JP2003341005A - Fire-retardant moisture absorbable and dischargeable foamed decorative material and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fire-retardant moisture absorbable and dischargeable foamed decorative material having an excellent fire retardancy and moisture absorbable and dischargeable properties, also having sufficiently high surface strength, easy in the coating formation of a foamed decorative layer and excellent in productivity, and a manufacturing method therefor. <P>SOLUTION: A foamed decorative layer 2, which comprises an aqueous emulsion resin containing sulfaguanidine and/or calcium sulfamate as the fire- retardant moisture absorbable and dischargeable agent, is provided on a substrate 1. The aqueous emulsion composition used in the coating formation of the foamed decorative layer 2 is prepared by compounding sulfaguanidine and/or calcium sulfamate with an aqueous emulsion with a moisture content of about 35-70 wt.% in an amount of about 15-40 pts.wt. per 100 pts.wt. of water. When this aqueous emulsion composition is used, it is gelled by this compounding to well perform the coating formation of the foamed decorative layer without becoming coating impossibility. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam decorative material used as a wallpaper or the like in a building such as a house and a method for producing the same, and particularly to a foam having flame retardancy and moisture absorption / release properties simultaneously. The present invention relates to a decorative material and a manufacturing method thereof.

[0002] Conventionally, a foam decorative material having a foam decorative layer provided on a base material such as a backing paper has been widely used as a wallpaper or the like.
Such wallpaper can easily ignite or ignite and cause a fire, or burn violently and spread rapidly during a fire, or generate black smoke or toxic gas to spread the damage caused by the fire. Some degree of flame retardancy is required so that it will not occur. For this reason, it is possible to use an inorganic paper mixed with inorganic fibers or inorganic powder as the backing paper, or to impregnate the backing paper with a flame retardant such as guanidine sulfamate or calcium sulfamate, or as a thermoplastic resin constituting a foam decorative layer. Flame-retardant resin such as polyvinyl chloride resin is used, or a hydrated metal salt such as aluminum hydroxide or magnesium hydroxide in a foam decorative layer, a halogen-based resin,
Generally, a flame retardant formulation is applied by adding a flame retardant such as phosphorus or nitrogen.

By the way, in recent years, with the increase in the airtightness of houses due to the spread of aluminum sashes, etc., water vapor generated in the room cannot escape to the outside, so that the humidity inside the room rises abnormally and the dew condensation on the wall surface occurs. It is becoming a problem that it may cause the generation of mildew. Further, it is not preferable for the resident's health that the humidity fluctuates drastically as the room temperature fluctuates. From such a viewpoint, it has been demanded that a building interior material such as a wallpaper be provided with a moisture absorbing / releasing function to mitigate the humidity fluctuation in the room.

Specific methods for adding a moisture absorbing / releasing function to foamed decorative materials such as wallpaper include sodium polyacrylate crosslinked products and polyvinyl alcohol crosslinked polymers,
Superabsorbent polymers such as starch-acrylic acid graft polymer, saponified methyl acrylate-vinyl acetate copolymer, and porous inorganic powders such as silica gel, zeolite, diatomaceous earth, etc. are used as a moisture absorbing / releasing agent in the foam cosmetic layer. Most commonly added. However, since the above-mentioned polyvinyl chloride resin has a very low moisture permeability, even if the super absorbent polymer or porous inorganic powder related to this resin is added, the movement of water is blocked by the polyvinyl chloride resin, which is not always sufficient. Can not be obtained.

In order to prevent water migration from being hindered by the resin, it is possible to form a film having excellent moisture permeability in place of the above polyvinyl chloride resin, for example, an acrylic or ethylene-vinyl acetate copolymer system. It is conceivable to use an aqueous emulsion resin such as. However, since such an aqueous emulsion resin is generally inferior in flame retardance to a polyvinyl chloride resin, it is necessary to add a large amount of flame retardant in order to impart flame retardancy equivalent to that of the conventional one, and the above-mentioned absorption Along with the addition of a moisture-releasing agent, the ratio of the resin component, which is the main constituent material of the foam decorative layer, is relatively decreased, which tends to cause a decrease in the surface strength of the foam decorative layer, and the formation of the foam decorative layer. At times, if an aqueous emulsion composition is mixed with the moisture absorbing / releasing agent for coating, the moisture absorbing / releasing agent absorbs water in the aqueous emulsion composition and gels, which makes coating difficult. Due to such problems, it has not yet been put to practical use.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in the prior art, and its object is to provide excellent flame retardancy and moisture absorption / release properties. It is to provide a flame-retardant moisture-absorbing and desorbing foamed decorative material having the above-mentioned properties, sufficient surface strength, easy formation of a foamed decorative layer by coating, and excellent productivity, and a method for producing the same.

[0007]

DISCLOSURE OF THE INVENTION The present invention is characterized in that a foamed decorative layer made of an aqueous emulsion resin containing guanidine sulfamate and / or calcium sulfamate is provided on a substrate. It is a flammable, moisture-absorbing and foaming decorative material.

Further, in the flame-retardant moisture-absorbing / releasing foamed decorative material, the content of guanidine sulfamate and / or calcium sulfamate is 5 to 25 parts by weight per 100 parts by weight of the aqueous emulsion resin. It is characterized by.

Further, in the present invention, an aqueous emulsion composition containing a foaming agent and guanidine sulfamate and / or calcium sulfamate is coated on a base material, dried and foamed by heating to form a foamed cosmetic layer. The method for producing a flame-retardant moisture-absorbing / releasing foamed decorative material is characterized in that

Further, in the above production method, the total amount of guanidine sulfamate and / or calcium sulfamate in the aqueous emulsion composition is such that the water content in the aqueous emulsion composition is 10%.
It is characterized by being 15 to 40 parts by weight per 0 parts by weight.

Further, in the above production method, the ratio of the weight of water to the sum of the weight of the resin component and the water contained in the aqueous emulsion composition is 35 to 70%. is there.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to the drawings.

The flame-retardant, moisture-absorbing and desorbing foamed decorative material of the present invention comprises, for example, as shown in FIG. 1, a foamed decorative layer 2 provided on a base material 1, the surface of which is conventional. Similar to the foamed decorative material, the pattern 3 may be printed, or the concavo-convex pattern 4 by embossing may be applied, if necessary.

The base material 1 serves as a support for the intended flame-retardant, moisture-absorbing and desorbing foam decorative material, and is heat resistant to such an extent that the foam decorative layer 2 is not significantly deformed by heat during foaming. The material is not particularly limited as long as it has
Specifically, paper such as thin paper, titanium paper, inorganic paper, or flame-retardant paper, cloth such as woven or non-woven fabric, synthetic resin film or sheet, wood veneer, plywood or metal plate, or the like, or Appropriate materials may be selected from those laminates, composites and the like according to the intended use.

The foam decorative layer 2 is a layer having an aqueous emulsion resin, which is a dried and solidified product of the aqueous emulsion composition, as a main component, and having a foamed structure by the action of the foaming agent added to the aqueous emulsion composition. In the present invention, the foamed decorative layer 2 contains guanidine sulfamate and / or calcium sulfamate. These may be contained alone or in a mixture of both.

The above-mentioned guanidine sulfamate and / or calcium sulfamate functions as a flame retardant for imparting flame retardancy to the foam decorative layer 2 and as a moisture absorbing / releasing agent for imparting hygroscopicity to the foam decorative layer 2. It has both functions. Therefore, as compared with the case where the flame retardant and the moisture absorbing / releasing agent are separately blended, the total blending amount of the flame retardant and the moisture absorbing / releasing agent in the foam decorative layer 2 is suppressed, and the proportion of the resin component is increased accordingly. ,
The foamed decorative layer 2 can have a sufficient surface strength.

The present invention does not exclude the addition of a flame retardant and / or a moisture absorbing / releasing agent other than the above-mentioned guanidine sulfamate and / or calcium sulfamate. The degree of flame retardancy and moisture absorption / desorption required for foamed cosmetics may vary depending on the application. Foaming resistance and moisture absorption / desorption can be achieved only by guanidine sulfamate and / or calcium sulfamate. This is because it is not always possible to design in the optimum range according to the application of the decorative material. Therefore, for example, in the case where the moisture absorption / release property is more important than the flame retardancy, other moisture absorbing / releasing agents are used together, or in the case where the flame retardancy is more important than the moisture absorption / release property. You may use together another flame retardant.

Further, in terms of flame retardancy or moisture absorption / desorption property, the former is, for example, combustion speed, calorific value, smoke amount, etc., and the latter is, for example, moisture absorption / desorption rate, saturated moisture absorption amount, etc. , And it is not always possible to optimize all parameters with guanidine sulfamate and / or calcium sulfamate alone. Therefore, in some cases, guanidine sulfamate and / or calcium sulfamate, another flame retardant, and another moisture absorbing / releasing agent may be used in combination. Even in such a case, as compared with the case of using only another flame retardant and another moisture absorbing / releasing agent, guanidine sulfamate and / or calcium sulfamate having a part of each function of both. By replacing with, it becomes possible to reduce the total blending amount of the flame retardant and the moisture absorbing / releasing agent.

The blending amount of guanidine sulfamate and / or calcium sulfamate in the foam decorative layer 2 is optional depending on the degree of flame retardancy and moisture absorption and desorption required for the intended foam decorative material, but is too small. If the effect is poor and too large, on the contrary, the surface strength of the foamed decorative layer 2 will be reduced, and it will dissolve into the water adhering to the surface, which will easily cause stickiness, dusting, stains, etc. It is desirable that the amount be 5 to 25 parts by weight per 100 parts by weight of the resin.

In the present invention, the use of guanidine sulfamate and / or calcium sulfamate as the flame retardant and moisture absorbing / releasing agent has an excellent advantage in the production of the flame retardant moisture absorbing / releasing foamed cosmetic material of the present invention. Have That is, in the present invention, the foamed decorative layer 2 is formed by coating an aqueous emulsion composition, and a moisture absorbing / releasing agent that is generally used in this aqueous emulsion composition (super absorbent polymer, porous inorganic powder, etc.). When water is added, the moisture absorbing / releasing agent absorbs the water in the aqueous emulsion composition, so that gelation of the aqueous emulsion composition occurs and coating is often difficult. In contrast, guanidine sulfamate and calcium sulfamate have high water solubility (both water 10
(Solubility with respect to 0 g is about 45 g), and since it is a low molecular weight compound, it does not extremely thicken. Therefore, as long as it is compounded within the range of solubility, there is no possibility of causing a coating failure accident. is there.

From the above point of view, the amount of guanidine sulfamate and / or calcium sulfamate to be added to the aqueous emulsion composition (when both are used in combination) is 40 parts by weight per 100 parts by weight of water in the aqueous emulsion composition. It is desirable that the number is equal to or less than a part. The lower limit of the blending amount is preferably 15 parts by weight or more per 100 parts by weight of water in order to obtain sufficient flame retardancy and moisture absorption / release.

Further, in order to obtain sufficient flame retardancy and moisture absorption / desorption properties with the blending amount within the above range, the water content of the aqueous emulsion composition is the resin component (aqueous emulsion resin).
It is desirable that it accounts for 35% by weight or more of the total of water and water. The upper limit of the water content is preferably 70% by weight or less in order to ensure sufficient coating suitability (film forming property, drying property, etc.).

In the present invention, even when a flame retardant other than guanidine sulfamate and / or calcium sulfamate and / or a moisture absorbing / releasing agent is used in combination, only another flame retardant and another moisture absorbing / releasing agent are used. Compared with the case of, by substituting a part of each of them with guanidine sulfamate and / or calcium sulfamate having both functions, it is possible to remove other flame retardants or moisture absorbing / desorbing agents that adversely affect coating suitability. It is possible to reduce the blending amount, and it is possible to secure sufficient coating suitability for the aqueous emulsion composition.

In the present invention, the type of the aqueous emulsion resin used in the foam decorative layer 2 is not particularly limited,
For example, acrylic resin, styrene resin, styrene-
One or more selected from butadiene rubber, vinyl acetate-based resin, ethylene-vinyl acetate copolymer-based resin, silicone-based resin, polyurethane-based resin, polybutene resin and the like can be used, and the structure of the resin particles is Although not particularly limited, an ordinary copolymer, a multilayer structure such as a core / shell, a simple blend, or the like can be optionally used.

Examples of the foaming agent for foaming the foamed resin layer 2 include inorganic foaming agents such as sodium hydrogencarbonate, sodium borohydride, ammonium carbonate, azodicarbonamide, azobisisobutyronitrile and oxybis. Organic foaming agents such as benzenesulfonyl hydrazide,
Heat-expandable hollow microspheres (microcapsule foaming agent) in which a low boiling point liquid is enclosed in a shell made of a thermoplastic resin can be used alone or in appropriate combination, but an aqueous emulsion having high air permeability The heat-expandable hollow microspheres, which have a high foaming effect on the base resin, are most preferably used.

The heat-expandable hollow microspheres are a foaming agent composed of microspheres that can be expanded and foamed by heating, and include, for example, polyacrylonitrile, a shell of acrylonitrile / methyl acrylate copolymer, etc. Examples thereof include spheres having a particle diameter of about 1 to 50 μm, preferably about 2 to 30 μm, which contain a low boiling point hydrocarbon such as ethane, propane, butane, isobutane, pentane, hexane, and heptane. Specific examples include those commercially available under the trade name "Microsphere" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.

The foaming initiation temperature of the heat-expandable hollow microspheres is usually about 120 ° C to 180 ° C. When the temperature is lower than 120 ° C., foaming is likely to occur when the aqueous emulsion composition is dried, and foaming occurs before the foaming layer is dried, so that a good foaming layer is obtained after heating and foaming. It is not preferable because it tends not to occur. If the temperature exceeds 180 ° C, the foamability will decrease,
Since the heating temperature during foaming is high, the resin may deteriorate, which is not preferable.

The content of the heat-expandable microspheres in the aqueous emulsion composition is usually about 3 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous emulsion composition. Parts by weight. When the content of the heat-expandable microspheres exceeds 30 parts by weight, the surface strength of the obtained foam decorative material tends to decrease, and 3
When the amount is less than the weight part, the expansion ratio is too low, and the volume feeling and the embossing suitability are insufficient, which is not preferable.

The aqueous emulsion composition used in the present invention contains guanidine sulfamate and / or
In addition to calcium sulfamate, flame retardant, moisture absorbing / releasing agent, foaming agent, if necessary, for example, an inorganic or organic filler, a colorant, a dispersant, an antiblocking agent, a thickener, an antifoaming agent, an ultraviolet absorbing agent. Agent, light stabilizer, antioxidant, matting agent,
Various additives such as lubricants, antifriction agents, antistatic agents, antibacterial agents and antifungal agents may be appropriately added.

The flame-retardant moisture-absorbing / releasing foamed decorative material of the present invention is produced by coating the above-mentioned aqueous emulsion composition on a substrate 1 such as paper or a synthetic resin film, drying and then foaming by heating. be able to. Examples of the coating method of the above aqueous emulsion composition include a knife coating method, a nozzle coating method, a die coating method, a lip coating method, a comma coating method, a gravure coating method, a rotary screen coating method and a reverse roll coating method. Can be mentioned.

After coating and drying the above aqueous emulsion composition, a foaming ink such as an oily or aqueous emulsion system and / or a non-foaming ink is used on the surface of the coating layer, for example, a gravure printing method or an offset printing method. Alternatively, the appropriate pattern 3 may be formed by printing by a screen printing method or the like. Further, after the foaming of the coating layer by heating, the mechanical embossing method of pressing the embossing plate onto the surface of the foamed coating layer, that is, the foamed decorative layer 2, or a part or the whole of the pattern 3 is a foaming accelerator or a foaming inhibitor. The concavo-convex pattern 4 may be formed on the surface of the foam decorative layer 2 by a chemical embossing method or the like in which printing is performed with an ink containing an agent or the like and then heat foaming is performed.

Further, the foam decorative layer 2 (or the pattern 3)
You may provide a surface protective layer (not shown) on it. However, it is necessary to pay attention to the material composition and film thickness having high moisture permeability so as not to impair the moisture absorption / release performance of the foam decorative layer 2. Specifically, it is most desirable to use an aqueous emulsion resin having high moisture permeability, and the film thickness can be up to about 30 μm at the maximum. Further, even an oil-based resin can be used as long as it is a urethane-based resin or the like having a relatively high moisture permeability,
It is desirable to keep the film thickness within a maximum range of 4 to 5 μm.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples are based on weight unless otherwise specified.

[Preparation of Aqueous Emulsion Composition] Aqueous emulsion compositions for use in the following Examples and Comparative Examples were prepared by blending commercially available raw materials in the weight ratios shown in Table 1. However, Comparative Example 2 and Reference Example 1
In the above, the composition was gelated at the time of compounding, and an aqueous emulsion composition which could be coated by a usual coating method was not obtained. Therefore, a foamed decorative material could not be prepared using these.

Table 1. Formulation Examples of Aqueous Emulsion Composition Comparative Example Reference Example Formulation 1 2 1 2 1 1 Aqueous Emulsion ¹⁾ 100 100 100 100 100 Guanidine Sulfamate 8.75 1.75 0 0 15 Calcium Sulfamate 8.75 1.75 0 0 15 Silica Gel Powder 0 0 0 15 0 microcapsule foaming agent 10 10 10 10 10 Note 1) ethylene-vinyl acetate copolymer system, solid content 50% by weight

[Examples 1 and 2 and Comparative Example 1] 100 basis weight
Each aqueous emulsion composition was coated on a flame-retardant paper for wallpaper of g / m ^{2 by} a knife coating method so that the coating amount after drying was about 100 g / m ^2, and then 120 ° C. for 2 minutes in an oven. It dried and the base layer was obtained. Next, a pattern was formed on these base layers by a gravure printing method using a water-based ink, followed by heating at 210 ° C. for 30 seconds to foam, and an uneven pattern was formed on the surface by embossing. 1
2 and the foamed decorative materials of Comparative Example 1 were produced.

Each of the foamed decorative materials was evaluated for flame retardancy as a semi-incombustible material with a cone calorimeter (ISO 5660, notification by the Ministry of Construction). The results are shown in Table 2.

Table 2. Results of Flame Retardancy Test Example 1 Example 2 Comparative Example 1 Reference total calorific value [MJ] 5.9 7.6 8.9 8 or less 200k over time [sec] 0 8 10 10 or less

Further, the moisture absorbing / releasing performance of each of the above foam decorative materials was evaluated under the following conditions. That is, first 25 ° C 5
After curing at 0% RH temperature and humidity for 24 hours, 25 ℃ 90
Put in the environment of% RH, measure the weight change over time,
After reaching a saturated state (however, it was regarded as saturated after 100 hours), the sample was returned to an environment of 25 ° C. and 50% RH, and the weight change with time was measured. The result is shown in FIG.

[0040]

As described above, according to the present invention, it has an excellent flame retardant effect and an excellent moisture absorbing / releasing performance,
Moreover, it has a remarkable practical advantage that it is possible to provide a flame-retardant moisture-absorbing / releasing foamed decorative material which can be easily produced without causing coating defects of the foamed decorative layer during its production. Is.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an embodiment of a flame-retardant moisture absorptive and desorptive foamed decorative material of the present invention.

FIG. 2 is a graph showing the evaluation results of moisture absorption / release performance of Examples 1 and 2 and Comparative Example 1.

[Explanation of symbols]

1 ... Base material 2 ... Foamed decorative layer 3 ... Design pattern 4 ... uneven pattern

Claims (5)

[Claims] 1. A flame-retardant moisture-absorbing / releasing foaming decorative material comprising a base material and a foaming decorative layer made of an aqueous emulsion resin containing guanidine sulfamate and / or calcium sulfamate. . 2. The flame retardant according to claim 1, wherein the content of guanidine sulfamate and / or calcium sulfamate is 5 to 25 parts by weight per 100 parts by weight of the aqueous emulsion resin. Foam cosmetic material that absorbs and absorbs moisture. 3. An aqueous emulsion composition containing a foaming agent and guanidine sulfamate and / or calcium sulfamate is coated on a substrate, dried and foamed by heating to form a foamed cosmetic layer. A method for producing a flame-retardant moisture-absorbing / releasing foamed decorative material. 4. The total content of guanidine sulfamate and / or calcium sulfamate in the aqueous emulsion composition is 15 to 40 parts by weight per 100 parts by weight of water contained in the aqueous emulsion composition. The method for producing a flame-retardant, moisture-absorbing and desorbing foam decorative material according to claim 3. 5. The ratio of the weight of water to the sum of the weights of the resin component and water contained in the aqueous emulsion composition is 35 to 70%, wherein A method for producing a flame-retardant, moisture-absorbing and releasing foamed decorative material.