JP2012036352A - Aqueous aerosol coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous aerosol coating composition which forms a snow-like object or a form when jetted to an object, and can maintain the texture and volume at jetting over a long period of time.SOLUTION: The aqueous aerosol coating composition is composed of an aqueous coating composition that contains at least two thermoplastic resins, having a different glass transition temperature, alcohol, and a propellant, wherein the arithmetic mean of the glass transition temperatures of the respective thermoplastic resins is 5-65°C, the aqueous aerosol coating composition forms the snow-like or foam-like jet formed object when jetted to the object, and a specific gravity of the jet formed object is 0.1 or less.

Description

  The present invention relates to a water-based aerosol coating composition, and more particularly, is a water-based aerosol coating composition comprising a thermoplastic resin and alcohol, and forms a snowy material or foam when used by being sprayed onto an object. The present invention relates to an aqueous aerosol coating composition.

Aerosol compositions are known that form foam, snow or foam when sprayed from a container.
In the above, the aerosol composition which forms a snow-like thing is used, for example in order to make pseudo artificial snow in a Christmas tree, a video effect, etc. In addition, the aerosol composition forming the foam is used as a pseudo product such as a foam for hair or a cosmetic foam. In any aerosol composition, it is required to show a real texture such as snow or cosmetics when sprayed on an object.
Conventionally known aerosol compositions forming snow-like materials are mainly composed of paraffin, whereas aerosol compositions forming foam are mainly composed of surfactants.
Snowy materials and foams formed from paraffin or an aerosol composition based on a surfactant as a main component, even if the snow texture and bulk (real volume) of the real thing are immediately after formation, There is a problem that the image quality is lowered and the texture is lowered. That is, there is a possibility that the paraffin or the surfactant in a foamed state that is sprayed on the object is defoamed, the bubbles gradually stick to each other and solidify, and eventually crack.
Therefore, it has been difficult to maintain a desired texture and volume over a long period of time when the object is painted thick.

Patent Document 1 discloses an aerosol composition in which a water-resistant phosphorescent pigment, a dispersant, and water are blended, and discloses a technique for obtaining pseudo artificial snow by spraying on an object.
When the disclosed technique of Patent Document 1 is used, pseudo artificial snow formed from finely and uniformly foamed foam can be obtained.
However, even if the technique disclosed in Patent Document 1 is used, it has been difficult to obtain an aerosol composition that can maintain a snowy shape for a long period of time. That is, since the dispersant used in the technology disclosed in Patent Document 1 is a surfactant, the foam disappears as water or the like evaporates, and gradually becomes a film and may solidify. For this reason, it has been difficult to deposit snowy material thickly and to maintain the texture and volume as real snow for a long time.

JP 2003-292945 A

  The present invention has been made to solve the above-described problems of the prior art, and forms a snow-like object or foam when injected onto an object, and maintains the texture and volume during injection over a long period of time. An aqueous aerosol coating composition that can be produced is provided.

但し、ｎ≧２
Ｔｇ：ガラス転移温度の算術平均値
Ｔｇ(ａｉ)：熱可塑性樹脂ａｉのガラス転移温度
Ａｉ：熱可塑性樹脂固形分全重量に対する熱可塑性樹脂ａｉの固形分の重量（％） The invention according to claim 1 is an aqueous aerosol coating composition comprising an aqueous coating composition containing at least two thermoplastic resins having different glass transition temperatures and an alcohol, and a propellant. The arithmetic average of the glass transition temperature calculated by the following formula (Equation 1) is 5 to 65 ° C., and forms an injection-formed product that exhibits a snow-like shape or a foam-like shape when sprayed on an object. The present invention relates to a water-based aerosol coating composition characterized by having a specific gravity of 0.1 or less.
(Equation 1)

However, n ≧ 2
Tg: arithmetic average value of glass transition temperature Tg (ai): glass transition temperature of thermoplastic resin ai Ai: weight of solid content of thermoplastic resin ai relative to total weight of thermoplastic resin solid content (%)

  The invention according to claim 2 relates to the aqueous aerosol coating composition according to claim 1, wherein the arithmetic average of the glass transition temperature is 5 to 15 ° C., and the injection-molded product has a foam shape.

  The invention according to claim 3 relates to the aqueous aerosol coating composition according to claim 2, wherein the content of the alcohol is 1 to 5% by weight based on the total amount of the aqueous coating composition.

  The invention according to claim 4 relates to the water-based aerosol coating composition according to claim 1, wherein the arithmetic average of the glass transition temperature is 15 to 65 ° C., and the injection-formed product exhibits a snow shape.

  The invention according to claim 5 relates to the aqueous aerosol paint composition according to claim 4, wherein the content of the alcohol is 5 to 15% by weight with respect to the total amount of the aqueous paint composition.

  The invention according to claim 6 relates to the aqueous aerosol coating composition according to any one of claims 1 to 5, comprising a foaming agent and / or a foam stabilizer.

According to the invention of claim 1, an aqueous aerosol coating composition comprising an aqueous coating composition containing at least two thermoplastic resins having different glass transition temperatures and an alcohol, and a propellant, The arithmetic average of the glass transition temperatures of the respective thermoplastic resins is 5 to 65 ° C., and when sprayed onto an object, a spray-formed product having a snow shape or a foam shape is formed, and the specific gravity of the spray-formed product is 0. .1 or less, it is possible to obtain a snow-like or foam-like injection-molded product made of fine foam, and even if the moisture contained in the snow-like or foam decreases (evaporates), the shape shrinks. It can prevent and maintain the shape at the time of injection. That is, a resin having a high glass transition temperature in the thermoplastic resin used becomes a foam skeleton that forms a snowy object or foam, and a resin having a low glass transition temperature forms a film and plays a role of a cushioning material. While maintaining the shape of the object or foam, pulverization with a slight impact can be prevented.
Accordingly, it is possible to obtain a snowy object or foam that can maintain the texture and bulk for a long period of time even when it is thickly applied to the object.

  According to the second aspect of the present invention, the arithmetic average of the glass transition temperature is 5 to 15 ° C., and the injection molding exhibits a foam shape. Since it does not easily occur, it is less likely to shrink and the shape during injection can be maintained.

  According to the invention which concerns on Claim 3, when the content of the said alcohol is 1 to 5 weight% with respect to the whole quantity of the said water-based coating composition, the foam which consists of a fine foam can be obtained. Furthermore, even when thick (bulky), the foam disappears and the shape can be maintained without forming a film.

  According to the invention of claim 4, the arithmetic average of the glass transition temperature is 15 to 65 ° C., and the injection-formed product exhibits a snow shape, so that shrinkage and powder due to a decrease (evaporation) of moisture over time It is possible to make a snow-like object that is difficult to be converted. That is, by reducing the water content, the foam is crushed, turned into a film and solidified, and a snow-like material that does not crack can be obtained.

  According to the invention which concerns on Claim 5, when the content of the said alcohol is 5 to 15 weight% with respect to the whole quantity of the said water-based coating composition, the snow-like thing consisting of a fine foam can be obtained. Furthermore, even when applied thickly, the foam is not crushed, so that it can be made into a snow-like material like the real thing.

  According to the invention which concerns on Claim 6, while it becomes easy to form foam by including a foaming agent and / or a foam stabilizer, stabilization of the formed foam can be aimed at.

Hereinafter, the water-based aerosol coating composition according to the present invention will be described in detail.
The aqueous aerosol coating composition according to the present invention is used by being sprayed onto an object to be coated. The injection molded object formed by injecting with respect to a target object is a snow form or a foam form.

  Here, the snow-like object and the foam in the present invention are defined as an injection-formed object having a specific gravity of 0.1 or less. The specific gravity is calculated by filling a specific gravity cup (JIS K 5600-2-4) with an injection-formed product and measuring the mass. The specific gravity is calculated for an injection-formed product formed under the conditions of a temperature of 20 ° C. and a relative humidity of 50%.

An injection molded product (snowy product or foam) having a specific gravity of 0.1 or less maintains its shape without substantially changing the bulkiness and texture immediately after the injection formation, even if the following accelerated drying test is performed. be able to.
In this case, the accelerated drying test means that an injection-formed product (snow-like material or foam) is placed in a paper cage made of a cube having a side of 3 cm (hereinafter referred to as 3 cm cube) at a temperature of 20 ° C. and a relative humidity of 50%. Filling and measuring the bulkiness (residual height of the injection-molded product in a paper bag) after one day.
In addition, the removal of the water | moisture content in an injection molding is accelerated | stimulated by using a paper basket. The drying rate at this time is approximately three times (at 20 ° C.) when the injection-formed product is formed on a non-water-absorbing target (for example, metal, resin plate, plant, etc.).
When the injection-molded product is snowy, the bulkiness after one day is 2.5 to 3 cm, while when foamed, the bulkiness after one day is 2.8 to 3 cm.

  The aqueous aerosol coating composition according to the present invention comprises an aqueous coating composition and a propellant.

<Water-based paint composition>
First, the aqueous coating composition used in the aqueous aerosol coating composition according to the present invention will be described in detail.
The aqueous coating composition used in the aqueous aerosol coating composition according to the present invention is composed of a thermoplastic resin and alcohol. At least two kinds of thermoplastic resins are used. Two or more thermoplastic resins may be used, or three, four or more resins may be used. The combination of thermoplastic resins is not particularly limited, but those having different glass transition temperatures are used in combination. In the present invention, when the glass transition temperatures are different, the same kind of resin is regarded as a different kind of resin.

The kind of thermoplastic resin is not particularly limited, and a resin that does not increase in viscosity when mixed with a propellant described later is selected. In the present invention, an emulsion (water-based paint) previously prepared from the following thermoplastic resin is used.
Examples of the thermoplastic resin suitably used in the present invention include an acrylic resin, a urethane resin, a vinyl acetate resin, and a vinyl chloride resin. In addition, a composite (copolymer) resin such as a styrene-containing acrylic resin (acrylic styrene resin), an acrylic silicon resin, or a vinyl chloride-acrylic resin can also be used.

  Here, the synthetic resin and the natural resin have a glass transition temperature. The glass transition temperature is a temperature at which the rigidity of the solid is lost, the viscosity is lowered, and the fluidity is rapidly increased, and is unique to each resin.

As described above, when two types of thermoplastic resins are used, resins having different glass transition temperatures are used. That is, the resin is selected so that a difference occurs in the glass transition temperature.
Moreover, when using 3 or more types of thermoplastic resins, you may select resin from which all glass transition temperatures differ, However, The thing which produces a difference in glass transition temperature in at least 2 types of resin is selected.

As described above, the thermoplastic resin is selected so as to be a combination that causes a difference in glass transition temperature between at least two kinds. More preferably, the combination is such that the difference in glass transition temperature is large. That is, one having a relatively high glass transition temperature (for example, about 50 to 100 ° C.) and one having a relatively low glass transition temperature (for example, about −50 to 30 ° C.) are selected.
Those having a relatively high glass transition temperature, for example, exhibit a hard property near room temperature of 20 to 30 ° C. (hereinafter referred to as a hard resin). On the other hand, those having a relatively low glass transition temperature exhibit a soft property due to increased fluidity at the above-mentioned temperature around room temperature (hereinafter referred to as soft resin).

The selected two or more types of thermoplastic resins are mixed (polymer blend) and used.
By blending the above-mentioned hard resin and soft resin, when sprayed onto an object as an aerosol, a bulky injection-molded product (snowy product or foam) excellent in texture and volume can be obtained.
By mixing the hard resin and the soft resin, the hard resin is connected with the soft resin. That is, the hard resins are bonded via the soft resin. By doing so, it can be set as the bulky injection formation of a snow form or a foam form instead of liquid when it injects with respect to a target object. In other words, a hard resin is artificially used as a core substance, and a soft resin surrounds it. If it is composed of only a soft resin, the shape (texture, volume) of the injection-molded product starts to collapse immediately after the formation, and may gradually become a film shape along the shape of the object.

The mixing ratio (weight ratio) of the thermoplastic resin to be mixed in the present invention is not particularly limited. However, when obtaining a snowy material, the soft resin and the hard resin are mixed at the same weight ratio or are softer than the hard resin. It is preferable to contain a large amount of resin. By mixing the soft resin and the hard resin in the above-described ratio, it is possible to obtain a snow-like material with a soft texture.
On the other hand, when obtaining a foam, it is preferable to contain more hard resin than soft resin. By blending more hard resin than soft resin, the above-mentioned pseudo core substance increases, and the soft resin can be supported. Therefore, a bulky shape can be maintained and a foam having excellent elasticity can be obtained.

A thermoplastic resin is mixed so that the arithmetic average of each glass transition temperature of a thermoplastic resin may be 5-65 degreeC.
When the arithmetic average of the glass transition temperature is less than 5 ° C., the fine foams forming the formed product are likely to stick to each other as the water content in the injection-formed product is lost, and the foam tends to disappear.
On the other hand, if it exceeds 65 ° C., even if it is sprayed onto the object, the glass transition temperature of the entire mixed resin is high, so that it is not possible to obtain an injection-molded product with a soft texture, which may solidify and become powdery. There is. That is, as the water evaporates immediately after spray application, it becomes solidified and cracked, and even with a slight impact, the shape cannot be maintained and the snowy object or foam may be broken.

  When the arithmetic average of the glass transition temperature is within the above-mentioned temperature range, it is possible to maintain a bulky snow-like or foam-like shape over a long period of 3 months or more in a normally used environment, for example, at a temperature of 20 ° C. and a relative humidity of 50%. An injection molding can be obtained. In other words, in the state where the above-mentioned 3 cm cubic paper basket is filled with the injection-molded product, the snowy material can maintain the bulkiness of 2.5 to 3 cm and the foam of 2.8 to 3 cm.

  The arithmetic average of the above glass transition temperature is calculated by the following equation (Equation 1). In (Equation 1), Tg is the arithmetic mean value of the glass transition temperature, Tg (ai) is the glass transition temperature of the thermoplastic resin ai, and Ai is the weight of the solid content of the thermoplastic resin ai relative to the total weight of the thermoplastic resin solid content. (%). Note that n is an integer of 2 or more.

但し、ｎ≧２

However, n ≧ 2

  For example, when two types of thermoplastic resins are mixed, the glass transition temperature of the hard resin is Tg (H), the glass transition temperature of the soft resin is Tg (L), and the mixing ratio of each resin solid content is A (H). : A (L), the arithmetic average (Tg) of the glass transition temperature is calculated by the following equation (Equation 2).

The alcohol used in the present invention is not particularly limited, and various alcohols can be used, but it is preferable to use a monohydric alcohol. Only 1 type may be used for alcohol and it can also be used in mixture of 2 or more types.
Examples of the alcohol include methanol, ethanol, isopropyl alcohol and the like, and these are preferably used. In particular, the use of ethanol is preferable because the above-described resin is easily dispersed and has a weak odor and is safe for the human body. The content of the alcohol is appropriately changed depending on a desired injection-formed product (snowy material, foam) as described later.

  The arithmetic average value of the glass transition temperature of the thermoplastic resin, the content of the thermoplastic resin, and the content of the alcohol vary depending on the desired injection-molded product. The following describes the cases of snow and foam.

<For forms>
When obtaining a foam, the arithmetic average of the glass transition temperature of the thermoplastic resin is 5 to 15 ° C, more preferably 8 to 10 ° C.
As the thermoplastic resin, acrylic resin and urethane resin are particularly preferably used among the above-described resins.
The content of the thermoplastic resin is 20 to 50% by weight in terms of resin solids with respect to the total amount of the aqueous coating composition. If it is less than 20% by weight, a sufficient amount of foam cannot be formed because the resin component is small, and a foam having excellent elasticity cannot be formed. On the other hand, if it exceeds 50% by weight, a foam having excellent elasticity can be obtained immediately after spray coating, but it becomes difficult to maintain a soft texture because it solidifies immediately after coating.
The content of the alcohol is 1 to 5% by weight with respect to the total amount of the aqueous coating composition. When it is less than 1% by weight, it is difficult to form a foam when sprayed onto an object, and a bulky injection-formed product cannot be obtained. On the other hand, if it exceeds 5% by weight, it is impossible to obtain a bulky and elastic foam.
In the case of obtaining a foam, it is sufficient if it satisfies at least the range of the arithmetic average value of the glass transition temperature described above, but the alcohol content is more preferable. By doing so, the solidification of the foam due to the decrease (evaporation) of moisture with time is less likely to occur, and since the shrinkage is less, the shape and texture (elasticity) immediately after spray coating can be maintained.

  Furthermore, the viscosity of the aqueous coating composition before spray coating, that is, the viscosity of the aqueous coating composition in a state of being accommodated in a container as the aqueous aerosol coating composition is preferably 200 to 1000 cps. When the viscosity is less than 200 cps, the foam tends to stick together when jetted, and the bulk becomes low and foam cannot be formed. On the other hand, when the viscosity exceeds 1000 cps, the texture of the foam is poor when jetted. Since it cannot be made into a soft foam, it is not preferable in any case.

<For snowy objects>
When obtaining a snow-like thing, the arithmetic average of the glass transition temperature of a thermoplastic resin shall be 15-65 degreeC, More preferably, it is 20-35 degreeC.
Among the above-mentioned resins, acrylic resins, urethane resins, vinyl chloride-acrylic copolymer resins, and styrene-containing acrylic resins (acrylic styrene resins) are preferably used as the thermoplastic resin.
The content of the thermoplastic resin is 10 to 40% by weight in terms of resin solid content with respect to the total amount of the aqueous coating composition. If it is less than 10% by weight, since the resin solid content is small when sprayed, the volume of the spray-formed product decreases with the evaporation of moisture, and it is impossible to obtain a snowy product formed from fine bubbles. On the other hand, if it exceeds 40% by weight, the viscosity of the aqueous coating composition increases, and the composition is atomized during spray coating, making it difficult to form a foam. That is, the composition is sprayed in a liquid state. Therefore, it cannot be made into a fine foam when sprayed, and it cannot be in a state where real snow falls.
The alcohol content is 5 to 15% by weight based on the total amount of the aqueous coating composition. If it is less than 5% by weight, there is a risk that a flat finish with no unevenness will occur when deposited on the object. On the other hand, if the content exceeds 15% by weight, the alcohol exhibits a defoaming effect, so that the formed foam is liquefied immediately after spray coating, and a snow-like material cannot be formed, so-called snow melting phenomenon occurs. It becomes difficult to deposit snow-like objects on the application object.

  Furthermore, the viscosity of the aqueous coating composition before spray coating, that is, the viscosity of the aqueous coating composition in a state of being accommodated in a container as the aqueous aerosol coating composition is preferably 50 cps or less. If the viscosity exceeds 50 cps, it cannot be efficiently injected when it is injected. That is, since the water-based aerosol coating composition is difficult to be atomized and cannot be made into a soft foam projectile with a texture, either case is not preferable.

  The snowy material or foam in the present invention has a specific gravity of 0.1 or less. By setting the specific gravity to be 0.1 or less, it is possible to obtain a stable snow-like material or foam that is extremely fine and whose texture and shape do not substantially change over a long period of time.

The aqueous coating composition used in the aqueous aerosol coating composition according to the present invention does not contain film-forming aids (film-forming aids) such as texanol, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate.
The film forming aid has an action of softening the resin and a defoaming property. Therefore, when the film forming aid is contained in the aqueous aerosol coating composition according to the present invention, the defoaming property of the film forming aid acts and the shape of the snowy material or foam cannot be maintained. Furthermore, when the water in the injection-molded product (snow-like material or foam) evaporates, the resin component of the emulsion resin (water-based coating composition) constituting the spray-formed product sticks to each other as the product gradually melts. Finally, it becomes a film.

Moreover, you may mix | blend a foaming agent and a foam stabilizer in a water-based coating composition.
Known foaming agents and foam stabilizers can be used.
Examples of the foaming agent include coconut oil fatty acid type, and examples thereof include, but are not limited to, N-coconut oil fatty acid acyl-L-glutamate sodium. The foaming agent is preferably contained in an amount of 3 to 10% by weight based on the total amount of the composition. By making a foaming agent into the above-mentioned range, it becomes easy to form foam, and also the formed foam can be stabilized.
Examples of the foam stabilizer include, but are not limited to, fatty acid diethanolamine salts and stearic acid (ammonium stearate). The foam stabilizer is preferably contained in an amount of 3 to 10% by weight based on the total amount of the composition. By setting the foam stabilizer to the above-described range, the foam size can be made uniform, and the foam can be stabilized in the same manner as the foaming agent.
In the present invention, only one of a foaming agent and a foam stabilizer may be blended, but it is preferable to blend both. By doing so, foam can be easily formed, and the foam can be stabilized, and a snowy object or foam excellent in texture and volume can be formed.

  Furthermore, you may mix | blend coloring agents, such as a pigment and dye, a fragrance | flavor, a flame retardant, antiseptic | preservative, and a rust preventive agent with an aqueous coating composition. In that case, it is preferable to select a blending amount that does not exhibit the defoaming property, or to select a non-foaming property.

  A water-based paint composition is contained in a container, and it is possible to form a snowy object or foam on an object without mixing air or other gas in advance. In the present invention, however, a propellant is contained. By making it, it is set as a water-based aerosol coating composition.

<Water-based aerosol coating composition>
The water-based aerosol coating composition according to the present invention will be described.
As described above, the aqueous aerosol coating composition according to the present invention is prepared from the above-described aqueous coating composition and a propellant.
The propellant contained is not particularly limited, and known ones can be used, but liquefied petroleum gas (LPG) and dimethyl ether (DME) are preferred.

The mixing ratio of the aqueous coating composition and the propellant (LPG, DME) when preparing the aqueous aerosol coating composition is preferably 87 to 83 vol%: 13 to 17 vol%. In addition, the sum of the ratio of each of a composition and a propellant is 100 vol%, and is not restricted to an integer ratio.
By setting it as the above-mentioned compounding ratio, when spraying a water-based aerosol coating composition, a foam can be formed efficiently and a snow-like thing or foam can be formed.

The atmosphere in the container in which the aqueous aerosol coating composition is contained in the container is 25 ° C. and the internal pressure is 0.4 to 0.5 MPa. Moreover, the diameter of the injection port (nozzle) which injects a water-based aerosol coating composition out of a container is set to 0.2-1.0 mm in diameter.
When obtaining a snowy object, the internal pressure is set to 0.4 to 0.5 MPa (25 ° C.) and the nozzle diameter is set to 0.2 to 0.6 mm. On the other hand, when obtaining a foam, the internal pressure is set to 0.4 to 0.5 MPa (25 ° C.), and for example, an erect spout is suitably used as the nozzle.
By setting the internal pressure and the nozzle diameter in the above range, a desired shape, that is, a snowy object or a foam is formed when the composition is spray-applied to an object. Any one of the above-mentioned water-based paint compositions is appropriately selected depending on whether a snowy material or a foam is desired.

<About use>
The use application of the snow-like thing or foam obtained by spraying the water-based aerosol coating composition which concerns on this invention is described below.
Snowy objects are suitable for decoration. Specifically, a real snow-like decoration can be applied to a display used in winter, such as a Christmas tree. It can also be used as simulated artificial snow in the event of a snowfall on a video or a stage.
By using the water-based aerosol coating composition according to the present invention, a snow-like material such as a real one can be obtained. Also, when a long-time decoration is required, the snow-like appearance (texture, volume) is not impaired. Furthermore, at the end of use, the snow-like object can be easily removed from the object by water washing or suction (vacuum cleaner or the like) and does not remain, and the object can be returned to its original state.

  Foams are also suitable for decoration, as are snowy objects. Specifically, it can be used as a fake product or object such as a hair or cosmetic foam or a mousse food. It can also be used as an insect repellent by sticking to the gaps in windows and doors. Furthermore, since the foam obtained in the present invention is formed from fine foam, it can also be used as a cushioning material or a heat insulating material during packaging, and is coated with a substance that causes odor to reduce odor. It can also be used as a deodorant.

  Hereinafter, the effect of the present invention will be made clearer by showing examples relating to the aqueous aerosol coating composition according to the present invention. However, the present invention is not limited to the following examples.

(Example)
<Test method>
In a two-component system in which two types of resins having different glass transition temperatures were combined, water-based aerosol coating compositions were prepared at the following blending ratios.
The obtained water-based aerosol coating composition was spray-applied so as to fill a 3 cm cubic paper bag, and the residual height (cm) of the injection-molded product immediately after spray application, 1 hour, 3 hours, and 24 hours Was measured. Moreover, spray coating was performed on 20 × 20 cm ² aluminum foil, and the appearance (texture, volume) after 1 hour, 3 hours, and 24 hours was compared with that immediately after spray coating.
In addition, the injection molding of Examples 1-3 is a snow-like thing, and the injection molding of Examples 4 and 5 is a foam.
The appearance of the injection-molded product was evaluated based on the following criteria by visual observation and touch.
A: Texture (softness) is not substantially different from that immediately after spray coating.
○: The texture is slightly degraded (hard).
Δ: The texture is slightly lowered (hard) and slightly filmy.
X: It is solidified and loses its softness and forms a film.
The test was conducted in an environment with a temperature of 20 ° C. and a relative humidity of 50%.

Example 1
As the resin, vinyl chloride-acrylic copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., Viniblanc 701) (Tg 73 ° C.) and acrylic resin (manufactured by Henkel Technologies Japan Co., Ltd., Yodosol AD180) (Tg-20 ° C.) are used. , And mixed (blended) at a weight ratio of 50:50.
To this mixed resin, 10% by weight of ethanol was added, and further, 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 6% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) were added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 26.5 degreeC.
LPG was added to the obtained composition to prepare an aqueous aerosol coating composition. The volume ratio of the aqueous coating composition to LPG is 87:13.
An aqueous aerosol coating composition was filled in an aerosol container and sprayed to obtain a snowy material.

Example 2
Acrylic resin (manufactured by Nichigo Movinyl Co., Ltd., Movinyl 972) (Tg100 ° C.) and urethane resin (manufactured by DIC Co., Ltd., Hydran APX501) (Tg-13 ° C.) are used as the resin at a weight ratio of 60:40. Mixed (blended).
6% by weight of methanol is added to this mixed resin, and further 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-L-sodium glutamate) and 7% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) are added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 54.8 degreeC.
LPG was added to the obtained composition to prepare an aqueous aerosol coating composition. The volume ratio of the aqueous coating composition to LPG is 85:15.
An aqueous aerosol coating composition was filled in an aerosol container and sprayed to obtain a snowy material.

Example 3
As the resin, vinyl chloride-acrylic copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., Viniblanc 902) (Tg 60 ° C) and acrylic resin (manufactured by Henkel Technologies Japan Co., Ltd., Yodosol AA180) (Tg-40 ° C) are used. , 62:38 by weight (blending).
14% by weight of methanol is added to the mixed resin, and further 10% by weight of a foaming agent (N-coconut oil fatty acid acyl-L-sodium glutamate) and 6% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) are added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 22.0 degreeC.
LPG was added to the obtained composition to prepare an aqueous aerosol coating composition. The volume ratio of the aqueous coating composition to LPG is 83:17.
An aqueous aerosol coating composition was filled in an aerosol container and sprayed to obtain a snowy material.

Example 4
Acrylic resin (manufactured by Nichigo Movinyl Co., Ltd., Movinyl 972) (Tg100 ° C.) and urethane resin (manufactured by DIC Co., Ltd., Hydran APX601) (Tg-13 ° C.) are used as the resin, and the weight ratio is 20:80. (Blend).
3% by weight of ethanol is added to this mixed resin, and 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 6% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) are added. Thus, an aqueous coating composition was obtained.
The arithmetic average of the glass transition temperature of this composition is 9.60 ° C.
LPG was added to the obtained composition to prepare an aqueous aerosol coating composition. The volume ratio of the aqueous coating composition to LPG is 87:13.
An aqueous aerosol coating composition was filled in an aerosol container and spray-coated to obtain a foam.

Example 5
Acrylic resin (manufactured by Nichigo Movinyl Co., Ltd., 972) (Tg100 ° C) and urethane resin (manufactured by DIC Co., Ltd., Watersol CD915) (Tg-50 ° C) are used as the resin, and the weight is 37:63 Mixed (blended) at a ratio.
4% by weight of methanol is added to the mixed resin, and further 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 7% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) are added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 5.50 degreeC.
LPG was added to the obtained composition to prepare an aqueous aerosol coating composition. The volume ratio of the aqueous coating composition to LPG is 85:15.
An aqueous aerosol coating composition was filled in an aerosol container and spray-coated to obtain a foam.

(Comparative example)
In a two-component system, an aerosol composition having an arithmetic average glass transition temperature outside the range of 5 to 65 ° C. or a specific gravity exceeding 0.1 was prepared as a comparative example.
This aerosol composition was evaluated by the same method as in the above examples.

Comparative Example 1
Acrylic resin (manufactured by Nichigo Movinyl Co., Ltd., Movinyl 972) (Tg100 ° C) and acrylic resin (manufactured by Henkel Technologies Japan Co., Ltd., Yodosol AD180) (Tg-20 ° C) are used as the resin, and the weight is 80:20. Mixed (blended) at a ratio.
To this mixed resin, 13% by weight of methanol was added, and further 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 6% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) were added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 76 degreeC.
LPG was added to the obtained composition to prepare an aerosol composition. The volume ratio of the aqueous coating composition to LPG is 87:13.
The aerosol composition was filled into an aerosol container and spray applied.

Comparative Example 2
Acrylic resin (manufactured by Henkel Technologies Japan Co., Ltd., Yodosol AD176) (Tg 70 ° C.) and urethane resin (DIC Co., Ltd., Watersol CD915) (Tg-50 ° C.) are used as the resin, and the weight ratio is 44:56. (Blend).
4% by weight of methanol is added to the mixed resin, and further 6% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 7% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) are added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 2.8 degreeC.
LPG was added to the obtained composition to prepare an aerosol composition. The volume ratio of the aqueous coating composition to LPG is 85:15.
The aerosol composition was filled into an aerosol container and spray applied.

Comparative Example 3
As the resin, vinyl chloride-acrylic copolymer resin (manufactured by Nissin Chemical Industry Co., Ltd., Viniblanc 701) (Tg 73 ° C.) and acrylic resin (manufactured by Henkel Technologies Japan Co., Ltd., Yodosol AD180) (Tg-20 ° C.) are used. , And mixed (blended) at a weight ratio of 50:50.
To this mixed resin, 10% by weight of ethanol was added, and further 2% by weight of a foaming agent (N-coconut oil fatty acid acyl-sodium L-glutamate) and 1% by weight of a foam stabilizer (aqueous ammonium stearate dispersion) were added. Thus, an aqueous coating composition was obtained.
In addition, the arithmetic average of the glass transition temperature of this composition is 26.5 degreeC.
LPG was added to the obtained composition to prepare an aerosol composition. The volume ratio of the aqueous coating composition to LPG is 85:15.
The aerosol composition was filled into an aerosol container and spray applied.

  The test results for Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1. Table 2 shows the specific gravity of Examples 1 to 5 and Comparative Examples 1 to 3. In addition, specific gravity measures the mass of the injection molding obtained by spray-coating to a specific gravity cup (JISK5600-2-4), and is computed from the mass and volume.

From the result of Table 1, in Examples 1-5, the reduction | decrease in bulkiness was not seen 24 hours after immediately after spray application. The bulk (residual height) of the snowy material after 24 hours in Examples 1 to 3 was about 93%, 90%, and 87% immediately after spray coating. It was confirmed that the bulk of the snowy material did not change substantially even after one month. On the other hand, the bulk (residual height) of the foam after 24 hours in Examples 4 and 5 was about 90% immediately after spray coating. It was confirmed that the bulk of the foam remained substantially unchanged after one month.
Moreover, the external appearance of any of Examples 1 to 5 was almost the same as that immediately after spray application, and the soft texture was maintained, and it was confirmed that there was no snow-like powdering or foam cracking. When the snow-like material or foam was actually touched in each time from immediately after application to 24 hours later, a soft tactile sensation was obtained.
From the results in Table 2, the specific gravity of the snowy material or foam of Examples 1 to 5 is significantly below 0.1, respectively, and the snowy material or foam of Examples 1 to 5 is formed from fine foam. It was confirmed that

On the other hand, in Comparative Examples 1 to 3, it can be seen that the texture and shape are not maintained from immediately after spray application until 24 hours later.
The injection-molded product of Comparative Example 1 had a soft textured snow immediately after spray application, and the volume was about 90% immediately after application after 24 hours. It was confirmed that it was pulverized.
The injection-molded products of Comparative Examples 2 and 3 contracted immediately after spray application, and a decrease in texture was confirmed. After 1 hour, Comparative Examples 2 and 3 did not exhibit a snowy shape, but became a film. In Comparative Example 2, since the arithmetic average of the glass transition temperature is low, it is considered that the bubbles adhered to each other as the water evaporated and dried. In Comparative Example 3, since the specific gravity is as large as 0.4, fine bubbles are not formed, and the evaporation of moisture immediately after injection is remarkable, and the bubbles are immediately eliminated.

  From the above results, when the arithmetic average of the glass transition temperature of the used thermoplastic resin is in the range of 5 to 65 ° C. and the specific gravity is 0.1 or less, the volume does not decrease, and It was found that a snowy object or foam capable of maintaining a soft texture without cracks was obtained.

  INDUSTRIAL APPLICABILITY The present invention is suitably used for winter decorations such as Christmas trees, decoration effects such as images and stages, and cosmetics and food products.

Claims (6)

An aqueous aerosol coating composition comprising an aqueous coating composition containing at least two thermoplastic resins having different glass transition temperatures and an alcohol, and a propellant, wherein each of the thermoplastic resins has the following formula ( The arithmetic average of the glass transition temperature calculated by the equation (1) is 5 to 65 ° C., and when sprayed onto an object, a spray-formed product having a snow shape or a foam shape is formed, and the specific gravity of the spray-formed product is 0 A water-based aerosol coating composition characterized by being 1 or less.
(Equation 1)

However, n ≧ 2
Tg: arithmetic average value of glass transition temperature Tg (ai): glass transition temperature of thermoplastic resin ai Ai: weight of solid content of thermoplastic resin ai relative to total weight of thermoplastic resin solid content (%)   2. The aqueous aerosol coating composition according to claim 1, wherein the arithmetic average of the glass transition temperature is 5 to 15 ° C., and the injection-molded product has a foam shape.   The aqueous aerosol coating composition according to claim 2, wherein the content of the alcohol is 1 to 5% by weight based on the total amount of the aqueous coating composition.   2. The aqueous aerosol coating composition according to claim 1, wherein the arithmetic average of the glass transition temperature is 15 to 65 ° C., and the spray-formed product exhibits a snow shape.   The aqueous aerosol coating composition according to claim 4, wherein the alcohol content is 5 to 15% by weight based on the total amount of the aqueous coating composition.   The aqueous aerosol coating composition according to any one of claims 1 to 5, comprising a foaming agent and / or a foam stabilizer.