JP5859851B2 - Silicate ester composition - Google Patents

Description

  The present invention relates to a silicate ester composition capable of stably releasing a functional substance such as a fragrance over a long period of time in an actual use mode.

2. Description of the Related Art In recent years, various considerations have been made on fiber product treatment compositions such as garment detergents and softeners that use persistent fragrances and sustainability-imparting ingredients because of increased awareness of the scent of textiles.
As a technique for imparting a durable scent to clothing, Patent Document 1 contains a specific silicate ester compound and a fatty alkyl quaternary ammonium compound, and imparts a long-lasting fragrance to the knitted fabric. Conditioner compositions are disclosed.
Patent Document 2 discloses a detergent composition containing a specific silicate compound and containing a fragrance imparting component that imparts a long-lasting fragrance to the knitted fabric.
In these technologies, a hydrolyzate of silicate ester is used as a perfume ingredient, and the silicate ester adhering to the fiber product is gradually hydrolyzed by moisture in the air, etc., thereby providing a durable scent. However, there is a problem that the effect of the silicate ester is not maintained because the decomposition of the silicate ester proceeds in the water-based product such as the cleaning agent for clothes and the softening finish.

A technique has also been proposed in which hydrolysis of a silicate ester in an aqueous product is suppressed and various functional substances such as a fragrance and an antibacterial agent are stably and gradually released over a long period of time in an actual usage mode.
For example, Patent Document 3 discloses a technique in which two specific types of functional substances to be introduced into a silicate compound are used in combination from the viewpoint of the LogP value (1-octanol / water partition coefficient).
Patent Document 4 discloses a technique using a silicate ester compound in which a hydrocarbon group having a specific chain length is bonded to a silicon atom.
Furthermore, in Patent Document 5, studies are made on the sustained release rate of various functional substances such as fragrances, flavors and antibacterial agents from silicate compounds.

JP-A-54-59498 Japanese Patent Laid-Open No. 54-93006 JP 2009-242798 A JP 2009-197055 A International Publication No. 01/79212

In Patent Document 3, a sufficient effect is realized when a functional compound having an alcoholic hydroxyl group is used as a functional substance to be released slowly, but a functional compound having a phenolic hydroxyl group having a higher acidity is used. In such a case, the suppression of decomposition in the aqueous product is not sufficiently realized. In particular, when phenol (hydroxybenzaldehydes such as vanillin and salicylic acid derivatives, hereinafter also referred to as “functional phenols”) in which a carbonyl group is directly bonded to the benzene ring is used, hydrolysis in water-based products is remarkable. It occurs, and the storage stability in the product is poor, and the sustained release effect is not fully expressed in the actual use mode.
Even when Patent Documents 4 and 5 are viewed, there is no particular study on the hydrolysis problem in the aqueous product that occurs specifically in such a functional phenol, and the decomposition and release of the functional phenol in the product is effective. There is no suggestion of a means that can be suppressed.

  An object of the present invention is to provide a silicate ester composition capable of stably and slowly releasing phenol having a carbonyl group directly bonded to a benzene ring, which is a functional substance such as a fragrance, over a long period of time in an actual usage mode. .

The inventors of the present invention provide a composition containing a silicate having a phenoxy group in which a carbonyl group is directly bonded to a benzene ring (hereinafter, also referred to as “functional phenoxy group”) and an alkoxy group derived from a tertiary alcohol. In an actual use mode, the present inventors have found that the functional phenol derived from the functional phenoxy group can be stably and stably released over a long period of time.
That is, the present invention provides the following [1] to [5].
[1] A silicate ester composition containing a silicon compound having a phenoxy group, wherein 70% by mass or more of the silicon compound is a silicate ester represented by the following formula (1) .
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to the benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, and two R ¹ O and R ² O are They may be the same or different.)
[2] A fragrance precursor composition that releases the R ¹ O contained in the silicate composition by hydrolysis.
[3] A fiber treatment agent that releases the R ¹ O contained in the silicate composition by hydrolysis.
[4] A method for producing a silicate composition having the following steps (A) and (B).
Step (A): Step of obtaining an alkoxysilane represented by the following formula (2) by reacting tetrahalogenated silane (SiX ₄ ) and tertiary alcohol (R ² OH) in the presence of a basic substance. (B): A step of obtaining a silicate ester represented by the following formula (1) by reacting the alkoxysilane obtained in the step (A) with a phenol having a carbonyl group directly bonded to the benzene ring.
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(R ² O) ₂ SiX ₂ (2)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to the benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, X represents a halogen atom, and two R ¹ O and R ² O may be the same or different.
[5] A fragrance precursor containing the silicate ester composition obtained by the above method.

  According to the present invention, it is possible to provide a silicate ester composition capable of stably and slowly releasing phenol having a carbonyl group directly bonded to a benzene ring, which is a functional substance such as a fragrance, over a long period of time in an actual usage mode. .

[Silicate ester composition]
The silicate ester composition of the present invention is a silicate ester composition containing a silicon compound having a phenoxy group, wherein 70% by mass or more of the silicon compound is represented by the following formula (1) It is a silicate ester composition.
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to the benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, and two R ¹ O and R ² O are They may be the same or different.)

The silicic acid ester composition of the present invention can be stably blended in an aqueous product and has good storage stability. In an actual use mode, a phenol (hereinafter referred to as a carbonyl group) directly bonded to a benzene ring that is a functional substance such as a fragrance. The reason why it can be stably released over a long period of time is not clear, but is considered as follows.
That is, in the formula (1), R ¹ O has a carbonyl group directly bonded to the benzene ring, so that the acidity of the phenolic hydroxyl group is greatly increased, so that it is easily hydrolyzed. However, since R ² O has a low electron withdrawing property and low acidity, the stability of the phenoxy group bonded to the silicon atom is appropriately increased, and the structure around the silicon atom is fixed by the bulk of R ² O, It is considered that the storage stability of the silicate ester is enhanced.

Further, since the insoluble or sparingly soluble themselves in water silicate ester compositions of the present invention, is believed to be present in water in an emulsion or micellar, in use, amenable to water R ¹ O is water It is considered that moderate and long-term sustained release performance is expressed by being gradually hydrolyzed upon contact with.
In the present invention, the “carbonyl group directly bonded to the benzene ring” refers to a carbonyl group bonded directly to the carbon atom constituting the benzene ring without any other atom.
“Slow release” means that hydrolysis proceeds gradually and functional phenol is released over a long period of time.
Hereinafter, each component and process used in the present invention will be described.

<Silicate ester>
The silicate ester used in the present invention is a compound represented by the following formula (1).
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to the benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, and two R ¹ O and R ² O are They may be the same or different.)

R ¹ O in the formula (1) represents a phenoxy group obtained by removing a hydrogen atom from a hydroxy group of a phenol (functional phenol) in which a carbonyl group is directly bonded to a benzene ring which is a functional substance such as a fragrance.
As the functional phenol, hydroxybenzaldehydes and salicylic acids are preferable, and among them, hydroxybenzaldehydes are more preferable from the viewpoint of the effect as a fragrance and the sustained release performance of the silicate ester composition.
As the hydroxybenzaldehyde, vanillin and ethyl vanillin are preferable from the viewpoint of the fragrance as a fragrance and the sustained release performance of the silicate composition.
As salicylic acid, a salicylic acid ester is preferable, and ethyl salicylate is more preferable.
The functional phenol is preferably a fragrance, more preferably a fragrance (cosmetic fragrance) or a flavor (food fragrance), and even more preferably a fragrance.
Preferable specific examples of a fragrance among R ¹ O are preferably vanillin, ethyl vanillin, and ethyl salicylate, and more preferably vanillin from the viewpoints of efficacy as a fragrance and the sustained release performance of a silicate ester composition.

R ² O in the formula (1) is an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol. The number of carbon atoms of the tertiary alcohol is preferably 4 to 15, more preferably 4 to 12, and more preferably 4 to 10 from the viewpoint of maintaining the storage stability of the silicate ester composition and improving the sustained release performance. 8 to 10 are more preferable.
The tertiary alcohol is preferably a fragrance, more preferably a fragrance (cosmetic fragrance) or a flavor (food fragrance), and even more preferably a fragrance.

Specific examples of fragrances among tertiary alcohols include myrcenols, terpineols, linalools, mugors and the like.
As myrcenols, myrcenol (2-methyl-6-methylene-7-octen-2-ol), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), tetrahydromyrcenol (2 , 6-dimethyl-2-octanol) and the like.
Examples of terpineols include terpineol (1-methyl-4-isopropyl-1-cyclohexen-8-ol), dihydroterpineol (1-methyl-4-isopropylcyclohexane-8-ol), and the like.
Examples of linalools include linalool (3,7-dimethyl-1,6-octadien-3-ol), dihydrolinalool (3,7-dimethyl-6-octen-3-ol), tetrahydrolinalool (3,7-dimethyl). -3-octanol), ethyl linalool (3,7-dimethyl-1,6-nonadien-3-ol), geranyl linalool (1,6,10,14-hexadecatetraen-3-ol) and the like. .
Examples of mugors include mugoles (2,6-dimethyl-3,5-octadien-2-ol and 3,7-dimethyl-4,6-octadien-3-ol), tetrahydromugor (2,6-dimethyl- 2-octanol and 3,7-dimethyl-3-octanol) and the like.

Specific examples of other fragrances include 2,6-dimethyl-2-heptanol, 2-methyl-3-buten-2-ol, ambrinol (2,5,5-trimethyl-octahydro-2-naphthol), osmenol (2,6-dimethyl-5,7-octadien-2-ol), 3,6-dimethyl-3-octanol, 4-tanol (4-methyl-1-isopropylbicyclo [3.1.0] hexane-4 -Ol), nerolidol (3,7,11-trimethyl-1,6,10-dodecatrien-3-ol), α-bisabolol (3-cyclohexene-1-methanol), patchouli alcohol (1,6-methano) Naphthalene-1 (2H) -ol), isophytol (3,7,11,15-tetramethyl-1-hexadecene-3-ol), sclareo (1-naphthalenepropanol), α, α-dimethylphenylethyl alcohol, p-methyldimethylbenzylcarbinol, dimethylphenylethylcarbinol, 3-methyl-1-phenyl-3-pentanol, florol (2-isobutyl- 4-methyltetrahydro-2H-pyran-4-ol) and the like.
Among these fragrances, from the viewpoint of matching the fragrance, myrcenols and linalools are preferable, and dihydromyrcenol and tetrahydrolinalool having a floral fragrance are more preferable.
When a tertiary alcohol other than a fragrance is used, a high odor threshold is preferable from the viewpoint of not harming the fragrance, and a low molecular weight is preferable from the viewpoint of molecular efficiency. The specific molecular weight is preferably 74 to 200, more preferably 74 to 180, and still more preferably 74 to 150. As such a tertiary alcohol, tert-butyl alcohol is preferred.

As described above, the silicate ester composition of the present invention contains a silicon compound having a phenoxy group, and 70% by mass or more of the silicon compound is a silicate ester represented by the formula (1). It is characterized by being.
The content of the silicon compound in the silicate composition is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass from the viewpoint of efficiently obtaining the effect of the silicate ester. Is more preferable.

[Method for producing silicate ester composition]
The method for producing a silicate composition of the present invention includes the following steps (A) and (B).
Step (A): Step of obtaining an alkoxysilane represented by the following formula (2) by reacting tetrahalogenated silane (SiX ₄ ) and tertiary alcohol (R ² OH) in the presence of a basic substance. (B): A step of obtaining a silicate ester represented by the following formula (1) by reacting the alkoxysilane obtained in the step (A) with a phenol having a carbonyl group directly bonded to the benzene ring.
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(R ² O) ₂ SiX ₂ (2)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to the benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, X represents a halogen atom, and two R ¹ O and R ² O may be the same or different.

(Process (A))
Step (A) is a step of obtaining (R ² O) ₂ SiX ₂ by reacting tetrahalogenated silane (SiX ₄ ) with tertiary alcohol (R ² OH) in the presence of a basic substance.
Examples of the halogen of the tetrahalogenated silane used in this step (A) include chlorine, bromine and iodine. The tetrahalogenated silane may have a plurality of types of halogen in one molecule, but preferably has only one type of halogen in one molecule. Specific examples include tetrachlorosilane (SiCl ₄ ) and tetrabromosilane (SiBr ₄ ), and tetrachlorosilane is preferred from the viewpoint of manufacturing cost and availability.

As the tertiary alcohol, the above-mentioned tertiary alcohol is preferable. From the viewpoint of maintaining the storage stability of the silicate ester composition and improving the sustained release performance, the tertiary alcohol preferably has 4 to 15 carbon atoms. 4 to 12 is more preferable, 4 to 10 is more preferable, and 8 to 10 is still more preferable.
The tertiary alcohol is preferably a fragrance, more preferably a fragrance or flavor, and even more preferably a fragrance.
Among the fragrances, myrcenols and linalools are preferable, and dihydromyrcenol and tetrahydrolinalol having a floral fragrance are preferable from the viewpoint of matching the fragrance.
As a specific example of the tertiary alcohol other than the fragrance, tert-butyl alcohol having a high odor threshold and a low molecular weight is preferable.

As a basic substance used in the step (A), from the viewpoint of neutralizing the hydrogen halide generated as a by-product and allowing the reaction to proceed rapidly, an amine, an alkali metal salt of an alcohol, an alkali metal hydroxide, Alkali metals are preferred. Furthermore, from the viewpoint of reducing side reactions such as a dimerization reaction while allowing the reaction to proceed rapidly, amine and alcohol alkali metal salts are more preferred, and amines are more preferred.
As the amine, a cyclic amine is preferable, and from the same viewpoint as described above, a heterocyclic amine having a nitrogen atom in the ring is more preferable, and imidazole and pyridine are further preferable.
Examples of the alkali metal salt of alcohol include sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

The reaction in the step (A) is preferably performed in an aprotic organic solvent from the viewpoint of suppressing side reactions while keeping the reaction system uniform. As the aprotic organic solvent to be used, ketone and ether are preferable from the same viewpoint as described above, and ketone is more preferable.
As a ketone, a C4-C6 ketone is preferable, a C4-ketone is more preferable, and 2-butanone is still more preferable.
The ether is preferably an ether having 4 to 6 carbon atoms, more preferably an ether having 4 carbon atoms, and specific examples thereof include diethyl ether and tetrahydrofuran.

In the reaction in the step (A), the inside of the reaction vessel is preferably replaced with an inert gas such as nitrogen from the viewpoint of preventing side reactions. The raw materials and the like are charged into a reaction vessel substituted with an inert gas. As the order, it is preferable that tetrahalogenated silane is placed in the reaction vessel and then a tertiary alcohol and a basic substance are added. In addition, it is preferable to dissolve them in the aprotic organic solvent described above.
The tertiary alcohol and the basic substance may be added separately, but they are preferably added in a mixed manner from the viewpoint of rapidly proceeding the reaction, and gradually added so that the reaction does not proceed rapidly.

The tertiary alcohol is preferably 2 equivalents or more with respect to the tetrahalogenated silane from the viewpoint of suppressing by-products.
Moreover, it is preferable from a viewpoint of the efficiency of reaction that the basic substance in a process (A) is 1-4 equivalent with respect to tertiary alcohol. Furthermore, the aprotic organic solvent in the step (A) is preferably 1 to 30 times by mass with respect to the tetrahalogenated silane.
The reaction temperature is preferably -10 to 40 ° C. Specifically, in order to suppress a rapid reaction at the time of preparation, the initial stage of the reaction is preferably performed at −10 to 10 ° C., and then the reaction is performed by raising the temperature to 20 to 40 ° C.
What is obtained by the step (A) is a mixture of alkoxysilanes, but (R ² O) ₂ SiX ₂ can be obtained as a main product. The reason why a disubstituted product of R ² O can be obtained as a main product is considered to be due to the bulkiness of R ² O derived from tertiary alcohol. According to the production method of the present invention, a large amount of disubstituted products can be obtained in this way, and thus the silicate represented by the formula (1) having excellent stability and sustained release performance can be obtained with high purity.

(Process (B))
In the step (B), the (R ² O) ₂ SiX ₂ obtained in the step (A) is further reacted with a phenol (functional phenol) in which a carbonyl group is directly bonded to the benzene ring. This is a step of obtaining a silicate ester composition containing the silicate ester represented by 1).
Examples of the functional phenol that can be used in the step (B) include those described above, and hydroxybenzaldehydes and salicylic acids are preferable. Among them, the efficacy as a fragrance and the sustained release performance of the silicate ester composition. From the viewpoint, hydroxybenzaldehydes are more preferable.
As hydroxybenzaldehyde, vanillin and ethyl vanillin are preferable from the viewpoint of the fragrance as a fragrance and the sustained release performance of the silicate composition.

In the step (B), it is preferable to use a basic substance, and an amine is more preferable from the viewpoint of reducing side reactions such as a dimerization reaction while allowing the reaction to proceed rapidly. As the amine, a cyclic amine is preferable, and from the same viewpoint as described above, a heterocyclic amine having a nitrogen atom in the ring is more preferable, and imidazole and pyridine are further preferable.
The reaction in the step (B) is preferably performed in an aprotic organic solvent from the viewpoint of suppressing side reactions while keeping the reaction system uniform. The aprotic organic solvent used is preferably a ketone from the same viewpoint as described above. The ketone is preferably a ketone having 4 to 6 carbon atoms, more preferably a ketone having 4 carbon atoms, and still more preferably 2-butanone.

In this step (B), it is preferable to add functional phenol to the reaction vessel holding (R ² O) ₂ SiX ₂ obtained in step (A), and to add a basic substance as well. Is preferred. Moreover, it is preferable to dissolve these in an aprotic organic solvent.
The functional phenol and the basic substance may be added separately, but it is preferable to add both in a mixed manner from the viewpoint of promptly proceeding the reaction, and gradually adding so that the reaction does not proceed rapidly. Is preferred.

The functional phenol is preferably used in an amount of 1 to 3 equivalents, more preferably 2 to 3 equivalents, based on the tetrahalogenated silane used in the step (A) from the viewpoint of stability.
Moreover, it is preferable that a basic substance is 1-4 equivalent with respect to functional phenol.
The aprotic organic solvent is preferably 1 to 30 times in mass with respect to the tetrahalogenated silane used in step (A).
The reaction temperature is preferably -10 to 60 ° C. Specifically, in order to suppress a rapid reaction at the time of preparation, the initial stage of the reaction is performed at −10 to 10 ° C., and then the temperature is increased to 20 to 50 ° C., more preferably 20 to 40 ° C. Preferably it is done.

  Although what is obtained by a process (B) becomes a mixture, the silicate ester composition which uses the silicate ester represented by Formula (1) which is excellent in storage stability and sustained release performance as a main product can be obtained. . The silicate ester composition thus obtained can release the functional phenol stably and stably over a long period of time, and has the same effect on the fragrance precursor containing the silicate ester composition and the fiber treatment agent. It is considered that can be given.

In the manufacturing method of the silicate ester composition of the present invention, after the step (B), there is a step (C) for removing the salt by contacting with water and a step (D) for removing the aprotic organic solvent. It is preferable.
(Process (C))
Step (C) is a step of removing salt by bringing water into contact with the reaction mixture containing the silicate composition obtained in step (B).
The salt removed in the step (C) is a salt composed of the basic substance generated in the steps (A) and (B) and a halogen derived from silane. In the step (C), when water and the reaction mixture are brought into contact with each other, it is preferable to add an alcohol having 1 to 4 carbon atoms such as ethanol to the water. From the viewpoint of suppressing pH fluctuation, sodium bicarbonate It is preferable to contact the reaction mixture with an aqueous solution in which a salt of a weak acid such as, etc. is dissolved.
The components that are insoluble or hardly soluble in water such as the washed silicate composition and the aprotic organic solvent are preferably extracted with a nonpolar organic solvent such as hexane.

(Process (D))
Step (D) is a step of removing the solvent from the mixture of components insoluble or hardly soluble in water obtained in step (C). In the step (D), the aprotic organic solvent and the nonpolar organic solvent used in the step (C) are removed by concentration under reduced pressure. Thereby, a highly pure silicate composition can be obtained.
In addition, in order to suppress that the density | concentration of the water | moisture content which remained before performing a process (D) raises and a hydrolysis arises, it is preferable to dehydrate previously with desiccants, such as sodium sulfate or magnesium sulfate.

[Perfume precursor composition]
Since the fragrance | flavor precursor composition of this invention contains the silicate ester composition of this invention, the fragrance | flavor which is a functional phenol is sustainedly released by hydrolysis.
The fragrance precursor composition of the present invention may contain an oil agent, a surfactant, and an organic solvent in addition to the silicate ester composition.
Since the fragrance precursor composition of the present invention can be blended in various products, the functional phenol can be stably released over a long period of time, and the fragrance derived from the functional phenol can be generated over a long period of time. .
Examples of products that can be blended with the fragrance precursor composition of the present invention include oil-based deodorant fragrance compositions, powder detergents, bar soaps, bathing agents, sanitary products such as diapers, and aerosol type deodorant compositions. Non-aqueous products such as products.
Furthermore, since the perfume precursor composition of the present invention is excellent in storage stability in an aqueous solution system, it includes perfumes, colons, water-based deodorant fragrances, various cosmetics such as dish detergent, liquid soap and lotion, It can be used for hair products such as shampoos, rinses, conditioners, styling agents, and liquid baths.
When a fragrance composition is constituted using the silicate ester composition of the present invention, the content of the silicate ester represented by the formula (1) in the fragrance composition is preferably 0.001 to 90 mass%. 0.01 to 10% by mass is more preferable.
Moreover, when comprising a deodorant composition, 0.0001-10 mass% is preferable, and, as for content of the silicate ester represented by Formula (1) in a deodorant composition, 0.001- 5 mass% is more preferable.
In addition, although the fragrance | flavor precursor composition of this invention contains a silicate ester composition, it is preferable that this silicate ester composition is manufactured with the manufacturing method of the above-mentioned this invention.

[Fiber treatment agent]
Since the fiber treatment agent of the present invention contains the silicate ester composition of the present invention, it can suppress rapid hydrolysis of the functional substance even when blended in an aqueous product. Functional phenol can be stably released over a long period of time, and various functions derived from the functional substance can be continuously expressed.
By using such a silicate composition of the present invention, it is possible to suppress hydrolysis in the product as much as possible even if it is a silicate ester to which a functional phenol having extremely poor stability in an aqueous product is bound. In an actual use mode, a favorable scent can be emitted and an excellent effect can be continuously expressed. In particular, it is useful in the application of fiber treatment agents such as clothing detergents and softeners.

  In the fiber treatment agent, the content of the silicate ester represented by the formula (1) is not particularly limited, and can be appropriately changed depending on the application. When a fiber treatment agent composition such as a detergent composition for clothes and a softener finishing composition is constituted using the silicate ester composition of the present invention, it is represented by the formula (1) in the fiber treatment agent composition. The content of the silicate ester is preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.

<Manufacture of silicate ester composition>
Example 1 (Production of Si (OVan) ₂ (OTHLin) ₂ )
Si (OVan) in which 4 chlorine atoms of tetrachlorosilane were replaced with 2 molecules of vanillin (HOVan) and 2 molecules of tetrahydrolinalol (3,7-dimethyl-3-octanol) (HOTHLin) according to the following procedure ₂ (OTLin) ₂ was produced.
A 300 ml four-necked flask equipped with a stirring blade and a dropping funnel was filled with nitrogen, and 30 ml of 2-butanone and 6.0 ml (52.5 mmol) of tetrachlorosilane were added thereto. On the other hand, 7.86 g (115 mmol) of imidazole and 16.6 g (115 mmol) of 3,7-dimethyl-3-octanol (HOTHLin) were mixed with 20 ml of 2-butanone to prepare a uniform solution and put into a dropping funnel, 300 ml The dropwise addition was performed over 40 minutes while the four-necked flask was immersed in an ice bath. The dropping funnel was washed with 5 ml of 2-butanone, added dropwise, and further stirred at 25 ° C. for 120 minutes. Next, 7.86 g (115 mmol) of imidazole and 16.0 g (115 mmol) of vanillin (HOVan) are mixed with 20 ml of 2-butanone to prepare a uniform solution, put into a dropping funnel, and the four-necked flask in an ice bath. It was dripped over 20 minutes, immersing. The dropping funnel was washed with 5 ml of 2-butanone, which was added dropwise, and further stirred at 25 ° C. for 90 minutes and at 40 ° C. for 30 minutes, and then returned to 25 ° C.
After 5 ml of ethanol and then 180 g of 5% aqueous sodium hydrogen carbonate solution were added to the four-necked flask, extraction was performed with 100 ml of hexane. This extraction operation was performed three times in total. The extract was dehydrated with sodium sulfate and concentrated under reduced pressure to obtain 35.9 g of a yellow oil.
When component analysis was performed by gas chromatography, bis (3,7-dimethyloctane-3-yl) bis (4-formyl-2-methoxyphenyl) orthosilicate was 46.3% in area ratio in this oil. Was included. As other components, 35.8% vanillin, 4.8% bis (3,7-dimethyloctane-3-yl) ethyl (4-formyl-2-methoxyphenyl) orthosilicate (vanillin monosubstituted), 3,7-dimethyl-3-octanol was included as an area ratio of 1.8%.
That is, the mass of bis (3,7-dimethyloctane-3-yl) bis (4-formyl-2-methoxyphenyl) orthosilicate in the silicon compound having a phenoxy group is 90.6%.

Example 2 (Production of Si (OVan) ₂ (ODHMir) ₂ )
According to the following procedure, Si (OVan) ₂ (ODHMir) _{2 in} which four chlorine atoms of tetrachlorosilane were replaced with two molecules of vanillin (HOVan) and two molecules of dihydromyrsenol (HODHMir) was produced.
A 300 ml four-necked flask equipped with a stirring blade and a dropping funnel was filled with nitrogen, and 30 ml of 2-butanone and 6.0 ml (52.5 mmol) of tetrachlorosilane were added thereto. On the other hand, 7.86 g (115 mmol) of imidazole and 16.4 g (115 mmol) of dihydromyrsenol (HODHMir) were mixed with 10 ml of 2-butanone to prepare a uniform solution, put into a dropping funnel, and a 300 ml four-necked flask was added. The solution was dropped over 10 minutes while immersed in an ice bath. The dropping funnel was washed with 5 ml of 2-butanone, added dropwise, and further stirred at 25 ° C. for 240 minutes. Next, 7.86 g (115 mmol) of imidazole and 16.0 g (115 mmol) of vanillin (HOVan) are mixed with 20 ml of 2-butanone to prepare a uniform solution, put into a dropping funnel, and the four-necked flask in an ice bath. It was dripped over 10 minutes, immersing. The dropping funnel was washed with 5 ml of 2-butanone, which was added dropwise, and further stirred at 25 ° C. for 120 minutes and at 50 ° C. for 30 minutes, and then returned to 25 ° C.
After 5 ml of ethanol and then 180 g of 5% aqueous sodium hydrogen carbonate solution were added to the four-necked flask, extraction was performed with 30 ml of ethyl acetate. This extraction operation was performed three times in total. The extract was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain 38.3 g of a yellow oil.
When component analysis was performed by gas chromatography, this oil contained bis (2,6-dimethyloct-7-en-2-yl) bis (4-formyl-2-methoxyphenyl) orthosilicate in an area ratio of 20 It was included at 1%. Other components include 33.4% vanillin, 21.1% dihydromyrcenol, bis (2,6-dimethyloct-7-en-2-yl) ethyl (4-formyl-2-methoxyphenyl) Orthosilicate was included as an area ratio of 2.8%.
That is, the mass of bis (2,6-dimethyloct-7-en-2-yl) bis (4-formyl-2-methoxyphenyl) orthosilicate in the silicon compound having a phenoxy group is 87.8%.

Comparative Example 1 (Production of Si (OVan) ₄ )
Tetrakis (4-formyl-2-methoxyphenyl) orthosilicate (Si (OVan) ₄ ) was obtained according to the procedure described in Example 24 of WO 01/79212.

Comparative Example 2 (Production of Si (OVan) ₂ (OTHLin) (OEt))
Si (OVan) ₂ (ODHMir) (OEt) in which two chlorines of tetrachlorosilane were replaced with two molecules of vanillin (HOVan), one molecule of tetrahydrolinalol (HOTHLin) and one molecule of ethanol according to the following procedure: Manufactured.
A 300 ml four-necked flask equipped with a stirring blade and a dropping funnel was filled with nitrogen, and 30 ml of tetrahydrofuran and 11.9 g (70 mmol) of tetrachlorosilane were added thereto. On the other hand, 6.1 g (77 mmol) of pyridine and 11.1 g (70 mmol) of tetrahydrolinalol (HOTHLin) were mixed with 15 ml of tetrahydrofuran to prepare a uniform solution, put into a dropping funnel, and while immersing the flask in an ice bath, It was added dropwise over 10 minutes. After stirring at 25 ° C. for 1 hour, 12.2 g (154 mmol) of pyridine and 21.3 g (140 mmol) of vanillin (HOVan) were mixed with 10 ml of tetrahydrofuran to prepare a homogeneous solution, put into a dropping funnel, and the flask was The solution was added dropwise over 10 minutes while immersed in an ice bath. After stirring for 3 hours, 3.2 g of ethanol (HOEt) was added and further stirred for 30 minutes.
The precipitate was removed by filtration and concentrated under reduced pressure to obtain (3,7-dimethyloctane-3-yl) ethylbis (4-formyl-2-methoxyphenyl) orthosilicate as a purple liquid.

Comparative Example 3 (Production of Si (OVan) (OTHGer) ₃ )
According to the following procedure, Si (OVan) (OTHGer) _{3 in} which the chlorine of tetrachlorosilane was replaced with one molecule of vanillin (HOVan) and three molecules of 2,6-dimethyl-3-octanol (HOTHGer) was prepared.
A 300 ml four-necked flask equipped with a stirring blade and a dropping funnel was filled with nitrogen, and 30 ml of 2-butanone and 6.0 ml (52.5 mmol) of tetrachlorosilane were added thereto. On the other hand, 11.8 g (173 mmol) of imidazole and 24.9 g (158 mmol) of 2,6-dimethyl-3-octanol were mixed with 20 ml of 2-butanone to prepare a uniform solution and put into a dropping funnel. While dropping the flask in an ice bath, dropwise addition was performed over 35 minutes. The dropping funnel was washed with 5 ml of 2-butanone, added dropwise, and further stirred at 25 ° C. for 60 minutes. Next, 3.93 g (58 mmol) of imidazole and 8.0 g (53 mmol) of vanillin were mixed with 20 ml of 2-butanone to prepare a uniform solution, put into a dropping funnel, and while immersing the four-necked flask in an ice bath, It was added dropwise over 10 minutes. The dropping funnel was washed with 5 ml of 2-butanone, added dropwise, and further stirred at 25 ° C. for 180 minutes.
10 ml of ethanol and then 180 g of 5% aqueous sodium hydrogen carbonate solution were added to the four-necked flask, followed by extraction with 100 ml of hexane. This extraction operation was performed three times in total. The extract was dehydrated with sodium sulfate and concentrated under reduced pressure to obtain 33.9 g of tris (3,7-dimethyloctyl) (4-formyl-2-methoxyphenyl) orthosilicate as a cloudy yellow oil.

<Manufacture of fiber treatment agent>
Silicate ester compositions produced in Examples 1 and 2 and Comparative Examples 1 to 3 and vanillin as Comparative Example 4, and an unscented liquid softening finish A having the composition shown in Table 1 prepared according to a conventional method, Each of the following methods was mixed to prepare a softener composition.
That is, 50 mL of the silicic acid ester compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 and vanillin to 0.5% by mass with respect to the unscented liquid softening finish A, respectively. The soft finish composition which is a fiber treatment agent was prepared by putting in a screw tube (Marume No. 7), cooling to 50 ° C. and then cooling.

<Scent sustainability evaluation>
In advance, using a commercially available weak alkaline detergent (trade name “Attack” manufactured by Kao Corporation), 24 cotton towels were repeatedly washed 5 times with Hitachi's fully automatic washing machine, model number “NW-6CY”. The excess drug was removed by drying (detergent concentration: 0.0667% by mass, use of 47 L of tap water, water temperature of 20 ° C., washing for 10 minutes, twice for rinsing).

  National Electric bucket, model number “N-BK2-A”, 5 L of tap water is poured into it, and softener finish composition (stored at 40 ° C. for 2 weeks after preparation) is 10 g / clothing 1.0 kg. The two cotton towels that were dissolved (preparation of the treatment bath) and pretreated by the above-described method after 1 minute were immersed for 5 minutes. Thereafter, the two cotton towels were transferred to a National electric washing machine, model number “NA-35”, and dehydrated for 3 minutes. After the dehydration treatment, it was left in a room at about 20 ° C. to dry overnight, and the dried towel was left in a room at about 20 ° C. for 1 week (suspended drying).

Immediately after the dehydration treatment, the towels after 1 day and 7 days were subjected to sensory evaluation on the fragrance intensity of vanillin by 10 professional panelists based on the following criteria to obtain an average value. In the evaluation after 1 day and after 7 days, sensory evaluation was performed on both the towel in a dry state and the towel after wet treatment (1 minute after wet) by the following method. The results are shown in Table 2.
<Wetting treatment>
Filled with distilled water into the trigger container (a polyethylene spray container that can spray the solution in the container in a mist) used in Reshesh (trade name, product of Kao Corporation) Wet treatment was carried out by pushing 1 cm (water weight 0.4 g) about 30 cm away from the towel. The evaluation was performed after 1 minute from wetting with distilled water, and then sensory evaluation was performed by 10 professional panelists based on the following criteria to obtain an average value.

Evaluation criteria 5: Very strong smell 4: Very strong smell 3: Strong smell 2: Smell (cognitive threshold)
1: Smell slightly (detection threshold)
0: Does not smell

  As is apparent from Table 2, the silicate ester composition of the present invention suppresses the rapid decomposition / release of phenol having a carbonyl group directly bonded to the benzene ring even in an aqueous product such as a softening finish. In the actual use mode, the functional phenol can be stably released over a long period of time.

Claims (11)

A silicate ester composition containing a silicon compound having a phenoxy group, wherein 70% by mass or more of the silicon compound is a silicate ester represented by the following formula (1).
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to a benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, and two R ¹ O and R ² O are They may be the same or different.)   The silicate ester composition according to claim 1, wherein the tertiary alcohol has 4 to 15 carbon atoms. The silicate ester composition according to claim 1 or 2, wherein the R ¹ O is a substituent obtained by removing a hydrogen atom from a hydroxy group of a fragrance. The silicate ester composition according to any one of claims 1 to 3, wherein the tertiary alcohol is at least one fragrance selected from myrcenols, terpineols, linalools, and mugors . The silicate composition according to any one of claims 1 to 4, wherein the R ¹ O is a substituent obtained by removing a hydrogen atom from a hydroxy group of vanillin or ethyl vanillin. The fragrance | flavor precursor composition which releases said R < ¹ > O contained in the silicate ester composition in any one of Claims 1-5 by hydrolysis. The fiber processing agent which releases said R < ¹ > O contained in the silicate ester composition in any one of Claims 1-5 by hydrolysis. The manufacturing method of the silicate ester composition which has the following process (A) and (B).
Step (A): Step of obtaining an alkoxysilane represented by the following formula (2) by reacting a tetrahalogenated silane (SiX ₄ ) with a tertiary alcohol (R ² OH) in the presence of a basic substance. (B): A step of obtaining a silicate ester represented by the following formula (1) by reacting the alkoxysilane obtained in the step (A) with a phenol having a carbonyl group directly bonded to the benzene ring.
(R ¹ O) ₂ (R ² O) ₂ Si (1)
(R ² O) ₂ SiX ₂ (2)
(Wherein R ¹ O represents a phenoxy group in which a carbonyl group is directly bonded to a benzene ring, R ² O represents an alkoxy group obtained by removing a hydrogen atom from a tertiary alcohol, X represents a halogen atom, and two R ¹ O and R ² O may be the same or different.   The manufacturing method of the silicate ester composition of Claim 8 which performs reaction of the said process (A) in an aprotic organic solvent.   The method for producing a silicate ester composition according to claim 9, wherein the aprotic organic solvent is a ketone having 4 to 6 carbon atoms.   11. The silicic acid according to claim 9 or 10, comprising a step (C) of removing a salt by bringing the reaction solution into contact with water after the step (B), and a step (D) of removing an aprotic organic solvent. A method for producing an ester composition.