JPS61127742A - Surface-coating material - Google Patents

Abstract

PURPOSE:To provide a surface coating material containing an adsorbent produced by adsorbing a useful volatile substance in the fine powder of a specific zirconium compound, and capable of releasing the useful volatile substance uniformly for a long period at a constant rate of release. CONSTITUTION:A useful volatile substance (e.g. perfume, deodorant, insecticide, etc.) is dissolved in an organic solvent having relatively low viscosity (e.g. methanol, ethyl acetate, etc.), and refluxed together with fine powder of a zirconium compound (the orthophosphate, condensed phosphate, phosphosilicate or hydrated oxide of zirconium) using a refluxing apparatus furnished with a condenser to effect the occlusion of the useful volatile substance in the pore of the material containing the zirconium compound. The product is heated at 60-90 deg.C in vacuum to remove the solvent. The zirconium adsorbent containing the occluded useful volatile substance is compounded to a surface- coating material (e.g. paint, printing ink, etc.) in an amount of 1-20wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surface coating material containing a volatile substance.

In this specification, a surface coating material refers to a material that can form a partial or full coating film, thin layer, sheet, etc. on the surface of an article or object using methods such as coating, spraying, printing, molding, and coating. Specifically, paint, printing ink,
Examples include paints, adhesives, polymer resins, and the like.

These surface coating materials are given specific functions depending on their type. That is, for example, paints are used to protect the surface of objects, such as moisture-proofing, corrosion-proofing, chemical-proofing, and insulation-proofing, and to add beauty through coloring, etc., and printing inks are used to print letters, letters, etc. on printed materials using printing machines. Used to print figures, patterns, etc. Adhesives as surface covering materials are used for adhering exterior sheets (for example, wallpaper) or surface decoration materials for articles and building materials, and polymer resins are used as paints or adhesives, as well as sheets or films. It is molded into shapes and used for surface protection, decoration, packaging, etc. of articles.

Such conventional surface coating materials are intended to exhibit their own unique functions, but in recent years, as lifestyles have improved, there has been a growing demand for product diversification and improved added value.

Therefore, the present inventor has proposed that by incorporating useful volatile substances such as fragrances, deodorants, and insecticides into the surface coating material, the coating material can be used to protect the surface of the paint, the printed surface of printing ink, the adhesive surface of adhesive, etc. We conducted various studies from the viewpoint that if it were possible to gradually dissipate the volatile substances mentioned above, it would be extremely beneficial for improving the living environment.

[Conventional technology]

Conventionally, as this type of technology, attempts have been made to incorporate fragrances into paints and printing inks as useful volatile substances.

In other words, the method of dissolving and diluting fragrances in a solvent and adding them directly to paints or printing inks does not provide long-lasting fragrance release;
A method is known in which the compound is added by being adsorbed onto a porous adsorbent.

However, in the former method of encapsulating in microcapsules,
A coating film coated or printed with paint or printing ink does not emit a scent by itself, and has the disadvantage that the scent cannot be generated unless external pressure is applied to destroy the microcapsules. There is also the problem that they are easily destroyed. On the other hand, in the latter method of adsorption to an adsorbent, the adsorbed perfume dissipates in a short period of time, and although the dispersion is too strong at the beginning, it usually stops after 20 to 60 days. Therefore, it is difficult to diffuse the scent at a constant rate over a long period of time at room temperature, and there are also drawbacks such as the fact that many products do not release the scent unless they are heated or warmed.

When a surface coating material contains a useful volatile substance, a particularly important requirement is that the volatile substance occluded in the carrier is emitted at a constant and appropriate emission rate over a long period of time.
Currently, no surface coating material is known that satisfies such requirements.

The present inventor has conducted various studies on volatile substance holders that can satisfy these requirements, and has found that a specific finely ground zirconium compound can satisfactorily meet these requirements.

Previously, certain zirconium compounds have been known to be used as selective adsorbents for extracting potassium from seawater and brine, or in paints and adhesives. is unknown except as a fragrance.

A solid flavoring material in which a flavoring material is occluded in a zirconium compound and a solid flavoring material for cigarettes in which the solid flavoring material is contained in a cigarette filter are disclosed in Japanese Patent Publication No. 57-22314. However, in the solid flavoring agent disclosed herein, the zirconium compound occluded with a flavoring agent is used only in the form of granules or powder, and the application of this to surface coating materials is not anticipated at all. The reason for this is that the surface of the zirconium compound adsorbent that occludes volatile substances is covered with a surface coating material, which is thought to prevent the volatile substances from dissipating. However, the present inventor has found that when a specific zirconium compound is made into a fine powder, volatile substances are occluded and added to a surface coating material to form a coating film or a thin layer, zirconium in the form of granules or powder The present invention was accomplished by discovering that, compared to a compound in which volatile substances are occluded, the volatile substances can be emitted in a more favorable state, that is, the emission of volatile substances can be maintained uniformly and at a constant rate for a longer period of time. It is something.

[Problem that the invention seeks to solve]

That is, an object of the present invention is to provide a surface coating material for paints, printing inks, adhesives, paints, polymer resins, etc., which has high added value and contains a volatile substance. The object of the present invention is to provide a surface coating material that allows the dispersion of sexual substances to occur uniformly and at a constant rate over a long period of time. Another objective is that it is relatively stable not only at normal temperature and pressure, but also under heat and pressure, does not hinder the formation of coating films, thin layers, sheets, etc., and does not adversely affect the original properties of the surface coating material. It is an object of the present invention to provide a surface coating material containing no volatile substances.

[Means for solving problems]

That is, the present invention contains an adsorbent in which useful volatile substances are occluded in fine powder of a zirconium compound selected from zirconium orthophosphates, condensed phosphates, phosphosilicates, and hydrous oxides. It is a surface coating material.

The zirconium compounds used as carriers for useful volatile substances in the present invention are as described above, and the condensed phosphates include heximetaphosphates, tripolyphosphates, and birophosphates. The carrier made of these zirconium compounds must be a fine powder having an average particle size of about 0.1 to 100 microns, preferably about 0.5 to 50 microns.

These zirconium compounds are obtained by using a dry or wet ball mill or the like to obtain granules of approximately 24 to 100 mesh obtained by a known method as disclosed in Japanese Patent Publication No. 57-22314 using zirconium oxychloride as a raw material. It is obtained by finely pulverizing the powder into the above particle size range. Table 1 shows the properties of this fine zirconium compound powder for zirconium phosphosilicate.

Table 1 The physical property values shown in Table 1 are values measured for fine powder with an average particle size of 3μ, and the specific surface area and pore volume are values measured using a pore distribution analyzer manufactured by Shimabara Seisakusho. The surface area hardly changes before and after pulverization, and the pore radius of zirconium compounds is mostly in the range of approximately 5 to 15 pores, so even if the zirconium compound is finely pulverized, there is no risk that its ability to absorb and retain volatile substances will decrease. It can be said that there is no.

Next, useful volatile substances that can be stored in the above-mentioned zirconium compound include, but are not limited to, fragrances, deodorants, insecticides, fungicides, biorepellents, bioattractants, etc. In addition, even if the substance itself is non-volatile, by dissolving it in a volatile solvent, the volatile substance referred to herein also includes a substance that evaporates along with the solvent.

In the above, the fragrance may be various natural fragrances or synthetic fragrances of vegetable and animal origin, as well as natural fruit juice extracts.
Particularly preferred are those with a floral or woody scent.

In addition, as deodorants, those whose main ingredient is abietic acid,
In addition to organic deodorants such as those containing green tea extract as a main component, inorganic deodorants such as chlorine dioxide can be used. In addition, unlike the usual method of using insecticides, which involves spraying a large amount of chemical solution at once to kill insects, the chemical solution is gradually released over a long period of time, so it is expected to be more effective in preventing pests from entering and preventing feeding damage. Examples of such agents include relatively low toxicity organic phosphorus agents, organic chlorine agents, carbamate agents, etc. Biorepellents include diethyltoluamide and its isomers, dimethyl phthalate, butopyrotuxyl, methyl salicylate, etc. as main ingredients, but rather than being used as a single compound, they are effective against various insects. Several types of compounds are used in combination.

Furthermore, examples of the fungicide include fungicidal drugs that are currently commercially available as antifungal paints, organic compounds such as mercury, copper, and zinc, and antifungal agents such as salicylanilide and pentachlorophenol.

These volatile substances may be used in combination of one or more types.

Next, as a method for occluding volatile substances in a zirconium compound support, volatile substances can be stored in alcohols such as methanol and ethanol, or relatively low viscosity substances such as benzene, ether, acetone, chloroform, hexane, and ethyl acetate. By dissolving the zirconium compound in an organic solvent and heating and refluxing it together with the zirconium compound holder using a known reflux device equipped with a cooling tube, it can be easily occluded into the pores of the zirconium compound holder. In this case, the heating temperature is determined by the boiling point of the organic solvent used, but the reflux time and the dilution concentration of the volatile substance with respect to the solvent are appropriately selected within a desired range depending on the type of carrier, volatile substance, and purpose of use. The longer the reflux time is, and the lower the concentration of volatile substances in the solvent, the more likely they are to be occluded by the support, but usually the reflux time is 10 to 1
20 minutes, the ratio of volatile substance to solvent is 1:5-1:
A range of 500 (weight ratio) is suitable. In addition, if the volatile substance is one that is likely to change in quality when heated, the zirconium compound support may be immersed in a solvent in which it has been dissolved for several hours to over 20 hours, with the cap tightly closed while stirring occasionally. Volatile substances can be occluded within the pores of the holder.

In the present invention, the holder which has been subjected to the above-mentioned heating reflux operation or dipping operation is dried under reduced pressure at 90° C. or lower, preferably 60° C. or lower to remove the solvent and obtain a solid material containing volatile substances.

The zirconium compound support has an extremely excellent ability to retain volatile substances, and this is thought to be due to the molecular structure of the zirconium compound. In other words, although the mechanism of occlusion of volatile substances in the zirconium compound support is not necessarily clear, the above-mentioned heating reflux or stirring/mixing operation allows substances with relatively large molecular weights that are difficult to be occluded by ordinary adsorbents to be absorbed. Due to the decrease in polarity and viscosity due to dissolution in the organic solvent and the swelling of the pores of the support, air is freely replaced between the eyebrows of the crystal lattice or in the pores, and the pore space is increased at room temperature when dissolved in the solvent. It is presumed that it is maintained for a long period of time due to contraction.

The zirconium adsorbent that has absorbed useful volatile substances as described above is mixed with surface coating materials such as paints, printing inks, paints, adhesives, or polymer resins, and applied to the surface of the target article or object. A partial or complete coating, thin layer, sheet, film, etc. is formed by means such as coating, spraying, printing, molding, and coating.

In this case, the amount of zirconium adsorbent mixed in the surface coating material varies depending on the type of surface coating material and the purpose of use, but is usually in the range of 1 to 20% by weight, and since the zirconium adsorbent is a fine powder, it can be mixed Easy to operate,
The dispersibility is also good.

[Action/Effect]

As explained in detail above, the surface coating material of the present invention contains an adsorbent in which useful volatile substances are occluded in fine zirconium compound powder, and is used to coat or coat the surface of the target article. When a thin layer is formed, it is thought that the dissipation of volatile substances is hindered, but in reality, the dispersion of volatile substances is uniformly carried out over a long period of time, and the effect is extremely satisfactory. found.

The reason for this is that when you microscopically observe the coating film or thin layer formed by the surface coating material, you can see that moisture in the air and air are constantly permeating, and volatile substances absorbed by the zirconium compound are being absorbed. It is assumed that the release occurs gradually and at a constant rate over a long period of time due to moisture in the air or contact with the air.

As an experimental example to demonstrate this, when the fragrance was simply infiltrated into paper, the fragrance completely volatilized in about 2 to 3 weeks;
Under the same conditions, a zirconium compound (zirconium orthophosphate) that occluded a fragrance was gradually released over a period of about 6 months; on the other hand, a zirconium compound that occluded a fragrance as a fine powder and mixed it into paint It was confirmed that when the paint of the invention was applied, the fragrance lasted for about one year. In other words, the dissipation of volatile substances occluded by zirconium compounds is affected by the moisture on the surface of the adsorbent and the diffusion rate due to air flow. , it can be seen that when the surface is covered with a surface coating material film, the dissipation is rather sustained at a constant rate over a long period of time.

In addition, the zirconium adsorbent that absorbs volatile substances is a transparent fine powder and is relatively stable even when heated, so it can be used as a surface coating material such as paint, printing ink, adhesive, or polymer resin. Even if mixed into the surface coating material, the original characteristics of the surface coating material will not be completely lost, and volatile substances occluded by heating drying after coating or heating operation during forming a thin film or sheet of polymer resin will not be lost. is not rapidly dissipated.

Therefore, by coating the surfaces of articles or objects made of paper, wood, plastic, metal, etc. with the surface coating material of the present invention by various means, it is possible to significantly improve the added value of these articles or objects. That is, when the volatile substance is a fragrance, for example, various articles that emit a scent for a long period of time can be provided, and when it is a deodorizing agent, it can be applied to interior materials of kitchens, toilets, etc. This will eliminate bad odors for a long period of time.

In the case of an insecticide, even if it is impossible to achieve an insecticidal effect, it can be sufficiently applied for the purpose of protecting articles from feeding damage caused by mosquitoes, blackflies, ticks, hair mites, termites, cockroaches, etc. Furthermore, by applying disinfectants, rustproofing agents, and various other solvent-soluble substances, the present invention can be applied to a wide range of applications.

〔Example〕

A more detailed explanation will be given below using examples.

In addition, in the following examples, % is weight % unless otherwise specified.
shows.

Example 1 An adsorbent was obtained in which zirconium phosphate silicate (hereinafter abbreviated as ZSP) finely pulverized to an average particle size of about 3 μm contained about 15% rI & hinokiol, which is a component of the aroma of cypress wood. The occlusion method is to dissolve 15 g of hinokiol in 250 mQ of 99% ethanol, and add the above ZSP fine powder 1 to this solution.
00g was added, and the mixture was heated under reflux for 30 minutes using a heating reflux device. After the reflux was completed, the mixture was transferred to an evaporator and dried under reduced pressure in a hot bath at 50'C to remove alcohol, thereby obtaining hinokiol adsorbent powder, which was designated as Sample Strain 1-1. Furthermore, sample magnets 2-1 and N13-1 were prepared using commercially available strawberry flavor and lily of the valley flavor, respectively, under exactly the same conditions as for hinokiol. In addition, zirconium hexametaphosphate (hereinafter abbreviated as ZPP) finely pulverized to an average particle size of about 3 μm was used as a carrier to absorb 25% of each of the three types of fragrances (
In the case of ZPP, it holds samples 1-2, 2-2, and N13-2, which have a large storage capacity (25% can be stored), and hydrated zirconium oxide (hereinafter abbreviated as ZOH) finely ground to an average particle size of 3μ. 15% each of the above three fragrances as a body
The occluded samples 1-3, 2-3, and 3 were prepared under exactly the same conditions as in the case where zsp was used as the carrier. Next, 100 g of each commercially available synthetic resin emulsion paint consisting of three components: acrylic resin, pigment, and water was added.
10 g of samples in which three types of fragrances were occluded were added to each of the above-mentioned zsp, zPP, and ZOH carriers, and thoroughly mixed using a homogenizer to prepare the paint of the present invention.

Each of these paints was applied to a thickness of 100 μm on a piece of wood and left in a room with no temperature control, avoiding direct sunlight, and changes in scent intensity and quality after painting were examined at regular intervals. The investigation was carried out using a olfactory test conducted by 10 sensory inspectors, using a scoring system with the strength of the initial scent of the painted product as 100. The results were as shown in Table 2. Note that the numerical values are average values of 1°.

From the results in Table 2, both hinokiol and strawberry flavorings showed almost no change in aroma intensity and aroma quality even after one year, while lily of the valley fragrance showed changes in aroma intensity and aroma quality. However, even after one year had passed, the practical effect was sufficient. Moreover, when ZSP, ZOH, and ZPP are compared as holding bodies, zsp is the most excellent. Note that ZPP has a large fragrance retention capacity, so ZPP is suitable for use when it is desired to strongly diffuse the fragrance of the fragrance.

Example 2 The three types of paints of the present invention prepared in Example 1 by occluding fragrance in zsp were applied to a thickness of 100 μm on wooden temporary sheets, and after painting, the paints were placed in a ventilation dryer and heated at 100”C and 150°C, respectively. We investigated changes in aroma intensity when heated.

The investigation method is the same as in Example 1. The result is the third
It was as shown in the table.

From the results in Table 3, it was found that even when heated to 150° C. for 5 minutes, the fragrance intensity decreased only slightly, and the release of fragrance due to instantaneous heat drying or heat molding was extremely small.

Example 3 An adsorbent was prepared in the same manner as in Example 1, in which about 15% of a commercially available strawberry flavor was occluded in zsp finely ground to an average particle size of about 2 μm.

Next, the particle size is 0.05-3μ, the degree of polymerization is 1000-1800
15% of this adsorbent was added to the vinyl chloride resin fine powder, and 4% of dioctyl phthalic acid was added as a plasticizer, mixed well, spread on a pre-heated aluminum plate using a vibrating drop method, and dried. Hold it in the container at 150℃ for 3 minutes,
A continuous molten coating was formed on the board. The coating thickness after solidification was approximately 300μ.

This coating film was left at room temperature under the same conditions as in Example 1, and changes in aroma intensity and aroma quality were examined at regular intervals over a period of one year. The investigation method is the same as in Example 1. The results are shown in Table 4.

Table 4 Example 4 Example 1 A deodorant made of green tea extract (commercial product name: Deodorant B) was added to ZPP finely ground to an average particle size of about 2μ.
An adsorbent with approximately 20% occlusion was prepared under the same conditions as above.

Next, 100 g of pelleted polyethylene was added to each
The mixture was softened and melted at 90° C., 2 g and 5 g of the above-mentioned adsorbent were added thereto, thoroughly kneaded, and immediately rolled out to produce sheets each having a thickness of 1 mm. Note that the sheet to which about 5% of adsorbent was added was slightly colored by green tea extract.

On the other hand, as a control, a polyethylene sheet to which no adsorbent was added was produced under the same conditions and compared with a sheet to which an adsorbent was added for the presence or absence of resin odor.

As a result, none of the adsorbent-added sheets that occluded the deodorizing agent had the chemical-like resin odor characteristic of the control polyethylene sheet.

Example 5 10 parts of chlordane, an insecticide, was dissolved in 300 parts of acetone, 00 parts of zspi with an average particle size of about 3 μm was added thereto, the mixture was sealed with occasional stirring and left overnight, then transferred to an evaporator and reduced pressure. The mixture was dried at 50°C to remove acetone. An anti-termite paint of the present invention was prepared by mixing 10 parts of this chlordane storage adsorbent powder with 100 parts of a commercially available acrylic resin water-soluble paint.

This paint was applied to the entire surface of a vinyl chloride disk and a wooden disk formed to a diameter of 301 m and a thickness of 2 nm to a thickness of approximately 501 μm.
A coating film was formed.

A termite damage test was conducted on this paint film formed sample using the following method.

That is, in a cylindrical glass insect rearing bottle with a diameter of 10 cm and a volume of 500 J, 1) 400 g of dry sand (particle size 0.5 to 1 mm) that had been sterilized for 2 hours at 5°C and 80 g of sterilized distilled water were placed.
g was added. The above-mentioned coating film forming sample and a vinyl chloride disk coated with only the paint without adding chlordane were charged into each of the rearing bottles prepared in this way as a control, and further 1. In each case, 100 termites were removed from their nests and placed in the nests for breeding.

The breeding conditions were a temperature of 25±2°C and a humidity of 75% in a dark place for one year. During this period, dead termites were removed and live termites were replenished, and the condition of termite feeding on the sample was visually observed at regular intervals.

The results are shown in Table 5.

Table 5 The indication of feeding damage in the table is as follows.

- No feeding damage, +: Slight feeding damage ++: Feeding damage, +++: Feeding damage to the extent that holes are formed From the results in Table 5, the samples coated with the paint of the present invention were not damaged by termites regardless of the difference in materials. It can be seen that it is not affected at all.

Example 6 In the same manner as in Example 1, an adsorbent powder was obtained in which about 15% hinokiol was occluded in zsp finely pulverized to an average particle size of about 1Oμ. Next, a commercially available water-soluble adhesive is first applied to a commercially available wallpaper paper sheet, and then granular vermiculite mixed with 5% adsorbent powder is applied to the adhesive-coated surface of the paper sheet so that the thickness is approximately uniform. It was distributed as desired. The amount of adsorbent powder to be sprayed was approximately 3 g per 1 rrr of the Gi sheets. Next, a commercially available quick-drying adhesive was sprayed on top of this, immediately placed in a dryer, dried at 150° C. for 2 minutes to fix the vermiculite mixture, and left to cool to room temperature to produce wallpaper.

This wallpaper was printed on a wall in a room that is not exposed to direct sunlight and left for one year, and the strength of the scent was investigated. As a result, it was confirmed that the scent was emitted at a roughly constant strength. In addition, 15
There was no effect of aroma release due to heating at 0'C for 12 minutes.

Example 7 An adsorbent was prepared by occluded about 18% of Stroheli fragrance into zsp finely ground to an average particle size of about 3 μm under the same conditions as in Example 1.

Next, this adsorbent powder was mixed in various proportions into a lithographic printing ink consisting of three components: oil, synthetic resin, and pigment, and a kneading test was conducted using a roll mixer. As a result, the mixing ratio of adsorbent powder is limited to about 20%, and if it is added more than that, the printing characteristics will deteriorate. Therefore, a range of 2 to 20%, preferably a range of 10 to 15% was appropriate from the viewpoint of the strength of the scent of printed matter. Printed matter that was lithographically printed using this printing ink lost its fragrance over a long period of time, and almost no change in the intensity or quality of the fragrance was observed for 6 months.

Claims (3)

[Claims] (1) It is characterized by containing an adsorbent in which a useful volatile substance is occluded in fine powder of a zirconium compound selected from zirconium orthophosphate, condensed phosphate, phosphosilicate, and hydrous oxide. surface coating material. (2) The surface coating material is paint, printing ink, paint, adhesive,
or the surface covering material according to claim 1, which is a polymer resin. (3) Claim 1 or 2, wherein the useful volatile substance is one or more substances selected from fragrances, deodorants, insecticides, fungicides, biorepellents, bioattractants, and rustproofing agents. Surface covering material according to item 2.