JPH0336542B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention generally relates to a method for producing a low-foaming aromatic substance for use as an aromatic deodorizer for toilets, rooms, cars, etc., and more specifically, the present invention relates to a method for producing a low-foaming aromatic substance that stably supports a fragrance, has good gel quality, and has an excellent appearance. Concerning a method for producing aromatic substances. Conventionally, methods for producing aromatic substances using hydrophilic foam gel as a fragrance carrier have been disclosed, for example, in Japanese Patent Publication No. 51-40115.
It is disclosed in the publication number etc. According to this known manufacturing method, unlike the aromatic material manufacturing method that uses agar, gelatin, etc. as a gelling agent,
There are many advantages such as there is no need to heat and cool the aromatic substance in the production process, the production process can be simplified, fragrance deterioration due to heating can be prevented, and a large amount of fragrance can be supported. However, in this known manufacturing method, a large amount of carbon dioxide gas is generated during the manufacturing process, so that the surface of the aromatic body has a poor appearance, and the prevention of fragrance deterioration is still not satisfactory. This type of aromatic body is generally stored in an opaque container for use, but for example, aromatic bodies can be shaped into various characters such as people or animals and placed in a transparent container or support stand (tray). When the aromatic material is intended to be used as a decorative item, products obtained by conventional manufacturing methods cannot be used as such because they have the drawbacks described above.In particular, it is a challenge to eliminate the unsightly appearance of the surface of the aromatic material. I was getting used to it. As a result of extensive research, the present inventors have discovered a manufacturing method that can solve the above problems while maintaining the advantages of the known manufacturing methods, and have arrived at the present invention. The gist of the present invention is an addition polymer diol of 1 to 95% by weight of bisphenol A and alkylene oxide, and an addition polymer polyol or organic Molecular weight 1000-1000, consisting of a mixture of 5-99% by weight polyol, a condensation polymer of polybasic acid and polyhydric alcohol.
10,000 polyol and polyisocyanate (however, the OH/NCO ratio in both reactions is 1/4 to 1/1.5). Mix and disperse to gel and foaming ratio 1.00.
This invention consists in a method for producing a low foaming aromatic material, which is characterized by obtaining an aromatic material with a molecular weight of ~1.10. Further, the present invention will be explained based on embodiments as follows. In order to achieve the object of the present invention, the polyol used in the present invention needs to contain at least 1 to 95% by weight of an addition polymer diol of bisphenol A and alkylene oxide,
In addition, addition polymer polyols of polyhydric alcohols or phenols other than bisphenol A and alkylene oxides, or condensation polymer polyols of organic polybasic acids and polyhydric alcohols 5 to 99
% by weight is used. Examples of polyisocyanates include tolylene diisocyanate, diphenyl metaisocyanate, diphenyl isocyanate, and naphthalene diisocyanate; examples of alkylene oxides include ethylene oxide, propylene oxide, styrene oxide, and butylene oxide; examples of polyhydric alcohols include ethylene glycol and propylene. Glycol, diethylene glycol, brene glycol, etc.; Phenols include hydroquinone, 4,6-di-tert-butylpyrocatechol, 3-hydroxy-2-naphthol, etc.; Organic polybasic acids include oxalic acid, maleic acid, Examples include phthalic anhydride and the like. The emulsion or solubilized perfume aqueous solution used in the present invention is obtained by adding water, other solvents, additives, etc. to natural or synthetic perfumes, or mixtures thereof. Flavoring agents include anise oil, bergamot oil, citronella oil, lemon oil, eucalyptus oil, geranium oil, lavender oil, rose oil, etc.; solvents include;
Lower alcohols such as ethyl alcohol, propyl alcohol, isopropyl alcohol, glycols such as ethylene glycol and propylene glycol; Other additives include surfactants, PH buffers, carbon dioxide gas neutralizers, etc. In the present invention, the OH/NCO ratio in the reaction between polyol and polyisocyanate is 1/4
It is necessary that it is in the range of 1/1.5 to 1/1.5, preferably 1/3 to 1/2. OH/NCO ratio is 1/1.5
If it is above, the gel strength will be weak when it reacts with water to form a gel, and if it is less than 1/4, the amount of free organic isocyanate in the urethane prepolymer will increase, and a larger amount of carbon dioxide will be generated by the reaction with water. This makes it easier to foam, resulting in a highly foamed product. Further, the molecular weight of the polyol used in the present invention needs to be 1000 to 10000, and 1000 to 10000.
If it is less than 10,000, a larger amount of carbon dioxide gas will be generated when reacting with polyisocyanate, and if it is more than 10,000, the viscosity of the urethane prepolymer will become too high, making it inconvenient to handle. In order to produce a low foaming aromatic body in the present invention,
1 to 95% by weight of addition polymer diol of bisphenol A and alkylene oxide, addition polymer polyol of polyhydric alcohol or phenols other than bisphenol A and alkylene oxide, or organic polybasic acid and polyhydric alcohol. After mixing and dispersing 5 to 50% by weight of a hydrophilic urethane prepolymer mixed with 5 to 95% by weight of a condensation polymer polyol, the mixture is immediately poured into a desired mold and allowed to stand at room temperature. put. In this way, an aromatic substance that gels over time is obtained by the following reaction mechanism. The reaction mechanism in this case is as follows. However, ~ indicates a prepolymer skeleton. (1) 〜NCO＋H ₂ O→〜NH ₂ ＋CO ₂ ↑ The gel body obtained by this reaction has a low foaming ratio of 1.00 to 1.10;
This is because the generation of carbon dioxide gas is suppressed during the reaction process of the urethane prepolymer. Although the mechanism by which this is suppressed is not clear, although carbon dioxide gas is generated in the reaction (1) above, the inclusion of a diol skeleton based on bisphenol A inhibits the reactions (2) and (3) above. It is presumed that this is because carbon dioxide gas is more likely to be promoted, and as a result, the generation of carbon dioxide gas is suppressed. If the hydrophilic urethane prepolymer is less than 5% by weight, the gel strength will be weak, and if it is more than 50% by weight, the amount of additives such as perfume will be too small and the desired aromatic effect will not be obtained. Since the present invention relates to the above manufacturing method,
A low-foaming aromatic substance can be obtained by suppressing the generation of carbon dioxide gas as much as possible during the production process of the aromatic substance. Therefore, the appearance of the surface of the aromatic body can be improved. Therefore, the aromatic body obtained by the present invention can be shaped into various characters such as people and animals and housed in a transparent container or placed on a support stand for use as an ornament. Can be done. In addition, by suppressing the generation of carbon dioxide gas, deterioration of the fragrance of the aromatic substance can be relatively reduced. In order to further clarify the present invention and its effects, Examples and Comparative Examples are given below. Example 1 0.4 mol of diol with an average molecular weight of 3000 obtained by addition polymerizing ethylene oxide to bisphenol A,
A mixture of 0.6 mol of a random copolymer triol with an average molecular weight of 3000 obtained by addition polymerizing glycerin at a molar ratio of ethylene oxide/propylene oxide of 80/20, and tolylene diisocyanate (TDI-
80) was reacted with 3 moles at 90°C for 2 hours by a conventional method to obtain a prepolymer (). As a comparative example, a molar ratio of ethylene oxide/propylene oxide to ethylene glycol of 80/
The molar ratio of 0.8 mol of random copolymer diol with an average molecular weight of 3000 added to glycerin and ethylene oxide/propylene oxide
A mixture of 0.2 mol of a random copolymer triol with an average molecular weight of 3000, which was subjected to addition polymerization in a ratio of 80/20, and 3 mol of tolylene diisocyanate (TDI-80) were reacted in a conventional manner at 90°C for 2 hours to form a prepolymer ( ) was obtained. Prepolymers () and () were mixed and stirred with water to form a reaction gel, and the amount of carbon dioxide gas generated was measured at a water temperature of 20°C and a room temperature of 20°C. The results were as shown in the table below.

[Table] As is clear from the above table, it can be seen that the urethane prepolymer of the present invention, by containing bisphenol A, generates an extremely small amount of carbon dioxide gas and has a small expansion ratio compared to the comparative example. Example 2 0.2 mol of diol with an average molecular weight of 3000 obtained by addition polymerizing ethylene oxide to bisphenol A,
0.6 mol of diol with an average molecular weight of 3000, which was added to ethylene glycol at a molar ratio of ethylene oxide/propylene oxide of 80/20, and an average molecular weight of 0.6 mol of diol, which was addition-polymerized to glycerin at a molar ratio of ethylene oxide/propylene oxide of 80/20.
A mixture of 3000 and 0.2 mol of triol was reacted with 2 mol of tolylene diisocyanate (TDI-80) at 90°C for 2 hours in a conventional manner to obtain a urethane prepolymer (). 35g of water and 5g of strawberry flavor of the following combination
and 2.5 g of Nonipol 100 (nonylphenol nonionic surfactant) manufactured by Sanyo Chemical Industries, Ltd.,
A perfume emulsion liquid was prepared. 7.5 g of urethane prepolymer () was added to this, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. After about 2 minutes, the reaction begins and the viscosity increases to about 5
After a few minutes, the reaction was completed, and a low-foaming aromatic body with elasticity and a foaming ratio of 1.01 times was obtained. Ethyl methyl phenyl glycidate with strawberry flavor 25% by weight Ethyl acetate 10 Benzyl acetate 10 Maltol 1 Henicyl alcohol 2 Benzylidene isopropylidene acetone 5 Ethyl butyrate 25 Linalool 2 Vanillin 5 Ethyl lactate 10 mill Butyrate 3 Total 100% by weight This product was a milky white homogeneous gel, and even after being left in a sealed container at 25°C for 1 month, it remained a milky white homogeneous gel with no change in odor. As a comparative example, an emulsion liquid was prepared by mixing 35 g of water, 5 g of the above strawberry flavor, and 2.5 g of Nonipol 100. Average molecular weight of ethylene glycol added to the solution at a molar ratio of ethylene oxide/propylene oxide of 80/20.
2000 diol and 3 moles of tolylene diisocyanate (TDI-80) were mixed at 90°C in a conventional manner.
7.5 g of the urethane prepolymer () obtained by reacting for a period of time was added, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. The reaction started after about 2 minutes, and was completed after about 4 minutes, yielding a highly foamed aromatic material with elasticity and an expansion ratio of 1.60 times. This product was a heterogeneous gel with large air bubbles here and there, and after it was sealed and left at 25°C for one month, the gel changed color slightly and the odor changed slightly. Example 3 A perfume emulsion liquid was prepared by mixing 32.5 g of water, 5 g of cologne perfume of the following formulation, and 2.5 g of Nonipol 100. To this was added 10 g of the urethane prepolymer () obtained in Example 2, and the mixture was strongly stirred for 20 seconds. After confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. The reaction started after about 1.5 minutes, and was completed after about 4 minutes, yielding a low-foaming aromatic material having an elasticity with a foaming ratio of 1.09 times. This is a pale yellow milky white homogeneous gel.
Even after it was sealed and left at 25°C for one month, it remained a pale yellow milky white homogeneous gel with no change in odor. Colon fragrance combined Bergamotsu oil 25 weights weight lemon oil 12 〃 petitigren 6 〃 ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ジ ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク ーク 〃 〃 ーク 〃 〃 Rose absolute 5 Sage 2 Musk ambrette 4 Hedeion 3 Lime oil 10 Total 100% by weight As a comparative example, 32.5 g of water, 5 g of cologne fragrance of the above combination, and 2.5 g of Nonipol 100 were mixed. ,
A perfume emulsion liquid was prepared. Example 1
Add 10g of the urethane prepolymer () obtained in
Stir vigorously for 20 seconds and check that it is homogeneous.
Transferred to a 100ml beaker. The reaction started after about 1.5 minutes, and was completed after about 4 minutes, yielding a highly foamed aromatic material with elasticity and an expansion ratio of 1.46 times. This gel is pale yellow and milky white, and is a slightly heterogeneous gel with large air bubbles here and there. After being sealed and left at 25℃ for one month, the gel changed color slightly and the odor also changed slightly. . As another comparative example, a perfume emulsion liquid was prepared by mixing 32.5 g of water, 5 g of the cologne perfume blended above, and 2.5 g of Nonipol 100. A urethane prepolymer obtained by reacting 1 mole of diol with an average molecular weight of 3000, which is obtained by addition polymerizing ethylene oxide to bisphenol A, and 2.5 moles of tolylene diisocyanate (TDI-80) at 90°C for 2 hours in a conventional manner. 10g of () was added and strongly stirred and dispersed to form a gel, but it was not uniformly dispersed, and in the end, water could not be completely included and the mixture separated into two layers: a gel layer and an aqueous layer. As another comparative example, a perfume emulsion liquid was prepared by mixing 32.5 g of water, 5 g of the cologne perfume blended above, and 2.5 g of Nonipol 100. To this, 0.2 mol of diol with an average molecular weight of 3000, which is obtained by addition polymerizing ethylene oxide to bisphenol A,
0.6 mol of diol with an average molecular weight of 3000, which was added to ethylene glycol at a molar ratio of ethylene oxide/propylene oxide of 80/20, and an average molecular weight of 0.6 mol of diol, which was addition-polymerized to glycerin at a molar ratio of ethylene oxide/propylene oxide of 80/20.
3000 with 0.2 mol of triol and 5 mol of tolylene diisocyanate (TDI-80) were reacted at 90°C for 2 hours using a conventional method. 10 g of urethane prepolymer () was added thereto and stirred vigorously for 20 seconds. After confirming that the mixture was uniform, it was transferred to a 100ml beaker. The reaction started after about 1 minute, and was completed after about 4 minutes, yielding a highly foamable aromatic material with an elastic expansion ratio of 1.90 times. This gel was pale yellow and milky white, and was a heterogeneous gel with large air bubbles here and there. After being sealed and left at 25°C for one month, the gel slightly changed in color and the odor had changed slightly. As another comparative example, a perfume emulsion liquid was prepared by mixing 32.5 g of water, 5 g of the cologne perfume blended above, and 2.5 g of Nonipol 100. To this, 0.005 mol of diol with an average molecular weight of 3000, which is obtained by addition polymerizing ethylene osaside to bisphenol A,
0.8 mol of a diol with an average molecular weight of 3000, which was addition-polymerized to ethylene glycol at a molar ratio of ethylene oxide/propylene oxide of 80/20, and 0.195 mole of a triol, an average molecular weight of 3,000, which was addition-polymerized to glycerin at a molar ratio of ethylene oxide/propylene oxide of 80/20. mol and 3 mol of tolylene diisocyanate (TDI-80) in a conventional manner.
Add 10g of urethane prepolymer () obtained by reacting at 90℃ for 2 hours, stir vigorously for 20 seconds,
After confirming that it was uniform, it was transferred to a 100ml beaker. The reaction started after about 1.5 minutes, and was completed after about 3 minutes, yielding a highly foamed aromatic material with an elastic expansion ratio of 1.40 times. Although this product has a lower foaming effect than the gel obtained using only the urethane prepolymer (1.46 times the foaming ratio of the comparative example of Example 3), the effect is not sufficient and there are some The gel was a slightly non-uniform pale yellow milky white gel with large air bubbles, and after it was sealed and left at 25°C for one month, the gel began to change color and the odor changed slightly. Example 4 32.5 g of water and 5 cologne fragrances used in Example 3
g, 2.5 g of ethylene glycol, and Nonipol.
100 and 2.5 g were mixed to prepare a fragrance emulsion liquid. Add 7.5g of the urethane prepolymer () obtained in Example 2 to the solution, stir vigorously for 20 seconds,
After confirming that it was uniform, it was transferred to a 100ml beaker. The reaction started after 2 minutes, and was completed after 5 minutes, yielding a low-foaming aromatic material with an elastic expansion ratio of 1.09 times. This is a pale yellow milky white homogeneous gel.
Even after it was sealed and left at 25°C for one month, it remained a pale yellow milky white homogeneous gel with no change in odor. As a comparative example, 32.5 g of water, 5 g of the cologne fragrance used in Example 3, and 2.5 g of ethylene glycol.
and 2.5 g of Nonipol 100 were mixed to prepare a fragrance emulsion liquid. Add 7.5g of the urethane prepolymer () obtained in Example 1 to the solution, stir vigorously for 20 seconds, confirm that it is homogeneous, and
Transferred to ml beaker. The reaction started after 2 minutes, and was completed after 5 minutes, yielding a highly foamable aromatic material with an elastic expansion ratio of 1.40 times. This gel was pale yellow and milky white with large bubbles here and there, and after it was sealed and left at 25°C for one month, the gel changed color and odor slightly. As another comparative example, 32.5 g of water, 5 g of the cologne fragrance used in Example 3, 2.5 g of ethylene glycol, and 2.5 g of Nonipol 100 were mixed.
A perfume emulsion liquid was prepared. 7.5 g of the urethane prepolymer () obtained as a comparative example of Example 2 was added to the solution, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. 2
The reaction started after 5 minutes and was completed after 5 minutes, yielding a highly foamed aromatic material with a foaming ratio of 1.60 times. This product was a pale yellow-white, brittle gel with a crumbly castella-like appearance, and was unsuitable as an aromatic agent due to its strength. Example 5 29 g of water, 10 g of the strawberry flavor used in Example 2, and 3.5 g of Nonipol 100 were mixed,
A perfume emulsion liquid was prepared. 7.5 g of the urethane prepolymer () obtained in Example 2 was added to the liquid, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. The reaction started after about 1 minute, and was completed after about 3 minutes, yielding a low-foaming aromatic material with an elastic expansion ratio of 1.05 times. This product was a milky white homogeneous gel, and when this aromatic substance was taken out of the beaker and left in the toilet, the fragrance lasted for approximately 50 days. The shape at that time was cylindrical, similar to the original shape. Example 6 34.97 g of water, 5 g of the cologne fragrance used in Example 3, 2.5 g of Nonipol 100, and 0.03 g of monoethanolamine were mixed to prepare a fragrance emulsion liquid. 7.5 g of the urethane prepolymer () obtained in Example 2 was added to the liquid, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker. The reaction started after about 1.5 minutes, and was completed after about 4 minutes, yielding a low-foaming aromatic material with a foaming ratio of 1.02 times. This is a pale yellow, milky white, homogeneous gel.
Even after it was sealed and left at 25°C for one month, it remained a pale yellow milky white homogeneous gel with no change in odor. Example 7 32.47 g of water, 5 g of the strawberry flavor used in Example 2, 2.5 g of ethylene glycol, 2.5 g of Nonipol 100, and monoethanolamine
A fragrance emulsion liquid was prepared by mixing 0.03g of the above ingredients. 7.5 g of the urethane prepolymer () obtained in Example 2 was added to the liquid, stirred strongly for 20 seconds, and after confirming that the mixture was homogeneous, the mixture was transferred to a 100 ml beaker.
The reaction started after about 1.5 minutes, and was completed after about 4 minutes.
A low foaming aromatic material having elasticity with a foaming ratio of 1.03 times was obtained. This is a milky white homogeneous gel, −15
No syneresis was observed when a cycle of freezing for 16 hours at ℃ and thawing at room temperature of 20℃ was repeated three times.

Claims (1)

[Claims] 1 Addition polymer diol of bisphenol A and alkylene oxide 1 to 95% by weight, polyhydric alcohol or addition polymer polyol of phenols other than bisphenol A and alkylene oxide, or organic polybasic acid and polyhydric alcohol A polyol with a molecular weight of 1,000 to 10,000, which is a mixture of 5 to 99% by weight of a condensation polymer polyol, is reacted with a polyisocyanate (however, the OH/NCO ratio in both reactions is 1/4 to 1/1.5). 5 to 50% by weight of hydrophilic urethane prepolymer obtained by
A method for producing a low-foaming aromatic material, which comprises mixing and dispersing the following in a perfume emulsion liquid and gelling the same to obtain an aromatic material with a foaming ratio of 1.00 to 1.10.