POLYMER

Abstract

The present application relates to a polymer, a method for preparing the same, and a use thereof. The present application provides a polymer, a method for preparing the same, and a use thereof. The present application can provide: a polymer, which has a composition for allowing a low solubility in polar and non-polar solvents and can be prepared in a simple polymerization manner, such as solution polymerization; and a use thereof.

Claims

1. A polymer comprising polymerized units of a first monomer of which homopolymer has a solubility parameter of less than 10.0 (cal/cm.sup.3).sup.1/2; polymerized units of a second monomer of which homopolymer has a solubility parameter of 10.0 (cal/cm.sup.3).sup.1/2 or more; and polymerized units of a vinyl monomer.

2. The polymer according to claim 1, wherein the vinyl monomer is an amide-based monomer, an ester-based monomer or an ether-based monomer.

3. The polymer according to claim 1, wherein the vinyl monomer is represented by Formula 6 below: ##STR00006## wherein, X is a nitrogen atom or an oxygen atom, Y is a carbonyl group or a single bond, R.sub.1 and R.sub.3 are each independently hydrogen or an alkyl group, or R.sub.1 and R.sub.3 are linked together to form an alkylene group, and R.sub.2 is an alkenyl group (provided that when X is an oxygen atom, R.sub.1 is not present).

4. The polymer according to claim 3, wherein in Formula 6 X is a nitrogen atom, Y is a carbonyl group, R.sub.1 and R.sub.3 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R.sub.2 is an alkenyl group having 2 to 8 carbon atoms.

5. The polymer according to claim 3, wherein in Formula 6 X is a nitrogen atom, Y is a carbonyl group, R.sub.1 and R.sub.3 are linked to each other to form an alkylene group having 3 to 12 carbon atoms, and R.sub.2 is an alkenyl group having 2 to 8 carbon atoms.

6. The polymer according to claim 3, wherein in Formula 6 X is an oxygen atom, Y is a single bond or a carbonyl group, R.sub.3 is an alkyl group having 1 to 20 carbon atoms, and R.sub.2 is an alkenyl group having 2 to 8 carbon atoms.

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

8. The polymer according to claim 1, wherein the first monomer is a compound represented by Formula 1 below: ##STR00007## 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 1, wherein the homopolymer of the second monomer has a 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.

10. The polymer according to claim 1, wherein the second monomer is a compound represented by Formula 2 or 3 below: ##STR00008## 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: ##STR00009## 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.

11. The polymer according to claim 1, comprising 50 to 99.9 parts by weight of the polymerized units of the first monomer, 0.1 to 20 parts by weight of the polymerized units of the second monomer and 1 to 30 parts by weight of the polymerized units of the vinyl monomer.

12. The polymer according to claim 1, further comprising polymerized units of a compound of Formula 5 below: ##STR00010## wherein, R.sub.1 to R.sub.6 are each independently hydrogen, a hydroxy group, an alkyl group, an alkoxy group, an alkenyl group, a (meth)acryloyl group, a (meth)acryloylalkyl group, a (meth)acryloyloxy group or a (meth)acryloyloxyalkyl group, provided that at least one is an alkenyl group, a (meth)acryloyl group, a (meth)acryloylalkyl group, a (meth)acryloyloxy group or a (meth)acryloyloxyalkyl group, and n is a number in a range of 0 to 20.

13. The polymer according to claim 1, 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.

14. The polymer according to claim 1, wherein the solubility is 20 or more in a solvent having a dielectric constant (25° C.) in a range of 4 to 15.

15. A method for preparing a polymer comprising a step of solution-polymerizing a monomer mixture comprising a first monomer of which homopolymer has a solubility parameter of less than 10.0 (cal/cm.sup.3).sup.1/2, a second monomer of which homopolymer has a solubility parameter of 10.0 (cal/cm.sup.3).sup.1/2 or more and a vinyl monomer in a solvent.

16. The method for preparing a polymer according to claim 15, wherein the vinyl monomer is an amide-based monomer, an ester-based monomer or an ether-based monomer.

17. The method for preparing a polymer according to claim 15, wherein the vinyl monomer is represented by Formula 6 below: ##STR00011## wherein, X is a nitrogen atom or an oxygen atom, Y is a carbonyl group or a single bond, R.sub.1 and R.sub.3 are each independently hydrogen or an alkyl group, or R.sub.1 and R.sub.3 are linked together to form an alkylene group, and R.sub.2 is an alkenyl group (provided that when X is an oxygen atom, R.sub.1 is not present).

18. The method for preparing a polymer according to claim 15, wherein the solvent has a dielectric constant (25° C.) in a range of 1 to 3.

19. The method for preparing a polymer according to claim 15, wherein the solvent is liquid paraffin.

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

Description

MODE FOR INVENTION

[0081] 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.

[0082] 1. Solubility Measurement of Polymer

[0083] Polymer solutions prepared in Examples or Comparative Examples were kept at a temperature of about 150° C. for about 60 minutes to volatilize the solvent. Subsequently, 1 g of the polymer, solvent volatilized, is collected. Subsequently, 1 g of the above collected polymer was 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 was un-dissolved, was removed. The transparent solution with removing the remaining polymer was sampled and dried at 150° C. for 30 minutes to remove the solvent, and the solid content was calculated through mass comparison. The concentration of the polymer dissolved in the solvent was measured through the solid content and the solubility was obtained by converting the measured amount to a value for 100 g of the solvent. If the solution was not transparent even after removing the remaining polymer, the solution was passed through a filter (0.45 μm NYLON) to obtain the transparent solution, and then the above process was carried out.

[0084] <Solubility Evaluation Criteria>

[0085] A: when the solubility is 15 or more

[0086] B: when the solubility is more than 10 and less than 15

[0087] C: when the solubility is more than 5 and up to 10

[0088] D: when the solubility is up to 5

[0089] 2. Molecular Weight Measurement

[0090] 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.

[0091] <Measurement Conditions>

[0092] Measuring instrument: Agilent GPC (Agilent 1200 series, U. S.)

[0093] Column: PL Mixed B two connected

[0094] Column temperature: 40° C.

[0095] Eluant: THF (Tetrahydrofuran)

[0096] Flow rate: 1.0 mL/min

[0097] Concentration: ˜1 mg/mL (100 μL injection)

[0098] 3. Calculation of Glass Transition Temperature

[0099] The glass transition temperature (Tg) was calculated depending on the monomer composition by the following Equation.

1/Tg=ΣWn/Tn  <Equation>

[0100] 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.

[0101] 4. Sebum Blurring Test

[0102] 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.

[0103] 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.

[0104] In-Vitro Test

[0105] 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.

[0106] <Evaluation Criteria>

[0107] 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.

[0108] In-Vivo Test:

[0109] 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.

[0110] <Evaluation Criteria>

[0111] 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.

[0112] 5. Water Resistance Test

[0113] 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).

[0114] <Evaluation Criteria>

[0115] A: when the mass decrease rate is at least 5%

[0116] B: when the mass decrease rate exceeds 5%

[0117] 6. NMR Evaluation Method

[0118] 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 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.

[0119] <Measurement Conditions>

[0120] Analysis instrument: 500 MHz NMR (Varian Unity Inova 500), 1H-NMR

[0121] Concentration: 10˜20 mg/mL, solvent: CDCl3

[0122] Temperature: 25° C.

[0123] Preparation of Polymers of Examples 1 to 3 and Comparative Example 1

[0124] The type of monomers and their portions applied to the polymers are shown in Table 1 below. As shown in Table 1, monomers are mixed and then introduced into isododecane as a solvent to have a monomer concentration of 35% by weight, and an appropriate amount of a thermal initiator (V-65, 2,2′-azobis(2,4-dimethyl valeronitrile) is introduced thereto and then the reactor is sealed. Subsequently, the dissolved oxygen is removed by bubbling with nitrogen at room temperature for about 30 minutes together with stirring and the nitrogen bubbling is further carried out for about 40 minutes while elevating the reaction mixture removing oxygen to a temperature of about 70° C. When the temperature increases to 70° C. through the above process, the polymerization reaction proceeds by the thermal initiator dissolved in the solvent. After performing the reaction for about 24 hours, the reaction is stopped by decreasing the temperature to room temperature. As a result of polymerizing polymers according to the compositions as shown in Table below and the above described methods, in the case of Comparative Example 1, the polymerization between monomers was not properly achieved and the monomers and the like were precipitated in the polymerization process, and thus the synthesis of the polymer was impossible.

TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 1 Polymer A B C D LMA 19 12 EHMA 30 27 IBOMA 55 55 64 66 PEGMA 5 10 12 10 EOEOEA 12 NVP 10 8 VA 5 Content unit: g LMA: lauryl methacrylate (solubility parameter of a homopolymer: 8.2 (cal/cm.sup.3).sup.1/2) EHMA: ethylhexyl methacrylate (solubility parameter of a homopolymer: 8.3 (cal/cm.sup.3).sup.1/2) IBOMA: isobornyl methacrylate (solubility parameter of a homopolymer: 8.1 (cal/cm.sup.3).sup.1/2) EOEOEA: ethoxyethoxy ethylacrylate (solubility parameter of a homopolymer: 10.6 (cal/cm.sup.3).sup.1/2) PEGMA: polyethyleneglycol monoethyl ether methacrylate (ethylene oxide unit addition mole: 9 moles, solubility parameter of a homopolymer: 10.8 (cal/cm.sup.3).sup.1/2) NVP: N-vinylpyrrolidone VA: vinyl acetate

[0125] 1. Evaluation of NMR

[0126] It can be seen that as a result of evaluating NMR for the polymer of Example 1 no 1H peak derived from ═CH2 of the double bond terminus is identified, whereby it can be confirmed that the polymerization has been carried out effectively. In addition, —CH2— and —CH— peaks adjacent to —COO— of EHMA and IBOMA forming the polymer and peaks derived from —OCH2CH2—O and —OCH3 of PEGMA were identified in the region of 5.0 pm to 2.8 ppm as an area value of 14. Furthermore, peaks derived from —NCH2— of NVP were identified in the region of 5.0 ppm to 2.8 ppm as an area value of 11. Meanwhile, 1H area value identified from —CH2CH— and —CH2CH2— derived from the polymer backbone, was 51 in 1.5 ppm to 0.5 ppm.

[0127] In the case of the polymer of Example 2, 1H peaks derived from ═CH2 of the double bond terminus were also little identified, —CH— peaks adjacent to —COO— of EHMA and IBOMA, —OCH2CH2—O and —OCH3 peaks of PEGMA, and peaks derived from —NCH2— of NVP were shown in the region of 5.0 ppm to 2.8 ppm, and the area value of peaks was 9. In addition, from —CH2— of the side chain and —CH3 derived from the meta-position, peaks having an area value of 37 were identified in the region of 2.5 ppm to 1.5 ppm, and 1H area value identified from —CH2CH— and —CH2CH2— derived from the polymer backbone was 54 in 1.5 ppm to 0.5 ppm.

[0128] In the case of Example 3, no 1H peak derived from ═CH2 of the double bond terminus was also observed, and —CH— peaks adjacent to —COO— of LMA and IBOMA, —OCH2CH2—O and —OCH3 peaks of PEGMA, and —COO—CH3 peak of VA were identified in the region of 5.0 ppm to 2.8 ppm as an area value of 11. In addition, from —CH2— of the side chain and —CH3 derived from the meta-position, peaks having an area value of 37 were identified in the region of 2.5 ppm to 1.5 ppm, and 1H area value identified from —CH2CH— and —CH2CH2— derived from the polymer backbone was 52 in 1.5 ppm to 0.5 ppm.

[0129] 2. Physical Property Evaluation Results

[0130] The results of measuring physical properties for each polymer of Examples were summarized and described in Table 2 below. However, in the case of Comparative Example, as monomers and the like were precipitated in the process of preparing the polymer, the polymerization was not achieved, and thus the evaluation of physical properties could not be performed. It can be confirmed from the following 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.

TABLE-US-00002 TABLE 2 Com- parative Example Example 1 2 3 1 Polymer A B C D Solubility Hexane C C C — Ethyl A A A — acetate Acetone B B B — Water C C C — Weight average 300,000 320,000 250,000 — molecular weight Glass transition 45 36 37 — temperature (° C.) Sebum blurring In-vitro 4.2 4.3 4.5 — test In-vivo 2200 2100 1700 — Water resistance test A A A —