Polymerizable composition, polymer capsule and fabric softener composition comprising the same

Abstract

A polymerizable composition, polymer capsules and a fabric softener composition are provided. The fabric softener composition includes polymer capsules in which cationic groups are introduced on the surfaces thereof, so that early release of a fragrance can be suppressed and aromas can be generated depending on rupture of a shell material of the polymer capsules by light friction at certain times. In addition, the polymer capsules have high adhesion to fibers and are not attached to fibers during washing to minimize the discharged fragrance, so that sufficient aromas can be provided even if a small amount of fragrance is used.

Claims

1. A polymerizable composition comprising a compound represented by Formula 3 below and a polymerizable monomer: ##STR00011## wherein, R.sub.9 and R.sub.15 are each independently hydrogen or an alkyl group, X.sub.2 and X.sub.3 are each independently an ester bond, an amide bond, a sulfonamide bond, a phosphoramide bond or an arylene group, Y.sub.2 and Y.sub.3 are each independently an alkylene group, R.sub.10, R.sub.11, R.sub.13 and R.sub.14 are each independently hydrogen or an alkyl group, R.sub.12 is an alkylene group or an arylene group, and Z.sup.− is an anion.

2. The polymerizable composition according to claim 1, wherein X.sub.2 and X.sub.3 in Formula 3 are each independently an ester bond or an arylene group, and R.sub.12 is an alkylene group having 2 to 12 carbon atoms.

3. The polymerizable composition according to claim 1, further comprising a compound represented by Formula 4 below: ##STR00012## wherein, R.sub.16 is hydrogen or an alkyl group, X.sub.4 is an ester bond, an amide bond, a sulfonamide bond, a phosphoramide bond or an arylene group, Y.sub.4 is an alkylene group, R.sub.17, R.sub.18 and R.sub.19 are each independently an alkyl group, an alkylalkanoate group or an aryl group, and Z.sup.− is an anion.

4. The polymerizable composition according to claim 3, wherein X.sub.4 in Formula 4 is an ester bond or an arylene group, and R.sub.17, R.sub.18 and R.sub.19 are each independently an alkyl group having 8 to 20 carbon atoms.

5. The polymerizable composition according to claim 3, wherein the polymerizable composition comprises the compound represented by Formula 4 in an amount of 1 part by weight to 30 parts by weight per 100 parts by weight of the polymerizable monomer.

6. The polymerizable composition according to claim 1, wherein the polymerizable composition comprises the polymerizable monomer in an amount of 15 wt% to 85 wt% relative to a total weight of the polymerizable composition.

7. The polymerizable composition according to claim 1, wherein the polymerizable composition comprises the compound represented by Formula 3 in an amount of 0.1 parts by weight to 15 parts by weight per 100 parts by weight of the polymerizable monomer.

8. The polymerizable composition according to claim 1, further comprising a fragrance.

9. The polymerizable composition according to claim 8, wherein the polymerizable composition comprises the fragrance in an amount of 15 parts by weight to 75 parts by weight per 100 parts by weight of the polymerizable monomer.

10. Polymer capsules comprising a shell material containing a unit of a compound represented by Formula 1 below and a unit of a polymerizable monomer: ##STR00013## wherein, R.sub.1 is hydrogen or an alkyl group, X is an ester bond, an amide bond, a sulfonamide bond, a phosphoramide bond or an arylene group, Y is an alkylene group, R.sub.2 and R.sub.4 are each independently hydrogen, an alkyl group, an alkylalkanoate group or an aryl group, R.sub.3 is an alkyl group, an alkylalkanoate group, an aryl group or a functional group represented by Formula 2 below, and Z.sup.31 is an anion: ##STR00014## wherein, * is a site bonded with N+ in Formula 1, R.sub.6 is an alkylene group or an arylene group, R.sub.5 and R.sub.7 are each independently an alkyl group, an alkylalkanoate group or an aryl group, Y.sub.1 is an alkylene group, X.sub.1 is an ester bond, an amide bond, a sulfonamide bond, a phosphoramide bond or an arylene group, R.sub.8 is hydrogen or an alkyl group, and Z.sup.−is an anion.

11. The polymer capsules according to claim 10, wherein cations derived from the compound represented by Formula 1 are present on the surfaces.

12. The polymer capsules according to claim 10, further comprising a fragrance supported therein.

13. A fabric softener composition comprising the polymer capsules of claim 10.

Description

PREPARATION EXAMPLE 1

Preparation of Crosslinkable Monomer XL1

(1) 57 g of 2-(N,N-dimethylamino)ethyl methacrylate, 50 g of 1,12-dibromododecane and 250 g of a mixed solvent (methanol: acetonitrile mixed in a mass ratio of 3:7) were placed in a 500 mL round bottom flask, stirred at 50° C. for 24 hours and reacted. As a result of performing NMR analysis of the reaction product, it was confirmed that the N—CH.sub.3 peak near 2.5 ppm was shifted to near 3.5 ppm, whereby it contained an N.sup.+—CH.sub.3 cation as in Formula A below. After the reaction, the resulting precipitate was removed with a vacuum filter, washed with acetone, and then dried to obtain a crosslinkable monomer XL1 of Formula A below:

(2) ##STR00007##

(3) In Formula A, R.sub.1 is a methyl group, R.sub.2 is an ethylene group, Z.sup.− is a bromine ion, and n is 10.

<NMR Analysis Results in Preparation Example 1—H.SUP.1 .NMR (ppm, DMSO-D.SUB.6.)>

(4) 6.07 (2H, vinyl), 5.76 (2H, vinyl), 4.51 (4H, CO.sub.2CH.sub.2C), 3.71 (4H, CCH.sub.2N.sup.+), 3.37 (4H, N.sup.+CH.sub.2C), 3.09 (12H, N.sup.+CH.sub.3), 1.90 (6H, C═C—CH.sub.3), 1.66 (4H, N.sup.+CCH.sub.2), 1.26 (16H, CCH.sub.2C)

PREPARATION EXAMPLE 2

Preparation of Crosslinkable Monomer XL2

(5) 35 g of N,N,N′,N′-tetramethyl-1,6-hexanediamine, 74 g of 4-vinylbenzyl chloride and 250 g of a mixed solvent (methanol: acetonitrile mixed in a mass ratio of 3:7) were placed in a 500 mL round bottom flask, stirred at 50° C. for 24 hours and reacted. As a result of performing NMR analysis of the reaction product, it was confirmed that the N—CH.sub.3 peak near 2.5 ppm was shifted to near 3.5 ppm, whereby it contained an N.sup.+—CH.sub.3 cation as in Formula B below. After the reaction, the resulting precipitate was removed with a vacuum filter, washed with acetone, and then dried to obtain a crosslinkable monomer XL2 of Formula B below.

(6) ##STR00008##

(7) In Formula B, R.sub.1 is hydrogen, R.sub.2 is a methylene group, Z.sup.− is a chlorine ion, and n is 4.

<NMR Analysis Results in Preparation Example 2—H.SUP.1 .NMR (ppm, DMSO-D.SUB.6.)>

(8) 7.60 (4H, aromatic), 7.11 (4H, aromatic), 6.72 (2H, vinyl), 5.76 (2H, vinyl), 5.25 (2H, vinyl), 4.50 (4H, Phenyl-CH.sub.2—N.sup.+), 3.38 (4H, N.sup.+CH.sub.2C), 3.10 (12H, N.sup.+CH.sub.3), 1.76 (4H, N.sup.+CCH.sub.2), 1.30 (4H, CCH.sub.2C)

PREPARATION EXAMPLE 3

Preparation of Cationic Surfactant S1

(9) 34 g of 2-(N,N-dimethylamino)ethyl methacrylate and 250 g of acetone were placed in a 500 mL round bottom flask and stirred, and 70 g of 1-bromohexadecane was slowly added in drops. After the introduction was completed, the reaction mixture was stirred at 35° C. for 48 hours and reacted. The precipitate generated after the reaction was removed with a vacuum filter, washed with hexane and then dried to obtain a cationic surfactant S1 of Formula C below.

(10) ##STR00009##

(11) In Formula C, R.sub.1 is a methyl group, R.sub.2 is an alkyl group having 16 carbon atoms, and Z.sup.− is a bromine ion.

<NMR Analysis Results in Preparation Example 3—H.SUP.1 .NMR (ppm, measurement Solvent: CDCl.SUB.3.)>

(12) 6.16 (1H, vinyl), 5.69 (1H, vinyl), 4.66 (2H, CO.sub.2CH.sub.2C), 4.19 (2H, CCH.sub.2N.sup.+), 3.62 (2H, N.sup.+CH.sub.2C), 3.52 (6H, N.sup.+CH.sub.3), 1.96 (3H, C═C—CH.sub.3), 1.76 (2H, N.sup.+CCH.sub.2), 1.26 (26H, CCH.sub.2C), 0.89 (3H, CCH.sub.3)

PREPARATION EXAMPLE 4

Preparation of Cationic Surfactant S2

(13) 53 g of N,N-dimethyldodecylamine and 250 g of acetone were placed in a 500 mL round bottom flask and stirred, and 40 g of 4-vinylbenzyl chloride was slowly added in drops thereto. After the introduction was completed, the reaction mixture was stirred at 35° C. for 48 hours and reacted. After the reaction, the resulting precipitate was removed with a vacuum filter, washed with hexane and then dried to obtain a cationic surfactant S2 of Formula D below.

(14) ##STR00010##

(15) In Formula D, R.sub.1 is a hydrogen atom, R.sub.2 is an alkyl group having 12 carbon atoms, and Z.sup.− is a chlorine ion.

(16) <NMR analysis results in Preparation Example 4 - H.sup.1 NMR (ppm, DMSO-D6)>

(17) 7.59 (2H, aromatic), 7.11 (2H, aromatic), 6.71 (1H, vinyl), 5.76 (1H, vinyl), 5.26 (1H, vinyl), 4.48 (2H, phenyl-CH.sub.2—N.sup.+), 3.35 (2H, N.sup.+CH.sub.2C), 3.12 (6H, N.sup.+CH.sub.3), 1.76 (2H, N.sup.+CCH.sub.2), 1.30 (18H, CCH.sub.2C), 0.90 (3H, CCH.sub.3)

PREPARATION EXAMPLE 5

Preparation of Polymer Capsules C1

(18) 2 g of cetrimonium bromide (CTAB) and 266 g of distilled water were placed in a 500 mL round bottom flask and stirred at 600 rpm for 30 minutes. A mixed liquid of 38 g of methyl methacrylate (MMA), 2 g of the crosslinkable monomer XL1 in Preparation Example 1, and 20 g of Comely 450 from IFF Co., Ltd. as a fragrance was introduced thereto, and then the reactor was sealed. The mixture was purged with nitrogen for 30 minutes with stirring to remove dissolved oxygen. After the reaction mixture was heated to a temperature of 60° C., 0.4 g of sodium persulfate (SPS) was introduced as a thermal polymerization initiator and after the reaction was performed for 5 hours, the reaction was completed to prepare the polymer capsules C1.

PREPARATION EXAMPLE 6

Preparation of Polymer Capsules C2

(19) 2 g of cetrimonium bromide (CTAB) and 266 g of distilled water were placed in a 500 mL round bottom flask and stirred at 600 rpm for 30 minutes. A mixed liquid of 38 g of styrene (ST), 2 g of the crosslinkable monomer XL2 in Preparation Example 2, and 20 g of Comely 450 from IFF Co., Ltd. as a fragrance were introduced thereto, and then the reactor was sealed. The mixture was purged with nitrogen for 30 minutes with stirring to remove dissolved oxygen. After the reaction mixture was heated to a temperature of 60° C., 0.4 g of sodium persulfate (SPS) was introduced as a thermal polymerization initiator and after the reaction was performed for 5 hours, the reaction was completed to prepare the polymer capsules C2.

PREPARATION EXAMPLES 7 TO 18

Preparation of Polymer Capsules C3 to C14

(20) The polymer capsules were prepared in the same method as the polymerization method shown in Preparation Example 5 and Preparation Example 6, except that the employed materials and their contents were adjusted as shown in Tables 1 to 3 below.

PREPARATION EXAMPLE 19

Preparation of Polymer Capsules B1

(21) The polymer capsules were prepared in the same manner as in Preparation Example 5, except that a nonionic crosslinkable monomer, ethylene glycol dimethacrylate (EGDMA), was used instead of XL1 in Preparation Example 1 as the crosslinkable monomer, and the results were shown in Table 3 below.

PREPARATION EXAMPLE 20

Preparation of Polymer Capsules B2

(22) The polymer capsules were prepared in the same manner as in Preparation Example 5, except that 2 g of a nonionic surfactant, Brij® L23 (Sigma Aldrich) was used as the surfactant, and a nonionic crosslinkable monomer, ethylene glycol dimethacrylate (EGDMA), was used instead of XL1 in Preparation Example 1 as the crosslinkable monomer, and the results were shown in Table 3 below.

(23) TABLE-US-00001 TABLE 1 C1 C2 C3 C4 C5 Surfactant Type CTAB CTAB CTAB CTAB CTAB Content 2 2 2 2 2 polymerizable monomer Type MMA ST MMA MMA ST Content 38 38 47.5 39.6 47.5 Crosslinkable monomer Type XL1 XL2 XL1 XL1 XL2 Content 2 2 2.5 0.4 2.5 Fragrance Type Comely 450 Comely 450 Comely 450 Comely 450 Comely 450 Content 20 20 12 20 12 Thermal polymerization Type SPS SPS SPS SPS SPS initiator Content 0.4 0.4 0.5 0.4 0.5 Water 248 248 248 248 248 Particle diameter (nm) 560 370 140 640 110 CTAB: cetrimonium bromide, MMA: methyl methacrylate, ST: stylene, EGDMA: ethylene glycol dimethacrylate, SPS: sodium persulfate, Content unit: weight (g)

(24) TABLE-US-00002 TABLE 2 C6 C7 C8 C9 C10 Surfactant Type S1 S2 S1 S1 S2 Content 2 2 2 2 2 polymerizable monomer Type MMA ST MMA MMA MMA Content 38 38 47.5 39.6 38 Crosslinkable monomer Type EGDMA DVB EGDMA EGDMA EGDMA Content 2 2 2.5 0.4 2 Fragrance Type Comely 450 Comely 450 Comely 450 Comely 450 Comely 450 Content 20 20 12 20 20 Thermal polymerization Type SPS SPS SPS SPS SPS initiator Content 0.4 0.4 0.5 0.4 0.5 Water 248 248 248 248 248 Particle diameter (nm) 670 440 65 870 710 CTAB: cetrimonium bromide, MMA: methyl methacrylate, ST: stylene, DVB: divinylbenzene, EGDMA: ethylene glycol dimethacrylate, SPS: sodium persulfate, Content unit: weight (g)

(25) TABLE-US-00003 TABLE 3 C11 C12 C13 C14 B1 B2 Surfactant Type S1 S1 S1 S1 CTAB Brij ® L23 Content 8 8 4 2 2 2 polymerizable Type MMA MMA MMA MMA MMA MMA monomer Content 38 39.6 38 38 38 38 Crosslinkable Type XL1 XL1 XL1 XL1 EGDMA EGDMA monomer Content 2 0.4 2 2 2 2 Fragrance Type Comely 450 Comely 450 Comely 450 Comely 450 Comely 450 Comely 450 Content 20 20 20 20 20 20 Thermal Type SPS SPS SPS SPS SPS SPS polymerization Content 0.4 0.4 0.4 0.4 0.4 0.4 initiator Water 242 242 246 248 248 248 Particle diameter (nm) 250 100 670 210 450 710 CTAB: cetrimonium bromide, MMA: methyl methacrylate, ST: stylene, EGDMA: ethylene glycol methacrylate, SPS: sodium persulfate, Content unit: weight (g)

Example 1. Preparation of Fabric Softener Composition

(26) A fabric softener composition was prepared using the polymer capsules C1 of Preparation Example 5. Specifically, the polymer capsules C1 of Preparation Example 5 were mixed with diester ammonium methosulfate, polyoxyethylene alkyl ether, ethylene glycol and additives (dye, preservative, antioxidant, defoamer, etc.) in the ratios of Table 4 below to prepare a fabric softener. The residual amount of water means purified water added so that the sum of all components is 100.

Examples 2 to 14. Preparation of Fabric Softener Compositions

(27) Fabric softener compositions were prepared in the same manner as in Example 1, except that the kinds and contents of the polymer capsules were adjusted as shown in Tables 4 to 6 below.

Comparative Example 1. Preparation of Fabric Softener Composition

(28) The non-encapsulated commercial fragrance Comely 450 (IFF), and diester ammonium methosulfate, polyoxyethylene alkyl ether, ethylene glycol and additives (dye, preservative, antioxidant, defoamer, etc.) were adopted in the composition of Table 6 below to prepare a fabric softener composition.

Comparative Example 2. Preparation of Fabric Softener Composition

(29) A fabric softener composition was prepared in the same manner as in Example 1, except that the polymer capsules B1 of Preparation Example 14 were used.

Comparative Example 3. Preparation of Fabric Softener Composition

(30) A fabric softener composition was prepared in the same manner as in Example 1, except that the polymer capsules B2 of Preparation Example 15 were used.

(31) The constituents of the fabric softener compositions according to Examples and Comparative Examples, their contents and their lingering aroma effect evaluation results were described in Tables 4 to 6 below.

(32) TABLE-US-00004 TABLE 4 Example 1 2 3 4 5 6 Polymer Type C1 C2 C3 C4 C5 C6 capsules Content* 4.7 (0.3) 4.7 (0.3) 7.9 (0.3) 4.7 (0.3) 7.9 (0.3) 4.7 (0.3) Surfactant 5 5 5 5 5 5 Emulsion stabilizing agent 0.5 0.5 0.5 0.5 0.5 0.5 Dispersion stabilizer 0.05 0.05 0.05 0.05 0.05 0.05 Others** suitable suitable suitable suitable suitable suitable amount amount amount amount amount amount Water residual residual residual residual residual residual amount amount amount amount amount amount Lingering aroma effect ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Surfactant: diester ammonium mehosulfate, Emulsion stabilizing agent: polyoxyethylene alkyl ether, Dispersion stabilizer: ethylene glycol, Not-encapsulated Fragrance: Comely 450 (IFF Co., Ltd.), Content unit: part by weight (g), Content* of polymer capsules: g number of capsule emulsion, where number in parentheses is the content (g) of the supported fragrance, **Others: to represent small amounts of additives such as pigments, antiseptics, antioxidants and defoamers

(33) TABLE-US-00005 TABLE 5 Example 7 8 9 10 11 12 Polymer Type C7 C8 C9 C10 C11 C12 capsules Content* 4.7 (0.3) 7.9 (0.3) 4.7 (0.3) 7.9 (0.3) 4.7 (0.3) 4.7 (0.3) Surfactant 5 5 5 5 5 5 Emulsion stabilizing agent 0.5 0.5 0.5 0.5 0.5 0.5 Dispersion stabilizer 0.05 0.05 0.05 0.05 0.05 0.05 Others** suitable suitable suitable suitable suitable suitable amount amount amount amount amount amount Water residual residual residual residual residual residual amount amount amount amount amount amount Lingering aroma effect ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Surfactant: diester ammonium mehosulfate, Emulsion stabilizing agent: polyoxyethylene alkyl ether Dispersion stabilizer: ethylene glycol, Not-encapsulated Fragrance: Comely 450 (IFF Co., Ltd.), Content unit: part by weight (g), Content* of polymer capsules: g number of capsule emulsion, where number in parentheses is the content (g) of the supported fragrance, **Others: to represent small amounts of additives such as pigments, antiseptics, antioxidants and defoamers

(34) TABLE-US-00006 TABLE 6 Example Comparative Example 13 14 1 2 3 Polymer Type C13 C14 B1 B2 capsules Content* 4.7 (0.3) 4.7 (0.3) 4.7 (0.3) 4.7 (0.3) Not-encapsulated fragrance 0.3 Surfactant 5 5 5 5 5 Emulsion stabilizing agent 0.5 0.5 0.5 0.5 0.5 Dispersion stabilizer 0.05 0.05 0.05 0.05 0.05 Others suitable suitable suitable suitable suitable amount amount amount amount amount Water residual residual residual residual residual amount amount amount amount amount Lingering aroma effect ⊚ ⊚ Δ Δ Δ

(35) As can be seen from Tables 4 to 6 above, it can be confirmed that the fabric softener compositions according to Examples 1 to 14 using the compounds of the present application show excellent lingering aroma effect. On the other hand, despite the use of the same fragrance, it can be seen that the fabric softener compositions using only the non-encapsulated fragrance show slight lingering aroma effect. Also, it can be confirmed that the fabric softeners in accordance with Comparative Example 2 and Comparative Example 3 without using the compounds of the present application show slight lingering aroma effect. Accordingly, it can be seen that the fabric softener compositions comprising the polymer capsules prepared from the polymerizable composition of the present application show excellent lingering aroma effect.