this example, evaluation items 3 and 5 are omitted. The results obtained are shown below (see also the results of Sample 1 of Example 3 above).

[0056]

[Table 6]

As will be described in connection with the above results, as can be understood from Comparative Samples 5 and 6, the desired performance may not be achieved depending on the blending amount of the base polymer.
For example, when the blending amount of the base polymer is 40 parts by weight,
In some cases, the content of the aerosol can is too viscous to spray well and not spread, resulting in uneven adhesive strength. Further, if the amount of the base polymer compounded is at most 0.5 part by weight, the concentration of the adhesive will be extremely low, and therefore satisfactory adhesive strength can only be obtained by repeating the coating operation many times. it can.

Example 6 Effect of Ratio of Base Polymer to Liquefied Gas for Injection on Adhesion Performance (2) To investigate the effect of ratio of base polymer to liquefied gas for injection on adhesion performance, belong to the following three groups. Sample 12
~ 17 and comparative samples 7-12 were used to repeat the procedure of Example 5 above. The components and blending amounts (parts by weight) used in each sample and the obtained results are as shown in the table below. Group A: Base polymer Acrylic polymer "Aroset 8101" Part X Liquefied gas for injection DME (Dimethyl ether) Z Part

[0059]

[Table 7]

Group B: Base Polymer Ethylene-Vinyl Acetate Copolymer X Part "EVA 40Y" Tackifier "Arcon P-90" Y Part Injectable Liquefied Gas DME (Dimethyl Ether) Z Part

[0061]

[Table 8]

Group C: Base polymer Styrene-based polymer “Clayton 1107” X part Tackifier “Picolite A125” Y part Liquefied gas for injection DME (dimethyl ether) Z part

[0063]

[Table 9]

[0064]

As described above, according to the present invention,
It is possible to provide an aerosol-type adhesive composition that does not require an organic solvent and water as a solvent for the base polymer.
Since the aerosol-type adhesive composition of the present invention does not require an organic solvent and water, the adhesive composition can be dried very quickly, and therefore, the waiting time after application in the bonding operation is unnecessary. . In addition, when applied to a porous adherend such as paper, there is no infiltration into the interior, and therefore no trace of application of the adhesive portion remains. Furthermore, when applied to an adherend made of an organic material such as plastic or having a surface treatment of an organic material, discoloration and deterioration of the surface of the adherend can be prevented.

When the aerosol type adhesive composition of the present invention containing a specific base polymer as a main component is filled in an aerosol container, the adhesive component is easily dissolved or dispersed by simply shaking the container several times. Then, it can be in a sprayable state like the conventional adhesive. Further, this adhesive has excellent aging characteristics and is stable without segregation and precipitation in the aerosol container even after aging. In fact
The adhesive composition of the present invention can exhibit a uniform dissolved or dispersed state in an aerosol container, and thus, when it is sprayed from the container, it does not cause clogging of the spray nozzle, and it is not covered. Does not occur. And
Whether the composition is in a dissolved state or in a dispersed state can be controlled by selecting the base polymer used in the composition, and therefore a uniform lace pattern (dissolved state) to a particulate pattern ( The pattern up to the dispersed state) can be obtained at any stage.

Further, the aerosol-type adhesive composition of the present invention is also excellent in adhesive strength, and the strength is such that it can hold thin or light materials such as paper and film. In addition, the adhesive composition of the present invention does not leave bleeding or wrinkles on the adherend such as paper even after drying.
Furthermore, since the aerosol-type adhesive composition of the present invention does not include an organic solvent as a solvent, it does not correspond to a dangerous substance,
It is possible to avoid environmental pollution and harm to the human body. In addition,
Although a liquefied gas for injection is also used, since this gas has a relatively low toxicity, it has an effect of significantly reducing the influence on human health. By the way, ACGIH (Am
erican Conference of Governmental Industrial Hygie
nists) allowable concentrations of various substances (T
LB) propane gas is 1000 ppm, butane gas is not set, and dimethyl ether is 1000 ppm.
Higher than the permissible concentration of organic solvents and relatively safe.
In addition, normal hexane, toluene, etc. are subject to regulation by the Industrial Safety and Health Act because they have effects on the central nervous system, but propane, butane and dimethyl ether are
It is not subject to such regulations.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C09K 3/30 G N R

Claims (6)

[Claims] 1. An aerosol-type adhesive composition, characterized in that an adhesive component containing a pressure-sensitive adhesive is dissolved or dispersed in a volatile component essentially consisting of a liquefied gas for injection. 2. The pressure-sensitive adhesive comprises one or more base polymers selected from the group consisting of acrylic polymers, silicone polymers, ethylene-vinyl acetate copolymers and styrene polymers, The aerosol-type adhesive according to claim 1, wherein the liquefied gas for injection contains one or more liquefied gases selected from the group consisting of n-butane, isobutane and dimethyl ether. Composition. 3. The adhesive according to claim 2, wherein the adhesive contains an acrylic polymer as a base polymer, and the liquefied gas for injection contains isobutane, n-butane or dimethyl ether as a main component. Aerosol type adhesive composition. 4. The adhesive comprises a silicon-based polymer as a base polymer, and the liquefied gas for injection is n-
The aerosol-type adhesive composition according to claim 2, which comprises butane or isobutane as a main component. 5. The aerosol type according to claim 2, wherein the adhesive contains ethylene-vinyl acetate copolymer as a base polymer, and the liquefied gas for injection contains dimethyl ether as a main component. Adhesive composition. 6. The aerosol-type adhesive composition according to claim 2, wherein the pressure-sensitive adhesive contains a styrene polymer as a base polymer, and the liquefied gas for injection contains dimethyl ether as a main component. .