POLYMER

Abstract

The present application relates to a polymer and a use thereof. The present application may provide a functional polymer which expresses a low solubility to a polar solvent and a non-polar solvent. If applied to the use of cosmetics such as mascara or to medical uses, the polymer in the present application may express a tolerance to diverse solvents such as sebum, sweat, tears and the like, and thus enables makeup to last, etc. Accordingly, the polymer may be applied to diverse uses and used in film forming agents, cosmetic compositions, or cosmetics, or the like.

Claims

1. A polymer comprising polymerized units of a first monomer having a homopolymer solubility parameter of less than 10.0 (cal/cm.sup.3).sup.1/2 and polymerized units of a second monomer having a homopolymer solubility parameter of 10.0 (cal/cm.sup.3).sup.1/2 or more, wherein the solubility at room temperature is 10 or less in a solvent having a dielectric constant (25° C.) in a range of 1 to 3, and the solubility at room temperature is 10 or less in a solvent having a dielectric constant (25° C.) in a range of 75 to 85.

2. The polymer according to claim 1, wherein the solubility at room temperature is 5 or less in a solvent having a dielectric constant (25° C.) in a range of 1 to 3.

3. The polymer according to claim 1, wherein the solubility at room temperature is 5 or less in a solvent having a dielectric constant (25° C.) in a range of 75 to 85.

4. The polymer according to claim 1, wherein the solubility at room temperature is 15 or more in a solvent having a dielectric constant (25° C.) in a range of 4 to 15.

5. The polymer according to claim 1, wherein the first monomer has a homopolymer solubility parameter in a range of 5 (cal/cm3).sup.1/2 to 9.5 (cal/cm.sup.3).sup.1/2.

6. The polymer according to claim 1, wherein the first monomer has a homopolymer solubility parameter in a range of 7 (cal/cm3).sup.1/2 to 9 (cal/cm.sup.3).sup.1/2.

7. The polymer according to claim 1, wherein the first monomer is alkyl (meth)acrylate or aromatic (meth)acrylate.

8. The polymer according to claim 1, wherein the first monomer is a compound represented by Formula 1 below: ##STR00004## wherein, Q is hydrogen or an alkyl group, B is a straight or branched alkyl group having 4 or more carbon atoms, an alicyclic hydrocarbon group, or an aromatic substituent.

9. The polymer according to claim 8, wherein the aromatic substituent is an aryl group or an arylalkyl group.

10. The polymer according to claim 8, wherein in Formula 1 Q is hydrogen or a methyl group and B is an alkyl group having 7 or more carbon atoms or an alicyclic hydrocarbon group having 6 to 18 carbon atoms.

11. The polymer according to claim 1, wherein the second monomer has a homopolymer solubility parameter in a range of 10.0 (cal/cm.sup.3).sup.1/2 to 15.0 (cal/cm.sup.3).sup.1/2.

12. The polymer according to claim 1, wherein the second monomer has a homopolymer solubility parameter in a range of 10.0 (cal/cm.sup.3).sup.1/2 to 13.0 (cal/cm.sup.3).sup.1/2.

13. The polymer according to claim 1, wherein the second monomer is a compound represented by Formula 2 or 3 below: ##STR00005## wherein Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen or an alkyl group, and m is any number: ##STR00006## wherein Q is hydrogen or an alkyl group, A and U are each independently an alkylene group, and X is a hydroxy group or a cyano group.

14. The polymer according to claim 13, wherein in Formula 2 Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms and m is a number in a range of 1 to 30.

15. The polymer according to claim 1, comprising 50 to 99.9 parts by weight of the polymerized units of the first monomer and 0.1 to 20 parts by weight of the polymerized units of the second monomer.

16. The polymer according to claim 1, comprising 70 to 99.9 parts by weight of the polymerized units of the first monomer and 5 to 20 parts by weight of the polymerized units of the second monomer.

17. A film forming agent comprising the polymer of claim 1.

Description

MODE FOR INVENTION

[0048] Hereinafter, the polymers of the present application and the like will be specifically explained through Examples and Comparative Examples, but the scope of the polymer is not limited to the following examples. In Examples and Comparative Examples below, each physical property was evaluated by the following methods.

[0049] 1. Solubility Measurement of Polymer

[0050] Polymer solutions prepared in Examples or Comparative Examples are kept at a temperature of about 150° C. for about 60 minutes to volatilize the solvent. 1 g of the polymer volatilizing the solvent is collected. 1 g of the above collected polymer is added to 5 g of a solvent (hexane, ethyl acetate, acetone or water) and stirred at room temperature for 30 minutes, and then the remaining polymer, which is un-dissolved, is removed. The transparent solution with removing the remaining polymer is sampled and dried at 150° C. for 30 minutes to remove the solvent. Through mass comparison of the remaining polymer in the solution removing the solvent the solid content is calculated. The concentration of the polymer dissolved in the solvent is measured through the solid content and the solubility is obtained by converting the measured amount to a value for 100 g of the solvent. If the solution is not transparent even after removing the remaining polymer, the solution is passed through a filter (0.45 μm NYLON) to obtain the transparent solution, and then the above process is carried out.

[0051] <Solubility Evaluation Criteria>

[0052] A: when the solubility is 15 or more

[0053] B: when the solubility is more than 10 and less than 15

[0054] C: when the solubility is more than 5 and up to 10

[0055] D: when the solubility is up to 5

[0056] 2. Molecular Weight Measurement

[0057] The weight average molecular weight (Mw) and molecular weight distribution (PDI) were measured under the following conditions by using GPC, and the measurement results were converted by using the standard polystyrene of Agilent system in preparing a calibration curve.

[0058] <Measurement Conditions>

[0059] Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

[0060] Column: PL Mixed B two connected

[0061] Column temperature: 40° C.

[0062] Eluant: THF (Tetrahydrofuran)

[0063] Flow rate: 1.0 mL/min

[0064] Concentration: ˜1 mg/mL (100 μL injection)

[0065] 3. Calculation of glass transition temperature

[0066] The glass transition temperature (Tg) was calculated depending on the monomer composition by the following Equation.

1/Tg=ΣWn/Tn   <Equation>

[0067] wherein Wn is a weight fraction of each monomer in the polymer, Tn is a glass transition temperature appearing when the monomer has formed a homopolymer, and the right-hand side of the equation is a result of summing all the calculated values after calculating the value (Wn/Tn) obtained by dividing the weight fraction of the used monomer by the glass transition temperature appearing when the monomer has formed a homopolymer for each monomer.

[0068] 4. Sebum Blurring Test

[0069] Composition A is prepared by dissolving a polymer prepared in each preparation example in isododecane as a solvent in a concentration of about 10% by weight, and dissolving ceresine, a synthetic wax and a microcrystalline wax in concentrations of 7% by weight, 6% by weight and 8% by weight, respectively at a temperature of about 90° C. Subsequently, Composition B is prepared by adding propylene carbonate and disteardimonium hectorite to the Composition A in concentrations of 8% by weight and 2% by weight, respectively and dispersing them uniformly for 20 minutes. Subsequently, iron oxide (CI 77499) is added thereto in a concentration of 6% by weight and then an appropriate amount of preservatives is added, followed by being dispersed for 30 minutes and then slowly cooled to about 28° C., to prepare a mascara formulation.

[0070] Sebum blurring test using the prepared mascara formulation was divided into an in-vitro test and an in-vivo test and carried out, the details of which are as follows.

[0071] In-Vitro Test

[0072] The mascara formulation is applied on a slide glass (glass plate) to a thickness of 30 μm and then completely dried at room temperature. After drying, water and sebum are dropped on the mascara by 0.1 g, respectively, and after being left to stand for 20 minutes, a cotton pad is placed thereon and reciprocated 30 times with a force of 200 gf, and then the degrees of being smeared on the cotton pad are compared and evaluated in accordance with the following criteria.

[0073] <Evaluation Criteria>

[0074] When the degrees of being smeared on the cotton pad were compared on a scale within a range of 0 to 5, by setting the case of smearing no mascara at all on the cotton pad to 5 and setting the case of applying the polymer of the following comparative example 1 as a control group (reference) to 3, the superior level relative to the control group was quantified to one decimal place as a relative comparison between samples.

[0075] In-Vivo Test:

[0076] Images are taken 6 hours after applying the prepared mascara formulation on eyelashes of a test subject, compared and evaluated according to the following criteria.

[0077] <Evaluation Criteria>

[0078] After a lapse of 6 hours, images are taken and shown as values by image-analyzing blurring areas. On image-analyzing, the area of blurring was quantified as a pixel unit and shown.

[0079] 5. Water Resistance Test

[0080] The above prepared mascara formulation is applied on a slide glass (glass plate) to a thickness of 30 μm and then completely dried at room temperature, and the dried sample is immersed in water at room temperature for about 30 minutes and then taken out to evaluate the water resistance depending on the following criteria according to mass decrease rates (=100×(1−B/A), unit:%, wherein A is the total mass of the slide glass applying the mascara formulation and B is the total mass of the slide glass measured after immersing it in water, then taking out and removing moisture).

[0081] <Evaluation Criteria>

[0082] A: when the mass decrease rate is at least 5%

[0083] B: when the mass decrease rate exceeds 5%

[0084] 6. NMR Evaluation Method

[0085] 0.1 g of the polymer solution prepared in Examples or Comparative Examples is collected and dissolved in 1 mL of the following solvent for NMR, and .sup.1H-NMR is measured according to the manufacturer's manual by using the following analysis instrument, whereby the components and conversion rate of the polymer can be identified. For example, when the non-polymerized monomer is present, a —H peak derived from ═CH2 of a double bond terminus in 1H-NMR spectrum is identified near at about 5.7 ppm to 6.4 ppm, and it is possible to identify the components of the prepared polymer through the area of —H peaks derived from each polymer structure.

[0086] <Measurement Conditions>

[0087] Analysis instrument: 500 MHz NMR (Varian Unity Inova 500), 1H-NMR

[0088] Concentration: 10˜20 mg/mL, solvent: CDCl3-d3

[0089] Temperature: 25° C.

EXAMPLE 1

[0090] As shown in Table 1 below, a monomer mixture in which EHMA (ethylhexyl methacrylate), IBOMA (isobornyl methacrylate) and EOEOEA (ethoxyethoxyethyl acrylate) were mixed in a weight ratio (EHMA:IBOMA:EOEOEA) of 25:60:15 was introduced into isododecane as a solvent to have the total monomer concentration of 35% by weight, and subsequently, the dissolved oxygen was removed by bubbling with nitrogen at room temperature for about 30 minutes together with stirring and the nitrogen bubbling was further carried out for about 40 minutes while elevating the reaction mixture removing oxygen to a temperature of about 70° C. If the temperature increased to 70° C. through the above process, the polymerization reaction proceeded while further introducing an appropriate amount of a thermal initiator (V-65) into isododecane as a solvent. After performing the reaction for about 24 hours, the reaction was completed by decreasing the temperature to room temperature to obtain a polymer solution.

EXAMPLES 2 TO 4 AND COMPARATIVE EXAMPLES 1 TO 3

[0091] The polymer solutions were obtained in the same manner as Example 1 except that the monomer types and proportions of the monomer mixture were changed as Table 1 below.

TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 4 1 2 3 Polymer A B C D E F G EHA 15 LMA 20 15 12 EHMA 30 CHMA 75 IBOMA 60 74 75 66 EOEOEA 10 10 10 10 PEGMA 6 12 TMSS 100 PVP 100 Mw 34 30 20 20 — — — Tg 39 31 38 42 40 175 — Content unit: g EHA: ethyl hexyl acrylate (homopolymer solubility parameter: 8.4 (cal/cm.sup.3).sup.1/2) LMA: lauryl methacrylate (homopolymer solubility parameter: 8.2 (cal/cm.sup.3).sup.1/2) EHMA: ethylhexyl methacrylate (homopolymer solubility parameter: 8.3 (cal/cm.sup.3).sup.1/2) CHMA: cyclohexyl methacrylate (homopolymer solubility parameter: 7.9 (cal/cm.sup.3).sup.1/2) IBOMA: isobornyl methacrylate (homopolymer solubility parameter: 8.1 (cal/cm.sup.3).sup.1/2) EOEOEA: ethoxyethoxy ethylacrylate (homopolymer solubility parameter: 10.6 (cal/cm.sup.3).sup.1/2) PEGMA: polyethyleneglycol monoethyl ether methacrylate (ethylene oxide unit addition mole: 9 moles, homopolymer solubility parameter: 10.8 (cal/cm.sup.3).sup.1/2) TMSS: trimethylsiloxysilicate (homopolymer solubility parameter: 7.5 (cal/cm.sup.3).sup.1/2) (Trimethyl siloxysilicate: Dow Corning MQ-1600 Resin) PVP: polyvinyl pyrrolidone (homopolymer solubility parameter: 11 (cal/cm.sup.3).sup.1/2, Aldrich K30) Mw: weight average molecular weight (×10000) Tg: glass transition temperature (unit: ° C.)

[0092] 1. Evaluation of NMR

[0093] As a result of evaluating NMR for the polymer of Example 1 1H peaks derived from ═CH2 of the double bond terminus were little identified, whereby it can be confirmed that the polymerization has been carried out effectively. In addition, —CH— peaks adjacent to —COO— of EHMA and IBOMA forming the polymer and peaks derived from —OCH2CH2O— of EOEOEA were observed in the region of 5.0 μm to 3.5 ppm, where an area value of peaks is 9. Furthermore, peaks derived from —CH2- of the side chain and —CH3 derived from the meta-position were identified in the region of 2.5 ppm to 1.3 ppm as peaks having an area value of 36, and 1H peaks identified from —CH2CH— and —CH2CH2- derived from the polymer backbone, were identified in the region of 1.3 ppm to 0.5 ppm as an area of 55.

[0094] For the polymer of Example 2, NMR was also equally evaluated. As a result of evaluation, 1H peaks derived from ═CH2 of the double bond terminus were little identified, whereby it could be confirmed that the polymerization has been carried out efficiently. In addition, —CH— peaks adjacent to —COO— of EHA and CHMA forming the polymer and peaks derived from —OCH2CH2O— of EOEOEA were identified in the region of 4.8 ppm to 3.4 ppm as an area value of 10. Furthermore, from —CH2- adjacent to —COO— of EHA forming the polymer, peaks having an area value of about 3 were identified in the region o 2.5 ppm to 2.0 ppm, and from —CH2- of the side chain and —CH3 derived from the meta-position, peaks having an area value of 57 were identified in the region of 2.0 ppm to 1.5 ppm. Furthermore, 1H area value identified from —CH2CH— and —CH2CH2- derived from the polymer backbone was about 29 in 1.5 ppm to 0.5 ppm.

[0095] In the case of the polymer of Example 3, 1H peaks derived from ═CH2 of the double bond terminus were little identified. In addition, —CH2- and —CH— peaks adjacent to —COO— of LMA and IBOMA forming the polymer and peaks derived from —OCH2CH2-O and —OCH3 of PEGMA appeared in the region of 4.7 ppm to 3.3 ppm, and the area value of the peaks was 17. Furthermore, peaks from —CH2- of the side chain and —CH3 derived from the meta-position were identified in the region of 2.0 ppm to 1.5 ppm as an area value of 72, and the area value of 1H peaks identified from —CH2CH— derived from the polymer backbone was 11 in the region of 1.5 ppm to 0.5 ppm.

[0096] In results of measuring NMR for the polymer of Example 4, 1H peaks derived from ═CH2 of the double bond terminus were also little observed. In addition, —CH2- and —CH— peaks adjacent to —COO— of LMA and IBOMA forming the polymer and peaks derived from —OCH2CH2O— of EOEOEA appeared in the region of 4.7 ppm to 3.3 ppm, and the area value of the peaks was 9. Furthermore, from —CH2- of the side chain and —CH3 derived from the meta-position, peaks having an area value of 36 were identified in the region of 2.0 ppm to 1.5 ppm, and 1H area value identified from —CH2CH— and —CH2CH2- derived from the polymer backbone was 55 in 1.5 ppm to 0.5 ppm.

[0097] Meanwhile, in the case of Comparative Example 3, the polymerization between monomers was not appropriately achieved, and monomers and the like were precipitated in the polymerization process, and thus the synthesis of the polymer was impossible.

[0098] 2. Physical Property Evaluation Results

[0099] The results of measuring physical properties for each polymer of Examples and Comparative Examples were summarized and described in Table 2 below.

TABLE-US-00002 TABLE 2 Comparative Example Example 1 2 3 4 1 2 Polymer A B C D E F Solubility Hexane D C D D A D Ethyl acetate A A A A A D Acetone C D D D A D Water D D D D D A Sebum In-vitro 3.9 4.0 3.8 4.0 3.0 3.3 blurring In-vivo 3200 3100 3200 3000 4500 3800 Water resistance test A A A A A B

[0100] It can be confirmed from the above results that in the case of the polymer satisfying the requirements of the present application, it exhibits a low solubility in polar solvents (water, acetone) and non-polar solvents (hexane) and exhibits an excellent solubility in solvents (ethyl acetate) having middle characteristics. Also, if such a polymer was applied, it was confirmed to have an excellent sebum resistance even in the sebum blurring test while securing water resistance.