Solid which releases a fragrant substance and/or a disinfectant
This ia a, division, of application, Ser. No. 721,141 filed Apr. 9, 1985, which is a continuation of application Ser. No. 524,007, filed August 17, 1983 both abd. 
     The present invention relates to a solid which releases a fragment substance and/or a disinfectant and more particularly to a solid which contains, in addition to the fragrant substance and/or a disinfectant, a sublimable carrier which when exposed to the environment releases the fragrant substance and/or disinfectant. 
     BACKGROUND OF THE INVENTION 
     Heretofore, para-dichlorobenzene has been used to form deodorizer blocks for use in restrooms. (See Seifen-Oele-Fette-Wachse, Vol. 108 p.529). Since para-dichlorobenzene is moderately toxic, it is desirable to find a substitute for this material. 
     Therefore, it is an object of the present invention to provide a solid which will release a fragrant substance when exposed to the environment. Another object of the present invention is to provide a solid which will release a disinfectant to the environment. Still another object of the present invention is to provide a solid containing a fragrant substance and/or a disinfectant and a sublimable carrier for the fragrant substance and/or disinfectant. A further object of this invention is to find a substitute for para-dichlorobenzene as a deodorizer which is less toxic. 
     SUMMARY OF THE INVENTION 
     The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing a solid containing a fragrant substance and/or a disinfectant and a sublimable carrier in which at least a portion of the sublimable carrier is selected from the group consisting of hexamethylcyclotrisiloxane, tetramethylcyclobutanedione and mixtures thereof, which when exposed to the environment releases the fragrant substance and/or disinfectant. 
     DESCRIPTION OF THE INVENTION 
     The solid prepared in accordance wtih this invention is suitable not only as a fragrance block for use in restrooms, but it is indeed suitable for the release of fragrant substances or disinfectants or fragrant substances and disinfectants, for example, in waiting rooms of any type, such as livng rooms, workroom, and lounges, as well as rooms in which objects are displayed or performances held, and public and private washrooms. 
     The solid of this invention can be support-free or it can be supported by supports such as paper, cardboard, or plastic films or it can contain such supports or be supported in containers which have at least one opening. 
     The solid can contain the same fragrant substances and disinfectants or the same fragrant substances or disinfectants as the previously known solids for the release of fragrant substances and/or disinfectants to the surrounding environment such as air or water. 
     One of the sublimable carriers contemplated by this invention for the fragrant substances and/or disinfectants is hexamethylcyclotrisiloxane. Hexamethylcyclotrisiloxane, which is a known compound, has been combined with fragrant substances and used heretofore in cosmetics. (See, for example, Chemical Abstracts, Vol. 91, 1979, Abstract 198797 k). 
     Hexamethylcyclotrisiloxane can be prepared in accordance with known methods or it can be prepared by heating a linear, branched, or cross-linked organopolysiloxane which consists of at least 50 mol percent of dimethylsiloxane units to at least 350° C. in the absence of substantial amounts of substances which attack the siloxane group, and simultaneously distilling off the cyclic dimethylpolysiloxanes formed during heating. 
     The sublimation rate of hexamethylcyclotrisiloxane, which is higher than that of p-dichlorobenzene, can be controlled by adjusting the size of the openings of the container in which the hexamethylcyclotrisiloxane, together with the fragrant substance and/or disinfectant, is exposed to the environment or by admixing a slow-subliming substance such as tetramethylcyclobutanedione with the hexamethylcyclotrisiloxane. A mixture containing 25 weight percent of hexamethylcyclotrisiloxane and 75 weight percent of tetramethylcyclobutanedione has about the same rate of sublimation as p-dichlorobenzene. 
     Tetramethylcyclobutanedione which is a known compound has the formula ##STR1## 
     Tetramethylcyclobutanedione is preferred when the solid is to be exposed in the presence of water, such as for example, when the solid is to be used in toilet fixtures. 
     Tetramethylcyclobutanedione has a pleasant wood-camphor odor, and is capable of binding basic substances such as ammonia. 
     If the solid of this invention contains both hexamethylcyclotrisiloxane and tetramethylcyclobutanedione, it preferably contains from 10 to 90 weight percent and more preferably from 20 to 30 weight percent of hexamethylcyclotrisiloxane and from 90 to 10 weight percent and more preferably from 80 to 70 weight percent of tetramethylcyclobutanedione, based on the total weight of hexamethylcyclotrisiloxane and tetramethylcyclobutanedione. 
     Preferably, the solid of this invention contains from 5 to 20 weight percent of a fragrant substance or disinfectant, based on the weight of the hexamethylcyclotrisiloxane, when the sublimable substances other than the fragrant substance or disinfectant consists of at least 50 weight percent hexamethylcyclotrisiloxane. When the fragrant substance or disinfectant is a solid the fraction of sublimable can also be larger. 
     Preferably, the solid of this invention contains from 5 to 20 weight percent of a fragrant substance or disinfectant, based on the weight of the tetramethylcyclobutanedione, when the sublimable substance other than fragrant substance or disinfectant consists of at least 50 weight percent tetramethylcyclobutanedione. 
     The solid prepared in accordance with this invention can contain other substances in addition to the hexamethylcyclotrisiloxane and/or tetramethylcyclobutanedione and the fragrant substance and/or disinfectant. The addition of the other substances makes it possible to add even greater amounts of fragrant substances and/or disinfectants than that indicated above. Examples of such other substances are pyrogenic silica or precipitated silica having a surface area of at least 50 m 2  /g, common salt, surfactants, insect repellents, deodorants, and dyes, as well as phosphates. The amount of silica having a surface area of at least 50 m 2  /g is preferably from 0.5 to 5 weight percent, based on the total weight of the solid. 
     Hexamethylcyclotrisiloxane and tetramethylcyclobutanedione can be mixed as powders or melts with the other components to form the deodorizer compositions of this invention. 
     In the following examples, all parts and percentages are by weight unless otherwise specified. 
    
    
     EXAMPLE 1 
     About 20 g of pulverized hexamethylcyclotrisiloxane are blended with 2 g of perfume oil (&#34;Sea Breeze&#34;, Dragoco) and molded into a cylinder. The cylinder thus formed is placed in a plastic container of corresponding size which has a large number of small openings. The contents of the plastic container are effective as a room air deodorizer until they are completely volatilized (25 days). 
     EXAMPLE 2 
     About 20 g of a hexamethylcyclotrisiloxane melt is blended with 2 g of orange terpenes and solidified in a round mold. The cylinder obtained in this manner is placed in a plastic container of corresponding size which has a large number of small openings. The contents of the plastic container remain effective as a room air deodorizer until they have completely volatilized (25 days). 
     EXAMPLE 3 
     About 18 g of pulverized hexamethylcyclotrisiloxane are blended at 60° C. with 12 g of &#34;Lilac&#34; perfume oil and 1 g of pyrogenic silica having a surface area of approximately 200 m 2  /g, and the melt thus formed is solidified in a polystyrene petri dish containing longitudinal slots in its top. The contents of the petri dish give off a pleasant odor for 28 days in a room measuring 45 m 3 . 
     
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Composition of the &#34;Lilac&#34; perfume oil                                    
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18.0 percent      Hydroxycitronellal                                      
1.7 percent       Cinnamyl alcohol                                        
8.0 percent       Terpineol                                               
18.0 percent      Benzyl alcohol                                          
20.0 percent      Phenethyl alcohol                                       
2.0 percent       Linalool                                                
0.5 percent       Phenylacetaldehyde                                      
6.0 percent       Anisaldehyde                                            
16.0 percent      Piperonal                                               
2.5 percent       Indole (10 percent)                                     
7.3 percent       Jasmine base                                            
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     EXAMPLE 4 
     A mixture containing 10 g of pulverized hexamethylcyclotrisiloxane, 30 g of tetramethylcyclobutanedione and 5 g of a lily of the valley composition is molded into a cube. The cube is hung loose in a room and remains effective as a room deodorizer until it has completely volatilized (23 days). 
     
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Lily of the valley composition                                            
                   Parts                                                  
______________________________________                                    
Hydroxycitronellal   50                                                   
a-Hexylcinnamaldehyde                                                     
                     4                                                    
Benzyl alcohol       4                                                    
Geraniol             3                                                    
Citronellol          3                                                    
Linalool             3                                                    
Citronellal          3                                                    
Linalyl acetate      2                                                    
Indole (10 percent)  1                                                    
cis-3-Hexenol (10 percent)                                                
                     l                                                    
Lauryl aldehyde (10 percent)                                              
                     1                                                    
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     EXAMPLE 5 
     About 45 g of pulverized tetramethylcyclobutanedione is blended with 7 g of lavender oil and molded into a cylinder. The cylinder thus obtained gives off a pleasant fresh odor until it has completely volatilized (68 days). 
     EXAMPLE 6 
     A mixture containing 
     
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60 percent   Tetramethylcyclobutanedione                                  
20 percent   Sodium chloride                                              
15 percent   Fragrant substance                                           
 1 percent   Bactericide (&#34;Preventol&#34;,                                    
             registered trademark, Bayer AG)                              
 4 percent   Pyrogenic silica having a sur-                               
             face area of approximately 200 m.sup.2 /g                    
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     is molded into a block weighing 10 g. The fragrance block thus obtained is used in toilet bowls. It eliminates odors for 29 days just as thoroughly as a 50 g fragrance block containing p-dichlorobenzene. 
     EXAMPLE 7 
     Molded fragrance blocks weighing 70 g which consists of 
     
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50 parts   tetramethylbutanedione                                         
20 parts   phosphates                                                     
20 parts   surfactants and a total of                                     
10 parts   bactericide, aromatic substance                                
           and dye                                                        
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     clean, disinfect, give off a fragrance, and eliminate undesirable odors in toilet bowls for 3 to 6 weeks, depending on the frequency of flushing.