Urethane-type polymers and use thereof

Abstract

A urethane polymer obtained by a reaction of: a monohydroxy compound (A), a polyethylene glycol (B), a monoglyceryl ether compound (C), and an isocyanate compound (D). This urethane polymer can be used as a urethane viscosity modifier excellent in long-term storage stability, similarly to alkali thickening-type viscosity modifiers, while having characteristics similar to those of existing urethane viscosity modifiers.

Claims

1. A urethane polymer obtained by a reaction of: a monohydroxy compound (A) represented by Formula (1),
R.sup.1OC.sub.2H.sub.4—O.sub.mH  (1) wherein R.sup.1 is an aliphatic hydrocarbon group having 24 to 36 carbon atoms, and m represents a number ranging from 0 to 1000; a polyethylene glycol (B) represented by Formula (2),
HOC.sub.2H.sub.4—O.sub.nH  (2) wherein n represents a number ranging from 20 to 500; a monoglyceryl ether compound (C) represented by Formula (3), ##STR00003## wherein R.sup.2 represents an aliphatic hydrocarbon group having 5 to 12 carbon atoms; and an isocyanate compound (D) represented by Formula (4),
R.sup.3NCO].sub.q  (4) wherein R.sup.3 represents a hydrocarbon group having 6 to 13 carbon atoms, and q represents the number 2.

2. The urethane polymer according to claim 1, wherein a reaction ratio of the components is 10 to 30 moles of the monohydroxy compound (A), 5 to 20 moles of the monoglyceryl ether compound (C) and 20 to 50 moles of the isocyanate compound (D) with respect to 10 moles of the polyethylene glycol (B).

3. The urethane polymer according to claim 1, wherein the reaction is conducted through addition of the isocyanate compound (D) to a mixture of the monohydroxy compound (A), the polyethylene glycol (B) and the monoglyceryl ether compound (C).

Description

EXAMPLES

(1) The present invention will be explained next in further detail on the basis of working examples and comparative examples. However, the present invention is not limited to these examples.

(2) <Synthesis of Urethane Polymers>

(3) (Starting Materials Used)

(4) A-1: 50-EO adduct of an alcohol having 32 carbon atoms (2-tetradecyloctadecanol)

(5) A-2: 250-EO adduct of an alcohol having 32 carbon atoms (2-tetradecyloctadecanol)

(6) A-3: 150-EO adduct of an alcohol having 28 carbon atoms (2-dodecylhexadecanol)

(7) A-4: 150-EO adduct of an alcohol having 24 carbon atoms (2-decyltetradecyl)

(8) B-1: polyoxyethylene glycol having a weight-average molecular weight of 11000

(9) B-2: polyoxyethylene glycol having a weight-average molecular weight of 8000

(10) C-1: 2-ethylhexyl glyceryl ether

(11) C-2: monododecyl glyceryl ether

(12) D-1: hexamethylene diisocyanate

(13) D-2: metaphenylene diisocyanate

(14) A′-1: 150-EO adduct of a C22 alcohol (2-decyldodecyl)

(15) C′-1: butyl glyceryl ether

(16) *EO adduct: ethylene oxide adduct

(17) (Synthesis Method)

(18) [Synthesis of Inventive Product 1]

(19) A four-necked flask having a capacity of capacity 2000 mL and equipped with a thermometer, a nitrogen introduction tube and a stirrer, was charged with 267 g (0.1 moles) of A-1, 550 g (0.05 moles) of B-1 and 10.2 g (0.05 moles) of C-1. The interior of the system was purged with nitrogen, after which the temperature was raised to 80 to 90° C., to melt the charge, with mixing until homogeneity. After verifying that all components were homogeneously mixed, 25 g (0.15 moles) of D-1 were added into the system, and the system was left to react at the same temperature for 3 hours, to yield Inventive product 1.

(20) [Synthesis of Inventive Products 2 to 9]

(21) Inventive products 2 to 9 were obtained through synthesis under conditions identical to those of the synthesis of Inventive product 1, but herein the starting materials and/or blending proportions thereof were modified as given in Table 1.

(22) [Synthesis of Comparative Products 1 to 5]

(23) Comparative products 1 to 5 were obtained through synthesis under conditions identical to those of the synthesis of Inventive product 1, but herein the starting materials and/or blending proportions thereof were modified as given in Table 1.

(24) [Comparative Products 6 to 8]

(25) Commercially available viscosity modifiers were used as Comparative products 6 to 8.

(26) Comparative product 6: hydroxymethyl cellulose (trade name: HEC, by Sumitomo Seika Chemicals Co. Ltd.)

(27) Comparative product 7: methyl cellulose (trade name: Mecellose MC, by Tomoe Engineering Co., Ltd.)

(28) Comparative product 8: carboxyvinyl polymer (trade name: Carbopol 980, by The Lubrizol Corporation)

(29) TABLE-US-00001 TABLE 1 Inventive products Comparative products 1 2 3 4 5 6 7 8 9 1 2 3 4 5 A-1 0.1  — — — 0.1  0.1  0.1  0.1  0.1  0.1  — 0.1  0.1  — A-2 — 0.1  — — — — — — — — 0.1  — — — A-3 — — 0.1  — — — — — — — — — — — A-4 — — — 0.1  — — — — — — — — — — B-1 0.05 0.05 0.05 0.05 — 0.05 0.05 0.05 0.05 0.05 0.05 — 0.05 0.05 B-2 — — — — 0.05 — — — — — — — — — C-1 0.05 0.05 0.05 0.05 0.05 0.03 0.1  0.01 — — — — 0.05 C-2 — — 0.05 — — — — — — — — — — — D-1 0.15 0.15 0.15 0.15 0.15 — 0.15 0.15 0.15 0.15 0.1  0.05 0.15 0.15 D-2 — — — — — 0.15 — — — — — — — — A′-1 — — — — — — — — — — — — — 0.1  C′-1 — — — — — — — — — — — — 0.05 — (Remarks) The numerical value units in the table are moles.

Example 1: Viscosity Test

(30) Inventive products 1 to 9 and Comparative products 1 to 8 were added to pure water, to a proportion of 1.5 mass %, and after complete dissolution, the storage modulus (G′) and loss modulus (G″) at a respective angular frequency (w), using a rheometer (viscoelasticity measuring device) were measured. The results are given in Table 2. Herein, G′ denotes the capability (elastic component) of maintaining the stress that is stored inside the measurement liquid, while G″ denotes the viscosity component for which energy that is imparted to the measurement liquid was dissipated in the form of heat. If G′ is higher than G″, the liquid has elastic properties (solid properties), and, accordingly, settling and separation of components within the liquid are unlikelier to occur. A constant difference between G′ and G″ denotes a viscous body behavior that is identical at all frequencies. The rheometer and measurement conditions are as follows.

(31) Equipment Used

(32) Equipment name: MCR301 (by Anton Paar GmbH)

(33) Measurement Conditions

(34) Measurement fixture: PP50 (parallel plate, φ50 mm)

(35) Measurement position: 0.5 mm (distance from stage to parallel plate)

(36) Strain (deflection angle): 5%

(37) Measurement temperature: 25° C.

(38) TABLE-US-00002 TABLE 2 Angular frequency (rad/s) 0.1 0.5 1 5 10 20 50 100 Inventive products 1 G′ 110 112 113 115 117 119 122 127 G″ 5 4 4 5 6 6 7 8 2 G′ 140 145 146 148 150 151 149 145 G″ 17 17 16 16 16 15 15 16 3 G′ 160 172 174 176 175 175 173 172 G″ 57 22 17 17 16 16 15 15 4 G′ 121 126 137 137 138 138 140 142 G″ 62 45 32 29 29 27 26 24 5 G′ 105 106 107 107 108 110 111 113 G″ 4 3 3 4 5 5 5 6 6 G′ 132 135 136 137 139 140 142 145 G″ 23 18 15 15 15 14 13 12 7 G′ 116 120 121 123 125 126 128 130 G″ 21 15 14 13 13 12 12 13 8 G′ 124 126 127 127 129 130 131 133 G″ 26 20 18 17 17 16 16 16 9 G′ 115 119 120 121 121 123 124 126 G″ 58 43 21 21 20 19 18 19 Comparative 1 G′ 27 95 116 122 112 83 75 74 products G″ 48 47 26 8 6 5 4 4 2 G′ 16 68 102 108 104 93 87 81 G″ 43 40 21 7 7 5 4 4 3 G′ — — — — — — — — G″ — — — — — — — — 4 G′ 33 99 120 124 125 120 115 109 G″ 45 13 13 12 12 11 11 10 5 G′ — — — — — — — — G″ — — — — — — — — 6 G′ 1.5 4.1 9.6 33 69 102 134 168 G″ 3.6 1.1 2.2 55 90 121 145 191 7 G′ 1.7 5.9 11 25 34 38 49 63 G″ 3.7 8.3 12 21 26 29 35 42 8 G′ 312 326 351 364 380 385 391 397 G″ 18 16 26 34 39 43 46 50 (Remarks) The units of G′ and G″ are Pa. Comparative product 3 did not dissolve in water, and could not be tested. Comparative product 5 failed to thicken an aqueous solution, and hence could not be tested.

(39) As Table 2 indicates, some of the inventive products exhibited a small difference between G′ and G″ at a region of low angular frequency, but G′ took on a larger value than G″ in all instances. This is thought to make the occurrence of component settling and/or separation in the liquid unlikely.

(40) By contrast, the comparative products exhibit angular frequency regions in which G′ is smaller than G″, with the exception of Comparative product 8. This is thought to make the occurrence of component settling and/or separation in the liquid likelier. In Comparative product 8, component settling and/or separation in the liquid does not occur readily, but an alkali thickener (sodium polyacrylate) is involved herein, and hence the comparative product is difficult to use without being influenced by pH.

Example 2: Stability Test

(41) Respective gels were produced by dissolving the viscosity modifiers of Inventive products 1 to 9 and Comparative products 1 to 2, 4 and 6 to 8 in pure water, to a proportion of 1 mass %. Thereafter, a titanium oxide powder was added to each of the produced gels, to a proportion of 5 mass %, and the whole was stirred of 1 hour in a stirrer, until homogeneity. Each gel having titanium oxide homogeneously dispersed therein was left to stand in a thermostatic bath at 25° C., and the behavior of the titanium oxide was observed visually. The results are given in Table 3.

(42) TABLE-US-00003 TABLE 3 Inventive products Comparative products 1 2 3 4 5 6 7 8 9 1 2 4 6 7 8 Result ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ Δ Δ X X ◯ (Remarks) ◯ = No change in appearance after 4 weeks Δ = Separation or settling at 3 days to 1 week X = Separation or settling in less than 3 day

(43) As Table 3 reveals, the appearance of Inventive products 1 to 9 and Comparative product 8 did not change even after four weeks, which was indicative of good storage stability of the dispersed solid. By contrast, separation or precipitation of titanium oxide, in a lapse of time from three days to one week, was observed in Comparative products 1, 2 and 4. Separation or precipitation of titanium oxide in fewer than three days was observed in Comparative products 6 and 7. These results are identical to the results of the viscosity test (Example 1) measured mechanically.

(44) As the above results reveal, the present invention succeeds in providing a novel urethane polymer that can be used as a urethane viscosity modifier with excellent long-term storage stability, similarly to alkali thickening-type viscosity modifiers, while having characteristics similar to those of existing urethane viscosity modifiers (specifically, for instance, good water resistance in a coating film when a product to which the urethane viscosity modifier has been added is made into a coating film, as well as low susceptibility to pH) The present invention also succeed also in providing a urethane viscosity modifier and a urethane viscosity modifier aqueous solution excellent in long-term storage stability, similarly to alkali thickening-type viscosity modifiers, while having characteristics similar to those of existing urethane viscosity modifiers.

(45) <Synthesis of Urethane Polymers>

(46) (Starting Materials Used)

(47) a-1: 50-EO adduct of an alcohol having 32 carbon atoms (2-tetradecyloctadecanol)

(48) a-2: 150-EO adduct of an alcohol having 24 carbon atoms (2-decyltetradecyl)

(49) b-1: polyoxyethylene glycol having a weight-average molecular weight of 11000

(50) c-1: monooctyl glyceryl ether

(51) c-2: monododecyl glyceryl ether

(52) d-1: hexamethylene diisocyanate

(53) d-2: metaphenylene diisocyanate

(54) a′-1: 150-EO adduct of a C22 alcohol (2-decyldodecyl)

(55) c′-1: butyl glyceryl ether

(56) *EO adduct: ethylene oxide adduct

(57) (Synthesis Method)

(58) A four-necked flask having a capacity of capacity 2000 mL and equipped with a thermometer, a nitrogen introduction tube and a stirrer, was charged with 267 g (0.1 moles) of starting material (a-1), 550 g (0.05 moles) of starting material (b-1) and 10.2 g (0.05 moles) of starting material (c-1). The interior of the system was purged with nitrogen, after which the temperature was raised to 80 to 90° C., to melt the charge, with mixing until homogeneity. After verifying that all components were homogeneously mixed, 25 g (0.15 moles) of starting material (d-1) were added into the system, and the system was left to react at the same temperature for 3 hours, to yield a urethane polymer (I-1).

(59) Urethane polymers (I-2) to (I-6) were obtained through synthesis under conditions identical to those of the synthesis of the urethane polymer (I-1), but herein the starting materials and/or blending proportions thereof were modified as given in Table 4. The units of the blending proportion in Table 4 are moles.

(60) TABLE-US-00004 TABLE 4 Starting Urethane-type polymers material I-1 I-2 I-3 I-4 I-5 I-6 a-1 0.1  — 0.1  — 0.1  0.1  a-2 — 0.1  — 0.1  — — b-1 0.05 0.05 0.05 0.05 0.05 0.05 c-1 0.05 0.05 — — 0.02 0.05 c-2 — — 0.05 0.05 0.03 — d-1 0.15 0.15 0.15 0.15 0.15 — d-2 — — — — — 0.15

(61) Urethane polymers for comparison (I′-1) to (I′-5) were obtained through synthesis under conditions identical to those of the synthesis of the urethane polymer (I-1), but herein the starting materials and/or blending proportions thereof were modified as given in Table 5. The units of the blending proportion in Table 5 are moles.

(62) TABLE-US-00005 TABLE 5 Starting Urethane-type polymers for comparison material I′-1 I′-2 I′-3 I′-4 I′-5 a-1 0.1  — 0.1 0.1  — a-2 — 0.1  — — — b-1 0.05 0.05 — 0.05 0.05 c-1 — — — — 0.05 d-1 0.15 0.1 0_05 0.15 0.15 a′-1 — — — — 0.1  c′-1 — — — 0.05 —

(63) <Preparation of Oil-in-Water Emulsified Compositions>

(64) (Starting Materials Used)

(65) I-1 to I-6: synthesized urethane polymers above

(66) I′-1 to I′-5: synthesized urethane polymers for comparison above

(67) I′-6: hydroxymethyl cellulose (trade name: HEC, by Sumitomo Seika Chemicals Co. Ltd.)

(68) I′-7: methyl cellulose (trade name: Mecellose MC, by Tomoe Engineering Co., Ltd.)

(69) I′-8: carboxyvinyl polymer (trade name: Carbopol 980, by The Lubrizol Corporation)

(70) Note) I′-6 to I′-8 are commercially available viscosity modifiers.

(71) II-1: liquid paraffin (0.85 to 0.89 g/ml (20° C.), by Wako Pure Chemical Industries)

(72) II-2: olive oil

(73) III: water

(74) IV-1: 1,2-propylene glycol

(75) IV-2: 1,3-butanediol

(76) IV-3: 1,2-hexanediol

(77) (Preparation Method)

(78) Herein, starting material (III) and starting material (I-1) were charged into a 1000 mL beaker, which was then heated at 50° C. until starting material (I-1) had dissolved completely. Thereafter, starting material (II-1) was added while under stirring at the same temperature. Once addition was over, the whole was stirred continuously for 10 minutes, to yield thereby an oil-in-water emulsified composition (Inventive product 10). The blending proportions (mass %) of the various starting materials were as given in Table 6 below, so as to yield a total 500 g of the oil-in-water emulsified composition.

(79) Oil-in-water emulsified compositions (Inventive products 11 to 20) were obtained by being prepared in accordance with the same preparation method as that of the oil-in-water emulsified composition of Inventive product 10, but herein the starting materials and/or blending proportions thereof were modified as given in Table 6.

(80) TABLE-US-00006 TABLE 6 Inventive products 10 11 12 13 14 15 16 17 18 19 20 I-1  1 — — — — —  1  0.5  1  1  1 I-2 —  1 — — — — — — — — — I-3 — —  1 — — — — — — — — I-4 — —  1 — — — — — — — I-5 — — — —  1 — — — — — — I-6 — — — — —  1 — — — — — II-1 30 30 30 30 30 30 — — 30 30 30 II-2 — — — — — — 30 70   — — — III 69 69 69 69 69 69 69 29.5 64 64 64 IV-1 — — — — — — — —  5 — — IV-2 — — — — — — — — —  5 — IV-3 — — — — — — — — — —  5

(81) Oil-in-water emulsified compositions (Comparative products 9 to 19) were obtained by being prepared in accordance with the same preparation method as that of the oil-in-water emulsified composition of Inventive product 10, but herein the starting materials and/or blending proportions thereof were modified as given in Table 7.

(82) TABLE-US-00007 TABLE 7 Comparative products 9 10 11 12 13 14 15 16 17 18 19 I-1  1 — — — — — — — — — — I-2 —  1 — — — — — —  1 — — I-3 — —  1 — — — — — — — — I-4 — — —  1 — — — — — — — I-5 — — — —  1 — — — — — — I-6 — — — — —  1 — — —  1 — I-7 — — — — —  1 — — — — I-8 — — — — — — —  1 — —  1 II-1 30 30 30 30 30 30 30 30 30 30 30 III 69 69 69 69 69 69 69 69 64 64 64 IV - 2 — — — — — — — —  5  5  5

Example 3: Evaluation of the Stability of Oil-in-Water Emulsified Compositions

(83) The prepared oil-in-water emulsified compositions of the above inventive products and comparative products were sealed in 100 mL screw tubes, and were left to stand in a thermostatic bath at 25° C. The state of each oil-in-water emulsified composition one hour, one week, one month, two months, three months and four months after having been set in the thermostatic bath was observed visually, and was evaluated in accordance with the below-described criteria.

(84) ◯: no change in the emulsified state

(85) Δ: transparent oil phase slightly appreciable at the top of the oil-in-water emulsified composition

(86) x: complete separation of aqueous phase and oil phase

(87) The evaluation results are given in Table 8. Instances of complete separation between the aqueous phase and the oil phase (rating x) were not further evaluated thereafter.

(88) TABLE-US-00008 TABLE 8 Evaluation results for stability 1 hour 1 week 1 month 2 months 3 months 4 months Inventive product 10 ◯ ◯ ◯ ◯ Δ X Inventive product 11 ◯ ◯ ◯ ◯ Δ X Inventive product 12 ◯ ◯ ◯ ◯ Δ X Inventive product 13 ◯ ◯ ◯ ◯ Δ X Inventive product 14 ◯ ◯ ◯ ◯ Δ X Inventive product 15 ◯ ◯ ◯ ◯ Δ X Inventive product 16 ◯ ◯ ◯ ◯ Δ X Inventive product 17 ◯ ◯ ◯ ◯ Δ X Inventive product 18 ◯ ◯ ◯ ◯ ◯ Δ Inventive product 19 ◯ ◯ ◯ ◯ ◯ ◯ Inventive product 20 ◯ ◯ ◯ ◯ ◯ Δ Comparative product 9 ◯ ◯ Δ X — — Comparative product 10 ◯ ◯ Δ X — — Comparative product 11 ◯ ◯ Δ X — — Comparative product 12 ◯ ◯ Δ X — — Comparative product 13 ◯ ◯ Δ X — — Comparative product 14 X — — — — — Comparative product 15 X — — — — — Comparative product 16 X — — — — — Comparative product 17 ◯ ◯ Δ X — — Comparative product 18 X — — — — — Comparative product 19 X — — — — —

(89) As the results of Table 8 indicate, the oil-in-water emulsified compositions of inventive products exhibit superior stability, in that separation between the aqueous phase and the oil phase is less likely to occur, over long periods of time, than in the case in the oil-in-water emulsified compositions of comparative products.

(90) <Preparation of Oil-in-Water Emulsified Compositions Containing a Powder>

(91) Next, oil-in-water emulsified compositions were prepared that contained a powder resulting from thorough mixing, in equal amounts, silicone-treated talc, silicone-treated mica, silicone-treated sericite and silicone-treated titanium oxide (all products of SA-series, by Miyoshi Kasei, Inc.), and the stability of the prepared compositions was evaluated.

(92) (Preparation Method)

(93) Herein, starting material (III) and starting material (I-1) were charged into a 1000 mL beaker, which was then heated at 50° C. until starting material (I-1) had dissolved completely. Thereafter, starting material (II-1) was added while under stirring at the same temperature. Once addition was over, the whole was stirred continuously for 10 minutes, and, thereafter, the powder was added, with continuous stirring for a further 10 minutes, to cause the powder to disperse homogeneously, and yield as a result an oil-in-water emulsified composition (Inventive product 21). The blending proportions (mass %) of the various starting materials were as given in Table 9 below, so as to yield a total 500 g of the oil-in-water emulsified composition.

(94) Oil-in-water emulsified compositions containing a powder (Inventive products 22 to 31) were obtained by being prepared in accordance with the same preparation method as that of the oil-in-water emulsified composition of Inventive product 21, but herein the starting materials and/or blending proportions thereof were modified as given in Table 9.

(95) TABLE-US-00009 TABLE 9 Inventive products 21 22 23 24 25 26 27 28 29 30 31 I-1  1 — — — — —  1 0.5  1  1  1 I-2 —  1 — — — — — — — — — I-3 — —  1 — — — — — — — — I-4 — — —  1 — — — — — — — I-5 — — — —  1 — — — — — — I-6 — — — — —  1 — — — — — II-1 15 15 15 15 15 15 — — 15 15 15 II-2 — — — — — — 15 35 — — — III 69 69 69 69 69 69 69 29.5 64 64 64 IV-1 — — — — — — — —  5 — — IV-2 — — — — — — — — —  5 — IV-3 — — — — — — — — — —  5 Powder 15 15 15 15 15 15 15 35 15 15 15

(96) Oil-in-water emulsified compositions containing a powder (Comparative products 20 to 30) were obtained by being prepared in accordance with the same preparation method as that of the oil-in-water emulsified composition of Inventive product 21, but herein the starting materials and/or blending proportions thereof were modified as given in Table 10.

(97) TABLE-US-00010 TABLE 10 Comparative products 20 21 22 23 24 25 26 27 28 29 30 I′-1  1 — — — — — — — — — — I′-2 —  1 — — — — — —  1 — — I′-3 — —  1 — — — — — — — — I′-4 — — —  1 — — — — — — — I′-5 — — — —  1 — — — — — — I′-6 — — — — —  1 — — —  1 — I′-7 — — — — — —  1 — — — — I′-8 — — — — — — —  1 — —  1 II-1 15 15 15 15 15 15 15 15 15 15 15 III 69 69 69 69 69 69 69 69 64 64 64 IV-2 — — — — — — — —  5  5  5 Powder 15 15 15 15 15 15 15 35 15 15 15

Example 4: Evaluation of the Stability of Oil-in-Water Emulsified Compositions Containing a Powder

(98) The prepared oil-in-water emulsified compositions containing a powder of the above inventive products and comparative products were sealed in 100 mL screw tubes, and were left to stand in a thermostatic bath at 25° C. The state of each oil-in-water emulsified composition after one hour, one week, one month, two months, three months and four months after having been set in the thermostatic bath was observed visually, and was evaluated in accordance with the below-described criteria.

(99) ◯: powder homogeneously dispersed

(100) Δ: transparent oil phase slightly appreciable at the top of the oil-in-water emulsified composition

(101) x: powder precipitated, and clearly observable separated oil phase at the top of the oil-in-water emulsified composition

(102) The evaluation results are given in Table 11. Instances of powder precipitation (rating x) were not further evaluated thereafter.

(103) TABLE-US-00011 TABLE 11 Evaluation results for stability 1 hour 1 week 1 month 2 months 3 months 4 months Inventive product 21 ◯ ◯ ◯ Δ X — Inventive product 22 ◯ ◯ ◯ Δ X — Inventive product 23 ◯ ◯ ◯ Δ X — Inventive product 24 ◯ ◯ ◯ Δ X — Inventive product 25 ◯ ◯ ◯ Δ X — Inventive product 26 ◯ ◯ ◯ Δ X — Inventive product 27 ◯ ◯ ◯ Δ X — Inventive product 28 ◯ ◯ ◯ ◯ Δ X Inventive product 29 ◯ ◯ ◯ ◯ ◯ Δ Inventive product 30 ◯ ◯ ◯ ◯ ◯ ◯ Inventive product 31 ◯ ◯ ◯ ◯ ◯ Δ Comparative product 20 ◯ X — — — — Comparative product 21 ◯ X — — — — Comparative product 22 ◯ X — — — — Comparative product 23 ◯ X — — — — Comparative product 24 ◯ X — — — — Comparative product 25 X — — — — — Comparative product 26 X — — — — — Comparative product 27 X — — — — — Comparative product 28 ◯ X — — — — Comparative product 29 X — — — — — Comparative product 30 X — — — — —

(104) As the results of Table 11 reveal, the oil-in-water emulsified compositions of inventive products exhibited superior stability, in that powder precipitation and/or separation between the aqueous phase and the oil phase is less likely to occur, over long periods of time, than in the case in the oil-in-water emulsified compositions of the comparative products.

(105) The above results indicate that the present invention succeeds in providing an oil-in-water emulsified composition having excellent product stability and in which a powder that is added to the composition can be dispersed stably over long periods of time, without using any surfactant as an emulsifier, and in providing a cosmetic that contains the oil-in-water emulsified composition.

(106) The present international application claims priority based on Japanese Patent Application No. 2012-261244, filed with the JPO on Nov. 29, 2012, and Japanese Patent Application No. 2013-090006, filed with the JPO on Apr. 23, 2013, the entire contents thereof being incorporated herein by reference.