Polymer Material

Abstract

The present application relates to a polymer material and a use thereof. The present application can provide a polymer material having both excellent biodegradability and absorptivity by using a polysaccharide component capable of efficient cross-linking while using no cross-linking agent that can adversely affect biodegradability, or using the relevant component to the minimum. The present application can also provide a use of the polymer material.

Claims

1. A polymer material comprising a polysaccharide component, wherein a centrifuge retention capacity of the polymer material according to EDANA method WSP 241.3 is 13 g/g or more, and a biodegradability of the polymer material according to KS M ISO 14851 standard is 70% or more.

2. The polymer material according to claim 1, wherein the polysaccharide component comprises a polysaccharide having a modified monosaccharide unitary body.

3. The polymer material according to claim 2, wherein the modified monosaccharide unitary body comprises a functional group of Formula 1 below: ##STR00007## wherein, M.sub.1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 bond is an ionic bond, and the carbon-carbon double bond in Formula above may form a cross-linked structure.

4. The polymer material according to claim 3, wherein a substitutional rate of the functional group of Formula 1 in the polysaccharide is in a range of 10% to 300%.

5. The polymer material according to claim 2, wherein the modified monosaccharide unitary body is represented Formula 2 below: ##STR00008## wherein, R.sub.1 is a hydroxy group, an amino group, or an alkylcarbonylamino group, L.sub.1 is an alkylene group or an alkylidene group, M.sub.1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 bond is an ionic bond, and a carbon-carbon double bond in Formula 2 above reacts to form a cross-linked structure.

6. The polymer material according to claim 2, wherein the modified monosaccharide unitary body comprises a functional group of Formula 3 below: ##STR00009## wherein, L.sub.2 is an alkylene group or an alkylidene group, and M.sub.2 is hydrogen or a metal, and when M.sub.2 is the metal, the O-M.sub.2 bond is an ionic bond.

7. The polymer material according to claim 6, wherein the substitutional rate of the functional group of Formula 3 in the polysaccharide is in a range of 10% to 300%.

8. The polymer material according to claim 2, wherein the modified monosaccharide unitary body is represented by Formula 4 below: ##STR00010## wherein, R.sub.2 is a hydroxy group, an amino group, or an alkylcarbonylamino group, L.sub.2 and L.sub.3 are each independently an alkylene group or an alkylidene group, M.sub.2 is hydrogen or a metal, and when M.sub.2 is the metal, the O-M.sub.2 bond is an ionic bond.

9. The polymer material according to claim 1, wherein the polysaccharide component comprises a polysaccharide including a modified monosaccharide unitary body having a functional group of Formula 1 below and a modified monosaccharide unitary body having a functional group of Formula 3 below: ##STR00011## wherein, M.sub.1 in Formula 1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 bond is an ionic bond, and a carbon-carbon double bond in Formula 1 above may react to form a cross-linked structure, and L.sub.2 in Formula 3 is an alkylene group or an alkylidene group, and M.sub.2 is hydrogen or a metal, and when M.sub.2 is the metal, the O-M.sub.2 bond is an ionic bond.

10. The polymer material according to claim 9, wherein the substitutional rate of the functional group of Formula 1 in the polysaccharide is in a range of 10% to 300%, and the substitutional rate of the functional group of Formula 3 is in a range of 10% to 300%.

11. The polymer material according to claim 1, wherein the polysaccharide component comprises a first polysaccharide containing a modified monosaccharide unitary body having a functional group of Formula 1 below and a second polysaccharide containing a modified monosaccharide unitary body having a functional group of Formula 3 below: ##STR00012## wherein, M.sub.1 in Formula 1 is hydrogen or a metal, and when M.sub.1 is the metal, the O-M.sub.1 bond is an ionic bond, and carbon-carbon double bond in Formula 1 above may react to form a cross-linked structure, and L.sub.2 in Formula 3 is an alkylene group or an alkylidene group, and M.sub.2 is hydrogen or a metal, and when M.sub.2 is the metal, the O-M.sub.2 bond is an ionic bond.

12. The polymer material according to claim 11, wherein a substitutional rate of the functional group of Formula 1 in the first polysaccharide is in a range of 10% to 300%, and a substitutional rate of the functional group of Formula 3 in the second polysaccharide is in a range of 10% to 300%.

13. The polymer material according to claim 11, comprising 10 to 4000 parts by weight of the second polysaccharide relative to 100 parts by weight of the first polysaccharide.

14. The polymer material according to claim 1, wherein the polysaccharide is included in a cross-linked state.

15. The polymer material according to claim 1, wherein the polysaccharide is included in a self-cross-linked state.

16. The polymer material according to claim 1, comprising no cross-linking agent, or comprising 10 parts by weight or less of a cross-linking agent relative to 100 parts by weight of the polysaccharide component.

17. An absorbent material comprising the polymer material of claim 1.

18. A sanitary article comprising the polymer material of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0102] FIG. 1 illustrates .sup.1H NMR analysis results of the polysaccharides prepared in Preparation Example 1.

[0103] FIG. 2 illustrates another .sup.1H NMR analysis results of the polysaccharides prepared in Preparation Example 2.

[0104] FIG. 3 illustrates yet another .sup.1H NMR analysis results of the polysaccharides prepared in Preparation Example 3.

[0105] Detailed Description Hereinafter, the present application will be described in detail through examples and comparative examples, but the scope of the present application is not limited by the following examples.

1. Evaluation of Centrifuge Retention Capacity (CRC)

[0106] Centrifuge retention capacity (CRC) was measured according to EDANA (European Disposables and Nonwovens Association) WSP 241.3. About 0.2 g (W.sub.0) of a sample (polymer material) was placed in a non-woven bag, sealed, and then submerged in a physiological saline solution. As the physiological saline solution, an aqueous NaCl solution with a concentration of 0.9 wt % was used. The submerged state was maintained for 30 minutes or so, water was removed from the bag for 3 minutes under a condition of 250 G using a centrifuge, and then the mass (g, W.sub.2) of the bag was measured. The same operation was performed on the same non-woven bag without the sample, and the mass (g, W.sub.1) was measured.

[0107] The CRC (g/g) was calculated by substituting the measurement results into Equation A below.

[0108] The evaluation was conducted under constant temperature and humidity conditions (231 C., relative humidity: 5010%).

[00001]$\begin{array}{cc}\mathrm{CRC}\left(g/g\right)=\left\{\left[W_2\left(g\right)-W_1\left(g\right)\right]/W_0\left(g\right)\right\}-1& \left[\mathrm{Equation}A\right]\end{array}$

2. Measurement of Biodegradability

[0109] Biodegradability was measured in the manner specified in KS M ISO 14851 standard. The biodegradability appears differently depending on the measurement method. For example, the KS M ISO 14855-1 is a method of measuring biodegradability through carbon dioxide under a composting condition, where a higher level of biodegradability is measured for the same material compared to other measurement methods, but in the actual environment, it does not represent the biodegradability of the material well. The KS M ISO 14851 standard is a method of measuring aerobic biodegradability of a polymer material in an aqueous solution medium (measurement of oxygen consumption by a closed respiratory system), where the biodegradability of this method well reflects the biodegradation characteristics of the material in the actual environment. The method of measuring biodegradability according to the KS M ISO 14851 standard is known.

PREPARATION EXAMPLE 1

[0110] A polysaccharide (modified starch) (Compound A) containing a modified monosaccharide unitary body of Formula A below was prepared in the following manner. The modified monosaccharide unitary body of Formula A below is a monosaccharide unitary body into which a maleic acid group (a substituent where M.sub.1 in Formula 1 is a hydrogen atom) is introduced.

##STR00005##

[0111] 20 g of starch and 50 mL of water were added to a 500 mL RBF (Round Bottom Flask), stirred at room temperature (about 25 C.), and then 50 mL of a 2.0 M NaOH solution was added thereto. As the starch, potato starch was used. The mixture was further stirred for 2 hours to be gelatinized, about 100 g of maleic anhydride was added thereto, and reacted at 65 C. for 5 hours or so. After completion of the reaction, the temperature was lowered to room temperature (about 25 C.), and acetone was added to generate a precipitate. The precipitate was recovered and dried in a vacuum drying oven at 40 C. for one day to obtain a solid target product (Compound A). The substitutional rate of the obtained target product (Compound A) can be obtained through a .sup.1H NMR analysis. The .sup.1H NMR analysis is performed at room temperature (about 25 C.) using a .sup.1H NMR spectrometer including a Varian Unity Inova (500 MHZ) spectrometer with a triple resonance 5 mm probe. In the .sup.1H NMR analysis, Bruker's Avance Neo instrument was used. 50 mg of the obtained target product (Compound A) and 200 mg of 30% DCI in D.sub.2O solution are mixed, stirred at 50 C. for 1 hour or so to induce a hydrolysis reaction, and then the .sup.1H NMR analysis can be performed. The substitutional rate of the maleic acid group to the starch was confirmed by the .sup.1H NMR analysis. FIG. 1 shows the results of .sup.1H NMR analysis performed on Compound A above, and the substitutional rate calculated based on this was about 98% or so.

PREPARATION EXAMPLE 2

[0112] Starch (Compound B) containing a modified monosaccharide unitary body of Formula B below was prepared in the following manner. The modified monosaccharide unit of Formula B below is a monosaccharide unitary body into which a functional group (substituent, wherein M.sub.2 in Formula 3 is sodium and L.sub.2 is a methylidene group) derived from sodium acetate is introduced.

##STR00006##

[0113] 20 g of starch and 50 mL of water were added to a 500 mL RBF (Round Bottom Flask), stirred at room temperature (about 25 C.), and then 50 mL of a 2.0 M NaOH solution was added thereto. As the starch, the same starch as in Preparation Example 1 was used. The mixture was further stirred for 2 hours to be gelatinized, about 100 g of sodium monochloroacetate was added thereto, and reacted at 65 C. for 5 hours or so. After completion of the reaction, the temperature was lowered to room temperature (about 25 C.), and acetone was added to generate a precipitate. The precipitate was recovered and dried in a vacuum drying oven at 40 C. for one day to obtain a solid target product (Compound B).

[0114] The results of the .sup.1H NMR analysis performed on the target product (Compound B) in the same manner as Preparation Example 1 are shown in FIG. 2. The substitutional rate confirmed from the results in FIG. 2 was about 120% or so.

PREPARATION EXAMPLE 3

[0115] Starch (compound C) simultaneously containing the modified monosaccharide unitary bodies represented by Formulas A and B of Preparation Examples 1 and 2 was prepared in the following manner. 20 g of starch and 50 mL of water were added to a 500 mL RBF (Round Bottom Flask), stirred at room temperature (about 25 C.), and then 50 mL of a 2.0 M NaOH solution was added thereto. As the starch, the same type as in Preparation Example 1 was used. The mixture was further stirred for 2 hours to be gelatinized, and about 14 g of sodium monochloroacetate and about 10 g of maleic anhydride were added thereto, and reacted at 65 C. for 5 hours or so. After completion of the reaction, the temperature was lowered to room temperature (about 25 C.), and acetone was added to generate a precipitate. The precipitate was recovered and dried in a vacuum drying oven at 40 C. for one day to obtain a solid target product (Compound C). The results of the .sup.1H NMR analysis performed on the target product (Compound C) in the same manner as Preparation Example 1 are shown in FIG. 3. The substitutional rate of the maleic acid group of the target product (Compound C) confirmed from the analysis results in FIG. 3 was about 37% or so, and the substitutional rate of the sodium acetate-derived functional group was about 68% or so.

EXAMPLE 1

[0116] 50 mL of distilled water, 2.5 g of the compound of Preparation Example 1 (Compound A), and 0.5 g of the compound of Preparation Example 2 (Compound B) were introduced into a 250 mL RBF (Round Bottom Flask), and the mixture was stirred in an oil bath at 35 C. for 30 minutes or more, whereby Compounds A and B were sufficiently dissolved in the distilled water. Then, an initiator was introduced thereto. As the initiator, about 0.03 g of ammonium persulfate was introduced. After introducing the initiator, the mixture was further stirred at a temperature of 70 C. or so for 4 hours or so to proceed cross-linking between Compounds A and B. After cross-linking, ethanol was introduced to precipitate a polymer material containing the cross-linked polymer, and then dried overnight in a vacuum drying oven at 40 C. after filtering to obtain a target polymer material.

EXAMPLES 2 TO 5 AND COMPARATIVE EXAMPLES 1 AND 2

[0117] Polymers were prepared in the same manner as in Example 1, except that the amounts of the compounds introduced for polymerization were changed as in Table 1 below. In the table below, the unit of content is g.

TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 4 5 1 2 Compound A 2.5 2 0.5 0.1 3 Compound B 0.5 1 1.5 2.9 3 Compound C 3

COMPARATIVE EXAMPLE 3

[0118] 50 mL of distilled water, 2.5 g of the compound of Preparation Example 1 (Compound A), 0.5 g of the compound of Preparation Example 2 (Compound B), 6.8 mg of polyethylene glycol diacrylate (number average molecular weight: 575 g/mol), 0.24 mg of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 3.6 mg of sodium persulfate were introduced into a 250 mL RBF (Round Bottom Flask), and the mixture was stirred in an oil bath at 35 C. for 30 minutes or more, whereby Compounds A and B were sufficiently dissolved in the distilled water. In a UV chamber at 80 C., the mixture was irradiated with ultraviolet rays for 60 seconds (irradiation dose: 10 mV/cm.sup.2), and then maintained for about 2 minutes to proceed cross-linking. After cross-linking, ethanol was introduced to precipitate a polymer material containing the cross-linked polymer, and then dried overnight in a vacuum drying oven at 40 C. after filtering to obtain a target polymer material.

[0119] The CRC and biodegradability measured for the polymers of the examples and comparative examples were summarized in Table 2 below and described.

TABLE-US-00002 TABLE 2 Comparative Example Example 1 2 3 4 5 1 2 3 CRC (g/g) 16.1 16.8 17.5 16.0 17.1 11.3 2.3 15.1 Biodegrad- 86 88 74 70 80 85 52 59 ability (%)

[0120] As in the results of Table 2, the polymer materials according to Examples of the present application simultaneously exhibited excellent absorption properties and biodegradability. Comparative Example 1 was a case where only Compound A was applied, and in this case, the biodegradability was secured to a certain extent, but the absorption characteristic was greatly reduced. Comparative Example 2 was a case where only Compound B was applied, and both absorption capacity and biodegradability were reduced. Comparative Example 3 was a case where the same materials as those of Example 1 were used, but a method using an acrylate-based cross-linking agent was applied instead of a self-cross-linking method, and in this case, absorption capacity was secured, but biodegradability was greatly reduced.