KR20080097772A - Polymer sensitive to ph change, active components delivery composition including the same and the manufacturing method thereof - Google Patents

Abstract

A pH-sensitive polymer soluble in the specific pH is provided to control the pH where polymer is dissolved, by controlling the content of a hydrophobic functional group and a pH-sensitive functional group and to use a delivery composition which emits an active material for the predetermined time, like a dish washer or a cloth washing machine. A pH-sensitive polymer is added with a pH-sensitive functional group of the chemical formula 1 and a hydrophobic functional group of the chemical formula 2 to a polyaspartate derivative compound. In the chemical formula 1, R1 is hydrogen or C1-C6 linear or branched alkyl group; R2 is C2-C10 alkyl group; R3 and R4 are C3-C6 alkyl group. In the chemical formula 2, R1 is hydrogen and C1-C6 linear or branched alkyl group and R5 is C6-C30 linear or branched saturated or unsaturated alkyl group.

Description

pH sensitive polymer, active ingredient delivery composition comprising same, and method for preparing the same {Polymer sensitive to pH change, active components delivery composition including the same and the manufacturing method

FIG. 1 shows N, N-di-normalbutylamino in pH sensitive polymers of Examples 1, 2, 3, and 5 and Comparative Example 1 prepared using a pH sensitive functional group, N, N-di-normalbutylaminopropylamine. It is a graph showing the change in pH sensitivity according to the change in the content of propylamine.

Figure 2 is a graph showing the pH sensitivity change in accordance with the content of octadecylamine in the pH sensitive polymers of Example 3 and Comparative Examples 2 to 4 prepared using a hydrophobic functional group octadecylamine.

Figure 3 is a graph showing the change in solubility according to the pH of the pH sensitive polymer prepared in Example 6.

Figure 4 is a graph showing the pH sensitivity change according to the pH sensitive functional groups in the pH sensitive polymer prepared in Example 3 and Comparative Examples 5 to 6.

Figure 5 is a graph showing the change in solubility according to the pH of the pH sensitive polymer prepared in Example 4.

6 is a graph showing the change in solubility of the flexible component coated with the pH sensitive polymer prepared in Example 3 with time at pH 7.0 and pH 11.0.

The present invention relates to a pH-sensitive polymer that has a change in solubility according to pH and its use, and more particularly, solubility changes in a specific pH range so that the active ingredient can be protected by coating encapsulation at a certain pH and released at a certain pH. A polymer that can be used as an active substance delivery composition and its use.

The effect is often maximized only when certain components are introduced at specific points in the process. For example, the soft or fragrance component is most effectively added to the rinsing process rather than the washing process during washing of clothes or dishes. The general treatment method is to add a softener such as the last rinse process, but this method has a disadvantage in that the flexible component or aroma must be added separately at a certain time. Another method is to control the release of the active ingredient by coating or encapsulating the active ingredient at the beginning, such as during the laundry process, and by controlling the solubility of the protective film as the external environment, such as pH, changes. Such a control method has the advantage that it is possible to control the release of specific components at the desired time while all the ingredients are added at once. In the washing process of clothing or tableware, the biggest difference in the washing process is that the actual washing is performed and the rinsing process in which the flexible or fragrance component is finally attached to the fiber or the dish to give an effect. In the pH of the washing water is 10 to 11, the pH of the rinsing water in the final rinsing process is reduced to 6 to 8.

Korean Patent Application No. 10-1998-0031572 discloses a polymer including a sulfonamide group, which is a functional group exhibiting pH sensitivity. The polymer is insoluble at pH 7 or below, and ionized and dissolved at pH 7 or above. In this case, since it has the opposite characteristics to the behavior in clothes or dishwashing agents, it can be said that a compound containing a cationic group and showing basicity is required to exhibit suitable behavior as a result.

U.S. Patent Publication Nos. 2003/0158072 A1 and 2003/0158344 A1 typically include air containing functional groups having basic properties such as dimethyl aminoethyl methacrylate or dimethyl aminopropyl methacrylate. The coalescence is discussed, and the solubility in water varies according to the pH change in the solution of the laundry detergent and distilled water. However, the copolymer described in the patent is composed of only hydrophobic functional groups and pH sensitive functional groups, so that only materials having hydrophobic or pH sensitive functions as the backbone of the polymer can be selected, thereby freeing the type and addition molar ratio of hydrophobic functional groups and pH sensitive functional groups. There is a limit to control.

It is an object of the present invention to provide a pH sensitive polymer whose solubility varies with pH and a method for producing the same.

It is an object of the present invention to provide a pH sensitive active ingredient delivery composition capable of releasing the active ingredient in the desired pH range by coating or encapsulating the active ingredient using a pH sensitive polymer.

In order to achieve the above object, the present invention provides a pH sensitive polymer compound in which a pH sensitive functional group of Formula 1 and a hydrophobic functional group of Formula 2 are added to a polyaspartate derivative compound having both hydrophilicity and biodegradability.

Formula 1

In the above formula, R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkyl group having 2 to 10 carbon atoms. R ₃ and R ₄ are alkyl groups having 3 to 6 carbon atoms,

Formula 2

Wherein R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₅ is a straight or branched chain saturated or unsaturated alkyl group having 6 to 30 carbon atoms.

The pH sensitive functional group of Chemical Formula 1 has a pKa value of about 9 to 11 and is insoluble at pH 9 or higher, and is a pH sensitive functional group represented by a tertiary amine ionized at pH 9 or lower and dissolved in water, for example, N, N- Di-normalbutylaminopropylamine, N, N-di-normalbutylaminoethylamine, N, N-di-isopropylaminoethylamine, and the like.

Examples of the hydrophobic functional group represented by Formula 2 include linear or branched hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl groups, and the like, and unsaturated alkyl groups include oleyl.

The pH sensitive functional group of Chemical Formula 1 may include 5 to 99 mol%, preferably 25 to 90 mol%, based on the reactable poly (amino acid) derivative. When the binding molar ratio of the pH sensitive functional group is 5 mol% or less, the content of the pH sensitive functional group is so low that the solubility does not decrease even at high pH, and the effect on the water solubility of the entire polymer is reduced.

The hydrophobic functional compound of Formula 2 includes 1 to 20 mol%, preferably 5 to 15 mol% relative to the reactable poly (amino acid) derivative. If no hydrophobic functional group is added at all, the hydrophilic / hydrophobic balance is not so high that the solubility does not decrease even when the pH is increased, whereas if the hydrophobic functional group is 20 mol% or more, the hydrophobicity of the polymer is so strong that it does not dissolve in water.

Therefore, the pH-sensitive polymer according to the present invention easily controls the physical properties of the polymer and the degree of pH sensitivity by easily adjusting the preparation conditions, such as the type and the addition molar ratio of the above-described pH-sensitive functional groups and hydrophobic functional groups in the preparation of the polymer copolymer. Can be adjusted and economical manufacturing is possible.

According to one embodiment of the invention the invention provides a pH sensitive polymer of formula 3:

Formula 3

Wherein x + y + z has a value of 4 to 600, and y is at least 1, R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₂ is ₂ carbon atoms It is an alkyl group of 10 to 10, R ₃ and R ₄ is an alkyl group having 3 to 6 carbon atoms, R ₅ is a straight or branched chain saturated or unsaturated alkyl group having 6 to 30 carbon atoms.

As the polyaspartate derivative compound having both hydrophilicity and biodegradability, which is one of the components constituting the pH sensitive polymer, it is preferable to add a functional group such as a hydroxy group or an ester group having nonionic properties to the polyaspartate compound. And poly (2-hydroxyethyl aspartamide) in which a hydroxy group is added to a polyaspartate compound. The molecular weight range of the polyaspartate derivative compound is not particularly limited, but is preferably in the range of 1,000 to 150,000. If the molecular weight is less than 1,000, the solubility in water is high, and if the molecular weight is more than 150,000, the hydrophilicity / hydrophobicity is not balanced, so that it may not be dissolved and precipitate in all pH ranges.

According to the present invention, the pH sensitive polymer may be obtained by additionally adding a pH sensitive functional group and a hydrophobic functional group to the polyaspartate derivative compound. For example, such a pH-sensitive polymer dissolves poly (succinimide) in dimethylformamide, adds a certain amount of a hydrophobic functional compound of Formula 2 to the solution, and then reacts by stirring at a temperature of 60 to 80 ° C. for 12 hours. Let's do it. After the pH sensitive functional compound of Formula 1 is added to the mixed solution, the mixture is further reacted at a temperature of 60 to 80 ° C. for 12 hours, and the temperature is lowered to 30 ° C., followed by addition of 2-aminoethanol for 6 hours. After the reaction is completed, the reaction product is removed from the solvent by precipitation, filtration or concentration to obtain the desired pH sensitive polymer.

The functional groups added to the polyaspartate derivatives commonly have a reactor composed of primary or secondary amines, and are used to make amide bonds with the polyaspartate derivatives.

Accordingly, the pH sensitive polymer according to the present invention includes a reactor composed of primary or secondary amines reacting with a polyaspartate derivative at the terminal and a tertiary amine group imparting pH sensitivity in the molecule, solubility in water according to pH. Has different ionization characteristics. In particular, the pH sensitive functional group of Formula 1 has a pKa value of about 9 to 11, is insoluble at pH 9 and above, and has a property of being ionized at pH 9 or lower and dissolved in water.

Another object of the present invention is to provide a pH sensitive active ingredient delivery composition comprising a pH sensitive polymer according to the present invention.

The pH sensitive delivery composition according to the present invention can be usefully used by adjusting to dissolve in a specific pH region desired. For example, in the washing process of washing clothes or dishwashing, the washing water has a pH of 10 to 11 in the general washing process, and the rinsing water in the final rinsing process has a pH of 6 to 8. Therefore, by adjusting the content of the pH-sensitive functional groups and hydrophobic functional groups to form a stable coating film without dissolution at pH 10 to 11, pH sensitivity that is dissolved at a low pH so that the coating film is dissolved at pH 9 or less appearing in the rinsing process When preparing a coating composition (delivery composition) comprising a polymer, and using such an active ingredient such as a flexible component for coating or encapsulation, in the washing process in the automatic washing of clothes or tableware, the flexible component or the like according to the present invention As the pH is lowered during the rinsing process, the polymer is dissolved and coated with the pH-sensitive polymer, so that the polymer may be dissolved to release the flexible component or aroma, which may be used as an effective release controlling agent to give the clothing or tableware a flexible effect.

The active ingredient encapsulated in the pH sensitive delivery composition of the present invention may be used without particular limitation, and non-limiting examples thereof include flavors, enzymes, fabric softeners, bleaches, bleach activators, softeners, fluorescent brighteners, antiwrinkle agents or And mixtures thereof. In addition to the aforementioned components, it may also include additives commonly known in the art, such as stabilizers, pH adjusters, antioxidants, preservatives, binders or disintegrants, and the like. In addition, when the active ingredient is a liquid, it can also be used in solid materials, such as zeolites, porous beads, starch, etc. in which the active ingredient is absorbed.

The method for producing the delivery composition according to the present invention can be used alone or in combination with conventional methods known in the art, such as spray drying, coating with a fluidized bed dryer, emulsification, matrix formation and the like.

Hereinafter, the present invention will be described in more detail with reference to the following Examples and Test Examples. However, the following Examples and Test Examples are only for illustrating the present invention, but the scope of the present invention is not limited thereto.

Example  1-6, Comparative example  1-6

The poly (succinimide) (PSI) used in the experiment was prepared with reference to the literature. (Masayuki Tomida et al., Polymer, Vol. 38, 1997, pp 4733 ~ 4736)

97 g of poly (succinimide) is dissolved in 600 ml of dimethylformamide, and a fixed amount of hydrophobic functional groups are added as shown in Table 1, followed by reaction at 60 ° C. for 12 hours. After adding pH sensitive functional groups to the mixture as shown in Table 1 below, the mixture was further reacted at 60 ° C. for 12 hours, lowered to 30 ° C., and then reacted for 6 hours by adding 2-aminoethanol. After the reaction was completed, the reaction product was slowly added to the diluted sodium hydroxide solution to precipitate the product, and the solvent was removed, followed by freeze drying at -52 ° C to prepare a polymer.

Sample name PSI ^{Note 1)} (g) pH sensitive functional groups ^{Note 2 )} (mole) Hydrophobic group ^{Note 3) (mole)} 2-ethanolamine (mole) Example 1 97 0.25 DBAPA 0.10 ODA 0.65 Example 2 97 0.50 DBAPA 0.10 ODA 0.40 Example 3 97 0.70 DBAPA 0.10 ODA 0.20 Example 4 97 0.70 DBAEA 0.10 ODA 0.20 Example 5 97 0.90 DBAPA 0.10 ODA - Example 6 97 0.70 DBAPA 0.10 DDA 0.20 Comparative Example 1 97 0.05 DBAPA 0.10 ODA 0.85 Comparative Example 2 97 0.70 DBAPA - 0.30 Comparative Example 3 97 0.70 DBAPA 0.20 ODA 0.10 Comparative Example 4 97 0.70 DBAPA 0.30 ODA - Comparative Example 5 97 0.70 DMAPA 0.10 ODA 0.20 Comparative Example 6 97 0.70 DEAPA 0.10 ODA 0.20

Note 1) poly (succinimide)

Note 2) DBAPA N, N-di-normalbutylaminopropylamine

      DBAEA N, N-di-normalbutylaminoethylamine

      DMAPA N, N-dimethylaminopropylamine

      DEAPA N, N-diethylaminopropylamine

Note 3) ODA octadecylamine

      DDA dodecylamine

Experimental Example  1. Evaluation of pH Sensitivity of Copolymer

In order to evaluate the solubility according to the pH of the pH-sensitive polymer prepared according to the present invention was tested as follows.

 20 mg of the polymer of Examples 1 to 6 or Comparative Examples 1 to 6 was dissolved in 20 ml of distilled water, and the pH was lowered to 4.0. Dilute sodium hydroxide solution was added to gradually change the pH up to 12.0, and the change in pH and transmittance at 500 nm was measured using a pH meter and an ultraviolet spectrometer. The results are shown in FIGS. 1 to 3.

As a result, it was confirmed that the polymers of Examples 1 to 6 were completely dissolved in the region of pH 9 or lower, and when the pH was 9 or higher, the solubility rapidly decreased and precipitation occurred.

On the other hand, the polymer of Comparative Example 1 added 0.05 mole of N, N-di-normalbutylaminopropylamine, which is a pH sensitive functional group, but did not decrease the solubility even in the region of pH 9 or more. This is because the content of pH-sensitive functional groups is so low that even if the ionization degree of tertiary amines present in N, N-di-normalbutylaminopropylamine at high pH (pH 9 or higher) is reduced, the effect on the water solubility of the entire polymer is small. to be.

In addition, as the amount of hydrophobic functional group added to the polymer increases, solubility generally decreased in the entire pH range. On the other hand, in Comparative Example 2, in which the hydrophobic functional group was not added at all, the hydrophilic / hydrophobic balance was not balanced, so that no soluble transition phenomenon occurred. In addition, in the case of Comparative Examples 3 to 4 in which 0.2 or 0.3 mole of hydrophobic functional group was added, the content of hydrophobic functional group was too high to dissolve in the entire pH range.

In addition, as a result of measuring the behavior of the polymer prepared by using different pH sensitive functional groups in Examples 3, 4 and Comparative Examples 5, 6, N, N-di-normal butylaminopropylamine and N, N-di-normal Polymers using butylaminoethylamine were insoluble at pH 9 or higher, while polymers using N, N-di-methylaminopropylamine and N, N-di-ethylaminopropylamine were dissolved in water at pH 9 or higher. Therefore, it was confirmed that a pH sensitive functional group suitable for the present invention should have a tertiary amine group having a pKa value of about 9 to 11, insoluble at pH 9 or higher, and ionized at pH 9 or lower to dissolve in water (FIG. 4). And FIG. 5).

Experimental Example  2. Solubility Evaluation

The solubility of the active ingredient coated with a pH sensitive polymer was measured in the following manner at pH 7.0, pH 11.0.

100 g of distearyldimethylammonium chloride granules having a flexible performance as a cationic surfactant were mixed while spraying an organic solvent dispersion in which 5 g of the polymer prepared in Example 3 was dissolved, followed by drying at 40 ° C. or more. The polymer-coated cationic surfactant granules were obtained. Prepare 100 ml of pH 7 or pH 11 solution in a beaker, use a mixer to stir at a constant speed, run the electrical conductivity meter connected to the computer, add 0.5 g of coated granules to the center with stirring and at this point It was set to zero. When the conductivity value did not rise for more than 2 minutes, the value was set to 100%, and the time point of reaching 99% based on 100% was called T ₉₉ and the solubility was evaluated. The dissolved solution was filtered through a 200 mesh mesh and the unfiltered material was dried and quantified. The remaining amount that was not dissolved compared to the initial amount was called insoluble substance (%). The results are shown in Table 2 and FIG.

pH 7.0 pH 11.0 No coating coating No coating coating T ₉₉ (second) 38 158 41 435 Insoluble matter (%) 1.3 1.9 1.5 8.9

Experimental results showed that the uncoated leaded component granules completely dissolved within 40 seconds and did not change even if the pH was changed. On the other hand, in the case of coating with the polymer prepared in Example 3 was 158 seconds when the pH was 7 it was found that the dissolution delayed to 435 seconds at pH 11 to protect the particles. After dissolution was completed, the amount of unfiltered material also increased from 1.9% at pH 7 to 8.9% at pH 11.

As a result, the pH-sensitive polymer of the present invention is coated or encapsulated with an active ingredient to form a stable coating film does not dissolve in the pH 9 or more in the aqueous solution, and confirms that the active film can be released by dissolving the coating film below pH 9 Could.

Example  7

Next, the flexible detergent composition having the components and contents of Table 3 was prepared by a conventional method using a high speed rotary mixer and a spray dryer.

Raw material weight % Nonionic Surfactant ^{Note 1 )} 15 Anionic Surfactants ^{Note 2 )} 7 Cationic Surfactant ^{Note 3 )} 5 Example 3 Polymer 0.25 Sodium carbonate 35 Zeolite 25 Pollution Dispersing Polymer 0.5 sulphate of soda 5.75 Fluorescent dyes 0.3 enzyme 0.5 incense 0.2 moisture 5.5 Sum 100

Note 1) 12 to 14 carbon atoms of the alkyl group, 9 mol of ethylene oxide average added moles

Note 2) linear alkylbenzenesulfonic acid

Note 3) Distearyldimethylammonium chloride (AROSURF TA-101, Goldschmidt)

The copolymer of the present invention forms a pH sensitive polymer by combining a hydrophilic poly (amino acid) derivative with a pH sensitive functional group of Formula 1 and a hydrophobic functional group of Formula 2, thereby providing a pH sensitive polymer that is soluble at a specific pH, in particular simply By adjusting the content of the pH-sensitive functional groups and hydrophobic functional groups to be added, it is possible to easily adjust the pH of the polymer is dissolved, it can be used as a delivery composition that must release the active material at a certain time, such as dishwasher or clothes washing machine.

Claims (11)

A pH-sensitive polymer compound characterized in that the poly-aspartate derivative compound is added with a pH sensitive functional group of Formula 1 and a hydrophobic functional group of Formula 2: Formula 1

In the above formula, R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkyl group having 2 to 10 carbon atoms. R ₃ and R ₄ are alkyl groups having 3 to 6 carbon atoms, Formula 2

Wherein R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₅ is a straight or branched chain saturated or unsaturated alkyl group having 6 to 30 carbon atoms. The pH sensitive polymer according to claim 1, wherein the pH sensitive functional group of Chemical Formula 1 is a tertiary amine having a pKa value of 9 to 11, insoluble at pH 9 or higher, and ionized at pH 9 or lower and dissolved in water. . The method of claim 1, wherein the pH-sensitive functional group of Formula 1 is N, N-di-normalbutylaminopropylamine, N, N-di-normalbutylaminoethylamine, N, N-di-isopropylaminoethylamine PH sensitive polymer, characterized in that selected from the group consisting of. The pH-sensitive polymer according to claim 1, wherein the hydrophobic functional group represented by Chemical Formula 2 is hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl group or oleyl group. The pH-sensitive polymer of claim 1, wherein the pH-sensitive functional group of Chemical Formula 1 is contained in an amount of 25 to 90 mol% based on the poly (amino acid) derivative capable of reacting. The pH-sensitive polymer according to claim 1, wherein the hydrophobic functional group of Chemical Formula 2 is contained in an amount of 5 to 15 mol% based on the reactable polyaspartate derivative. The pH-sensitive polymer according to claim 1, wherein the polyaspartate derivative compound is added with a hydroxyl group or an ester group having a nonionic property to the polyaspartate compound. The pH-sensitive polymer of claim 1, wherein the polyaspartate derivative compound has a molecular weight in the range of 1,000 to 150,000. PH sensitive polymers of Formula 3: Formula 3

Wherein x + y + z has a value of 4 to 600, and y is at least 1, R ₁ is hydrogen or a straight or branched chain alkyl group having 1 to 6 carbon atoms, and R ₂ is ₂ carbon atoms It is an alkyl group of 10 to 10, R ₃ and R ₄ is an alkyl group having 3 to 6 carbon atoms, R ₅ is a straight or branched chain saturated or unsaturated alkyl group having 6 to 30 carbon atoms. 10. An active ingredient delivery composition comprising the pH sensitive polymer of claim 1. A flexible detergent composition containing a flexible component coated or encapsulated with the pH sensitive polymer of any one of claims 1 to 9.

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