Polymer material

Abstract

The invention relates to polymer materials and uses thereof. The present application can provide a polymer material having excellent biodegradability and absorbability by using a polysaccharide into which a specific functional group is introduced. The invention also provides application of the polymer material.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2023-0008024, filed on January 19, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present invention relates to polymer materials and their uses. Background Art

[0003] A hydrogel polymer or hydrogel is generally defined as a cross-linked hydrophilic polymer.

[0004] Such polymers can be used as materials known as SAPs (Super Absorbent Polymers). SAPs are materials that can absorb tens to thousands of times their own weight in water. SAPs are used in a variety of applications, such as sanitary products such as sanitary items or diapers, medical products, household materials, agricultural materials, gardening materials, transportation materials, civil engineering and construction materials, materials related to electrical and electronic devices, or water treatment agents.

[0005] The most widely used hydrogel polymers used as SAPs are polymers made from vinyl-based materials such as cross-linked polyacrylic acid.

[0006] Such materials are relatively inexpensive and have excellent water absorption capacity, but cause various problems because they remain semi-permanently even after treatment.

[0007] In order to solve such problems, various attempts have been made to manufacture SAP from so-called biodegradable materials.

[0008] However, materials known to date do not form SAPs with balanced physical properties. For example, the most representative physical property required of SAPs is absorption capacity. However, in SAPs made of biodegradable materials known to date, at least one of absorption capacity and biodegradability cannot be satisfactorily ensured, or in some cases, both physical properties cannot be ensured at appropriate levels. Summary of the Invention

[0009] Technical issues

[0010] The present application aims to provide a polymer material capable of simultaneously ensuring excellent absorption capacity and biodegradability and use thereof.

[0011] Technical Solution

[0012] Among the physical properties mentioned in this specification, when the measurement temperature and / or pressure affect the physical property value, unless specifically mentioned otherwise, the relevant physical properties mean physical properties measured at room temperature and / or normal pressure.

[0013] In the present application, the term room temperature is a natural temperature without heating or cooling, and may mean, for example, any temperature within the range of about 10°C to 30°C, or a temperature around 23°C or 25°C.

[0014] In the present application, the term normal pressure is a pressure when it is not particularly reduced or increased, and it may mean a pressure around normal atmospheric pressure, for example, around 740 mmHg to 780 mmHg.

[0015] Among the physical properties mentioned in this specification, when measuring a physical property value affected by humidity, the physical property means a physical property measured at natural humidity without special adjustment at the temperature and pressure of measurement unless otherwise specified.

[0016] In this specification, unless otherwise indicated, the term alkyl or alkyl group means an alkyl or alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such an alkyl or alkyl group may be linear, branched or cyclic. Such an alkyl or alkyl group may also be optionally substituted with one or more substituents.

[0017] In this specification, unless otherwise stated, term alkylene or alkylene group means by separating two hydrogen atoms from alkane and being connected to the functional group of other object, wherein it has the structure of separating two hydrogen atoms from the different carbon atoms of alkane.Such alkylene or alkylene group can be alkylene or alkylene group with 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms.Such alkylene or alkylene group can be linear, branched or cyclic.Such alkylene or alkylene group also can optionally replace through one or more substituents.

[0018] In this specification, unless otherwise indicated, term alkylidene or alkylidene group means the functional group that is connected to other object by separating two hydrogen atoms from alkane, wherein it has the structure that separates two hydrogen atoms from one carbon atom of alkane.Such alkylidene or alkylidene group can be alkylidene or alkylidene group with 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom, 1 to 8 carbon atom or 1 to 4 carbon atom.Such alkylidene or alkylidene group can be linear, branched or cyclic.Such alkylidene or alkylidene group also can optionally replace through one or more substituents.

[0019] In this application, the term hydrogel polymer material means an absorbent material comprising cross-linked polymers, and such materials may also be referred to as hydrogels.

[0020] In the present specification, the term absorbent material means a material that exhibits at least one of the properties of moisture content, centrifuge retention capacity (CRC) and absorption capacity under pressure (AUP) as defined in the present specification.

[0021] For example, when the polymer material is an absorbent material, the lower limit of the moisture content of the polymer material may be approximately 40%, 45%, 50%, or 55% by weight, and the upper limit may be approximately 70%, 65%, or 60% by weight. The moisture content may also be greater than, equal to, or greater than any of the aforementioned lower limits, or within a range of less than, equal to, or less than any of the aforementioned upper limits while also being greater than, equal to, or greater than any of the aforementioned lower limits. Moisture content is the amount of water contained in the polymer material relative to the total weight of the polymer material to be measured, and can be calculated by the weight of the polymer material including water and the weight of the dry polymer material. For example, during the process of drying a polymer material in a crumb state by increasing the temperature of the polymer material via infrared heating, the moisture content can be calculated by the weight loss due to evaporation of water from the polymer material. The drying process used to measure moisture content may include increasing the temperature from room temperature to approximately 50°C, followed by vacuum drying for approximately 6 hours while maintaining the temperature at 50°C. The polymer material may exhibit the stated moisture content before or after crosslinking.

[0022] For example, when the polymeric material is an absorbent material, the lower limit of the centrifuge retention capacity (CRC) according to EDANA (European Disposables and Nonwovens Association, European Disposables and Nonwovens Association) method WSP241.3 of the polymeric material can be 10g / g, 15g / g, 20g / g, 25g / g, 30g / g, 35g / g, 40g / g or 45g / g or so, and its upper limit can be 60g / g, 55g / g, 50g / g, 45g / g, 40g / g or 35g / g or so. Centrifuge retention capacity (CRC) can be greater than or equal to, or greater than any one of the above-mentioned lower limit, or less than or equal to, or less than any one of the above-mentioned upper limit, or in the range of being greater than or equal to, or greater than any one of the above-mentioned lower limit while being less than or equal to, or less than any one of the above-mentioned upper limit. The polymeric material can show the centrifuge retention capacity before or after cross-linking.

[0023] For example, when the polymer material is an absorbent material, the polymer material is subjected to the WSP method according to EDANA (European Disposables and Nonwovens Association). The lower limit of the absorption capacity under pressure (AUP) at 0.7 psi of 242.3 can be about 1.5 g / g, 2 g / g, 2.5 g / g, 3 g / g, 3.5 g / g, 4 g / g, 4.5 g / g, 5 g / g, 5.5 g / g, 6 g / g, 6.5 g / g, 7 g / g, 7.5 g / g, 8 g / g, 8.5 g / g, 9 g / g, 9.5 g / g, 10 g / g, 12 g / g, 14 g / g, 16 g / g, 18 g / g, or 19 g / g, and the upper limit thereof can be about 40 g / g, 35 g / g, 30 g / g, 20 g / g, 15 g / g, 10 g / g, 8 g / g, 6 g / g, or 4 g / g. The absorption capacity (AUP) can be greater than, equal to, or greater than any of the aforementioned lower limits, or less than, equal to, or less than any of the aforementioned upper limits, or within the range of less than, equal to, or less than any of the aforementioned upper limits while greater than, equal to, or greater than any of the aforementioned lower limits. The polymeric material can exhibit the centrifuge retention capacity before or after crosslinking.

[0024] If a polymeric material exhibits at least one of the properties of water content, centrifuge retention capacity, and absorption capacity under pressure as described above, the relevant material can be defined as an absorbent material. The polymeric material can exhibit any one, two or more, or all of the water content, centrifuge retention capacity, and absorption capacity under pressure.

[0025] As mentioned above, the polymer material can simultaneously exhibit excellent absorbability and biodegradability.

[0026] In this specification, a biodegradable material means a material that exhibits a degree of biodegradability as defined herein.

[0027] For example, if the polymeric material is biodegradable, the lower limit of the biodegradability of the polymeric material can be about 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, or 99%, and the upper limit can be about 100%, 98%, 96%, 94%, 92%, 90%, 88%, 86%, 84%, 82%, 80%, 78%, or 76%. The biodegradability can be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within the range of less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits. The biodegradability is measured in the manner described in the Examples of this specification.

[0028] The polymer material of the present application can be both an absorbent material and a biodegradable material as described above.

[0029] The term polymeric material means the material comprising polymer.Polymer can mean the material formed by making two or more unit bodies be connected by covalent bonds.In an example, polymer can mean the structure comprising wherein two or more unit bodies are connected by covalent bonds and has the material of a certain level or larger molecular weight.The scope of molecular weight is not restricted.In an example, with regard to weight average molecular weight (Mw), the lower limit of the molecular weight of polymer can be 500g / mol, 1,000g / mol, 10,000g / mol, 100,000g / mol, 1,000,000g / mol or 10,000,000g / mol or so, and its upper limit can be 10,000,000,000g / mol, 1,000,000,000g / mol, 100,000,000g / mol or 10,000,000g / mol or so. The weight average molecular weight can be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within the range of less than or equal to, or less than any of the above upper limits and greater than or equal to, or greater than any of the above lower limits.

[0030] The weight average molecular weight is a value measured in the manner described in Examples of this specification.

[0031] In one example, the polymer content in the polymer material can have a lower limit of about 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% by weight, and an upper limit of about 100%, 98%, 96%, 94%, 92%, or 90% by weight. The ratio can be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within a range of less than or equal to, or less than any of the above upper limits and greater than or equal to, or greater than any of the above lower limits.

[0032] The polymeric material of the present application may comprise a polysaccharide component.

[0033] The term polysaccharide component refers to a polysaccharide or a mixture of polysaccharides. In the case of a mixture of polysaccharides, the mixture can be a mixture of one type of polysaccharide (i.e., when two or more molecules of the same type of polysaccharide are present) or a mixture of two or more types of polysaccharides. Here, two or more types of polysaccharides can also mean different types of polysaccharides and can also include polysaccharides of the same type but with different physical properties, such as molecular weight. A polysaccharide component contains only polysaccharides.

[0034] The term polysaccharide has a meaning known in industry. Polysaccharides generally refer to polymer molecules in which two or more units are linked by covalent bonds. The covalent bonds linking the units are generally glycosidic bonds. Typically, structures in which two units are linked by a covalent bond, such as a glycosidic bond, are referred to as disaccharides. In this specification, unless otherwise indicated, disaccharides are also included in the scope of polysaccharides.

[0035] The unit body forming polysaccharide can be the biomolecule being made up of carbon, hydrogen and oxygen, or the biomolecule being made up of carbon, hydrogen, oxygen and nitrogen.In this manual, term biomolecule is interpreted as having the implication of common application in industry.Typically, as the example of biomolecule in industry, known monosaccharide is such as glucose, galactose, fructose or xylose, disaccharide is such as sucrose, lactose, maltose or trehalose, polyol is such as sorbitol or mannitol, oligosaccharide is such as maltodextrin, dextrin, raffinose, stachyose or oligofructose and / or amino sugar is such as glucosamine or N-acetylglucosamine etc., but the type of biomolecule in this application is not limited to aforementioned.

[0036] If the polymer (e.g., polysaccharide component) contained in the polymer material is in a cross-linked state and has an absorption capacity, the relevant polymer material can be referred to as a hydrogel polymer material or hydrogel in this article. In one example, the polymer material can also be in a powder state formed by a grinding process, etc.

[0037] In the polymer material of the present application, the polysaccharide component may be in a cross-linked state. Here, cross-linking means a state in which two or more molecules of polysaccharide are connected by one or more chemical bonds. Cross-linking may also be formed by chemical substances other than polysaccharides (which are referred to as so-called cross-linking agents), and may be formed by reactions between functional groups contained in the polysaccharide. In this specification, when the cross-linking of the polysaccharide is carried out by reactions between functional groups contained in the polysaccharide without applying other cross-linking agents, the relevant cross-linked polysaccharide may be referred to as a self-cross-linked polysaccharide component.

[0038] In the present specification, the polymer material may include at least a self-crosslinked polysaccharide component among the above types of cross-linked polysaccharides.

[0039] In one example, based on the gross weight of the polymeric material, the polymeric material can include a self-crosslinked polysaccharide component in a certain amount or more. For example, the lower limit of the ratio of the self-crosslinked polysaccharide component in the polymeric material can be about 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%, and its upper limit can be about 100 wt%, 98 wt%, 96 wt%, 94 wt%, 92 wt%, or 90 wt%. The ratio can be greater than or equal to, or greater than any one of the above-mentioned lower limits, or less than or equal to, or less than any one of the above-mentioned upper limits, or in the range of being less than or equal to, or less than any one of the above-mentioned upper limits and being greater than or equal to, or greater than any one of the above-mentioned lower limits.

[0040] In another example, the ratio of the cross-linking agent that makes the polysaccharide component cross-link in the polymeric material can be limited to a certain amount or less.Here, cross-linking agent is the substance that forms the chemical bond that polysaccharide component is connected, and it means the different substances except polysaccharide.For example, the upper limit of the ratio of the cross-linking agent in the polymeric material can be 10 weight %, 9 weight %, 8 weight %, 7 weight %, 6 weight %, 5 weight %, 4 weight %, 3 weight %, 2 weight %, 1 weight %, 0.5 weight %, 0.1 weight %, 0.05 weight %, 0.01 weight %, 0.005 weight % or 0.001 weight % or so, and its lower limit can be 0 weight % or so.The ratio of cross-linking agent can be less than any one in the above-mentioned upper limit, or be less than or equal to, or be less than any one in the above-mentioned upper limit and be greater than or equal to, or be greater than any one in the above-mentioned lower limit simultaneously.

[0041] In the present application, the crosslinking of polysaccharides is carried out without the use of a crosslinking agent, or while minimizing the amount of the crosslinking agent used. If a crosslinking agent other than the polysaccharide is used, the biodegradability of the polymer material may be reduced. However, since the crosslinking efficiency of the polysaccharide is generally reduced when a crosslinking agent is not used, it is not easy to obtain a polymer material with desired properties (e.g., absorption properties). In the present application, by applying a polysaccharide with one or more properties among the polysaccharides to be described below and / or applying a self-crosslinking reaction in a manner to be described below, a polymer material having excellent physical properties (e.g., absorption capacity) while having excellent biodegradability in a self-crosslinked state can be provided.

[0042] For example, the self-crosslinked polysaccharide may comprise amylose and amylopectin. As is known, amylopectin and amylose are types of polysaccharides found primarily in plants, and the starch of the polysaccharide is composed of amylose and amylopectin. Amylose is composed of glucose molecules linked by α(1→4) glycosidic bonds and has a linear chain structure, while amylopectin has a relatively short and highly branched chain. Compared to amylopectin, amylose is relatively easy to crystallize, and amylopectin has a relatively higher solubility in water than amylose.

[0043] The ratio of amylose to amylopectin in the polysaccharide component and the molecular weight of the relevant polysaccharide component may be greatly correlated with the self-crosslinking efficiency or the absorption capacity and biodegradability of the polymer material.

[0044] As the ratio of amylopectin in the polysaccharide component decreases and the ratio of amylose increases, the biodegradability of the material increases, but the absorption capacity tends to decrease slightly. In addition, as the molecular weight of the polysaccharide component increases, the biodegradability of the material decreases, but the absorption capacity tends to increase.

[0045] For example, F according to the following Equation 1 of the polymer material or the polysaccharide component may be within a predetermined range.

[0046] [Equation 1]

[0047]

[0048] In Equation 1, P is the ratio of amylopectin in the polysaccharide component, M is the ratio of amylose in the polysaccharide component, and Mw is the weight average molecular weight of the polysaccharide component.

[0049] F in Equation 1 is a factor representing the amount of amylose and amylopectin in the polysaccharide component and the molecular weight of the polysaccharide component. For example, the value of F increases with increasing molecular weight of the polysaccharide component and / or increasing ratio of amylopectin in the polysaccharide component.

[0050] The polysaccharide component, in which the ratio of amylose to amylopectin and the molecular weight are controlled, can be effectively cross-linked to form a material having excellent absorption capacity and degree of biodegradability.

[0051] In Equation 1, P and M are ratios of amylopectin and amylose measured in the manner described in Examples of the present specification, and the unit thereof is %.

[0052] In Equation 1, Mw is the weight average molecular weight of the polysaccharide component, which is measured in the manner described in Examples of this specification, and its unit is g / mol.

[0053] The lower limit of F in Equation 1 may be about 4, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, or 8.2, and the upper limit thereof may be about 20, 18, 16, 14, 12, 10, 9, 8, 7, 6, or 5. F may be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within a range of less than or equal to, or less than any of the above upper limits while greater than or equal to, or greater than any of the above lower limits.

[0054] Within such a range, the polysaccharide component can be effectively cross-linked to form a polymer material having excellent absorption capacity and biodegradability.

[0055] In Equation 1, the ranges of Mw, M, and P can be adjusted to appropriate levels.

[0056] For example, the lower limit of Mw in Equation 1 can be 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, 750,000 g / mol, 800,000 g / mol, 850,000 g / mol, 900,000 g / mol, 950,000 g / mol, 1,000,000 g / mol, 1,500,000 g / mol, or 2,000,000 g / mol. / mol, 2,000,000g / mol, 2,500,000g / mol, 3,000,000g / mol, 3,500,000g / mol, 4,000,000g / mol, 4,500,000g / mol, 5,000,000g / mol, 5,500,000g / mol , 6,000,000g / mol, 6,500,000g / mol, 7,000,000g / mol, 7,500,000g / mol, 8,000,000g / mol, 8,500,000g / mol, 9,000,000g / mol, 9,500,000g / mol, 10,0 00,000g / mol, 20,000,000g / mol, 30,000,000g / mol, 40,000,000g / mol, 50,000,000g / mol, 60,000,000g / mol, 70,000,000g / mol, 80,000,000g / mol, 90,000,000g / mol, 100,000,000g / mol, 110,000,000g / mol, 120,000,000g / mol, 130,000,000g / mol, 140,000,000g / mol, 150,000,000g / mol, 160,00 0,000 g / mol, 170,000,000 g / mol, or 180,000,000 g / mol, and its upper limit can be 10,000,000,000 g / mol, 5,000,000,000 g / mol, 1,000,000,000 g / mol, 900,000,000 / mol, 800,000,000 / mol, 700,000,000 / mol, 600,000,000 / mol, 500,000,000 / mol, 400,000,000 / mol, 300,000,000 / mol, 200,000,000 / mol, 150,000,000 / mol, 100,000,000 / mol, 90,000,000 / mol, 80,000,000 / mol, 70,000,000 / mol, 60,000,000 / mol, 50, 000,000 / mol, 40,000,000 / mol, 30,000,000 / mol, 20,000,000 / mol, 10,000,000 / mol, 9,000,000 / mol, 8 The Mw may be greater than or equal to, or greater than, any of the aforementioned lower limits, or less than or equal to, or less than, any of the aforementioned upper limits, or within the range of less than or equal to, or less than, any of the aforementioned upper limits and greater than or equal to, or greater than, any of the aforementioned lower limits.

[0057] The lower limit of P in Equation 1 may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, and the upper limit thereof may be about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 35%, or 20%. P may be greater than or equal to, or greater than any of the aforementioned lower limits, less than or equal to, or less than any of the aforementioned upper limits, or within a range of less than or equal to, or less than any of the aforementioned upper limits and greater than or equal to, or greater than any of the aforementioned lower limits.

[0058] The lower limit of M in Equation 1 may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, and the upper limit thereof may be about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 35%, or 20%. M may be greater than or equal to, or greater than any of the aforementioned lower limits, less than or equal to, or less than any of the aforementioned upper limits, or within a range of less than or equal to, or less than any of the aforementioned upper limits and greater than or equal to, or greater than any of the aforementioned lower limits.

[0059] In one example, the sum of the above M and P in the polysaccharide component may be 100%.

[0060] In one example, when the polysaccharide of the polysaccharide component is a modified polysaccharide to be described below, that is, a polysaccharide into which an acidic group such as a carboxyl group has been introduced by maleation or carboxyalkylation, the functional group introduced into the modified polysaccharide may be introduced into either amylose or amylopectin, or may be introduced into both. The reaction for introducing the functional group described below may occur in both amylose and amylopectin, but more effective modification may be possible when the content of amylopectin is greater than that of amylose.

[0061] As the polysaccharide component, a suitable type can be selected and used from among the above-mentioned polysaccharides, as long as it contains at least a polysaccharide containing amylose and amylopectin. Combining one or two or more known polysaccharides to form a polysaccharide component so that F in Equation 1 is 4 or greater can be applied to the polymer material.

[0062] In the present application, the self-crosslinking of polysaccharides can be carried out using so-called acidic polysaccharides. As is known, acidic polysaccharides are polysaccharides having such acidic groups, examples of which may include carboxyl groups, phosphate groups, phosphite groups and / or sulfate groups or their salts.

[0063] For proper self-crosslinking, the degree of substitution of the acidic polysaccharide or the acidic polysaccharide component can be adjusted. The degree of substitution is an indicator of the amount of acidic groups present in the acidic polysaccharide or the polysaccharide component, wherein such a degree of substitution can be, for example, a value obtained before the polysaccharide or the polysaccharide component achieves a crosslinked structure.

[0064] For example, the lower limit of degree of substitution can be about 0.4, 0.45, 0.5, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or 1, and its upper limit can be about 2.5, 2, 1.5, 1.1, 1.05, 1, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65 or 0.6. The degree of substitution can be greater than or equal to or greater than any one in the above-mentioned lower limit, or less than or equal to or less than any one in the above-mentioned upper limit, or less than or equal to or less than any one in the above-mentioned upper limit while being greater than or equal to or greater than the scope of any one in the above-mentioned lower limit. Within the scope of the degree of substitution, the crosslinking of polysaccharide can be effectively carried out, and the physical properties (for example, absorption capacity and / or biodegradability etc.) of the resulting polymeric material can be stably ensured. When the degree of substitution is high, the number of acidic groups, which are hydrophilic functional groups, in the polysaccharide or polysaccharide component increases, which may be advantageous in terms of absorption properties. However, too many acidic groups excessively promote the crosslinking reaction, which may reduce the absorption properties after crosslinking. Therefore, considering these points, an appropriate degree of substitution can be selected.

[0065] In this specification, the degree of substitution is an indicator of the degree to which an acidic group exists in a polysaccharide or a polysaccharide component, which is, for example, a value indicating the degree to which a functional group such as a hydroxyl group present in each unit body contained in the polysaccharide or the polysaccharide component is substituted by a predetermined acidic group (e.g., a carboxyl group), and is an average value of each unit body present in the polysaccharide. For example, if the unit body is a glucose (grape sugar / glucose) unit, three hydroxyl groups are present in the relevant unit before modification, and therefore, if all hydroxyl groups are replaced by functional groups of the above formula 1, the degree of substitution of the relevant unit is 3. However, the degree of substitution of a polysaccharide is the average value of the degree of substitution of each unit body present in the relevant polysaccharide, so that, for example, in a polysaccharide containing 5 glucose (glucose) units, if the degree of substitution of each unit is 1, 0, 2, 3 and 1, the degree of substitution of the polysaccharide becomes 1.4, which is an average value. The degree of substitution can be determined by the degree of substitution of the polysaccharide. 1 H NMR analysis was performed to determine the presence of hydroxyl groups and substituted functional groups in the polysaccharide. 1 H NMR analysis is quantitative, so the degree of substitution can be determined and, if necessary, the polysaccharide before modification can be considered. 1 The degree of substitution was calculated from the results of HNMR analysis. 1 Methods for quantifying functional groups by H NMR analysis are known.

[0066] In the present application, self-crosslinking of polysaccharides can be performed, for example, using such an acidic polysaccharide or a polysaccharide or polysaccharide component having carboxyl groups as acidic groups. Since the polysaccharide itself contains hydroxyl groups, the hydroxyl groups contained in one molecule of the polysaccharide can undergo an esterification reaction with the carboxyl groups contained in the acidic polysaccharide, thereby causing self-crosslinking.

[0067] The type of polysaccharide component having carboxyl groups is not particularly limited. For example, self-crosslinking can be performed by using a polysaccharide which itself has carboxyl groups, such as so-called CMC (carboxymethyl cellulose), or a polysaccharide in which carboxyl groups are introduced by processes such as maleation or carboxyalkylation.

[0068] The self-crosslinked polysaccharide component may comprise polymer chains comprising monosaccharide units linked by glycosidic bonds (ie, polysaccharide chains to be crosslinked), and crosslinks connecting the polymer chains.

[0069] At this time, cross-links may be connected to the monosaccharide units.

[0070] Here, the cross-linking bond may be a bond represented by Formula 1 below.

[0071] [Formula 1]

[0072]

[0073] In Formula 1, X1 is an oxygen atom or NR 11 , where R 11 is a hydrogen atom, an alkyl group or an alkylcarbonyl group, and L1 is an alkylene group, an alkylidene group or a bond of the following formula 2, and L2 is represented by a single bond or -(CH2)-O-.

[0074] [Formula 2]

[0075]

[0076] In Formula 1, X1 shown on the far left can be directly linked to a monosaccharide unit of the polymer chain.

[0077] In the case where X1 in Formula 1 is an oxygen atom, starch or the like is used as a polysaccharide for cross-linking, and in the case where X1 is NR 11 In the case of chitosan or chitin, etc. are used for cross-linking.

[0078] R 11 The alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, or a methyl group, and such an alkyl group may be linear, branched or cyclic, which may be optionally substituted with one or more substituents.

[0079] In Formula 1, when L2 is a single bond, L2 does not exist. That is, in Formula 1, when L2 exists, L2 can be directly connected to the monosaccharide unit of the polymer chain, and when L2 is a single bond, the oxygen atom on the left side of L2 in Formula 2 can be directly connected to the monosaccharide unit.

[0080] In the case where the self-crosslinking of the polysaccharide is carried out by a polysaccharide having a carboxyl group such as CMC (carboxymethyl cellulose) or a polysaccharide having a carboxyl group introduced by carboxyalkylation or the like, L1 in Formula 1 may generally be an alkylene group or an alkylidene group. In Formula 1, when L1 is a functional group of Formula 2, it is a case where the self-crosslinking is carried out by a carboxyl group introduced by so-called maleation or the like.

[0081] In Formula 1, when L1 is Formula 2, any one of the carbon atoms of the carbonyl group in Formula 2 is connected to X1 on the left side of L1 in Formula 1, and the carbon atom on the right side of the carbon-carbon double bond is connected to the carbon atom of the carbonyl group on the right side of L1.

[0082] One or more bonds of Formula 1 above may be present in the self-crosslinked polysaccharide component.

[0083] The type of the monosaccharide unit is not particularly limited, and it can be typically a monosaccharide unit constituting a polysaccharide. For example, such a monosaccharide unit can be a glucose unit, a glucosamine unit, an N-acetylglucosamine unit, or the like.

[0084] Such monosaccharide units generally include a ring structure comprising carbon atoms and oxygen atoms as ring-constituting atoms. The ring structure of the monosaccharide unit is generally a six-membered cyclic ring structure (when the ring atoms include only 5 carbon atoms and 1 oxygen atom), but may also have a ring structure of 6 or more membered rings. When the ring structure is a six-membered ring or more, the ring atoms may be carbon atoms, or heteroatoms such as oxygen or nitrogen atoms.

[0085] In the case of a self-crosslinking structure, the bond of the above Formula 1 may be directly connected to a carbon atom of the ring structure of the monosaccharide unit, or may be connected via a methylene group (—CH 2 —).

[0086] At least one or both of the leftmost X1 and the rightmost oxygen atom (if L2 is a single bond, it means the oxygen atom connected to the right side of the carbonyl group, and if L2 is not a single bond, it means the oxygen atom of -(CH2)-O-) in Formula 1 can be directly connected to the carbon atom of the ring structure, or can be connected via a methylene group (-CH2-).

[0087] Here, the matter connected via a methylene group (-CH2-) is the case where there is only a methylene group (-CH2-) between X1 on the leftmost side of the above formula 1 or the rightmost oxygen atom of formula 1 (if L2 is a single bond, it means the oxygen atom connected to the right side of the carbonyl group, and if L2 is not a single bond, it means the oxygen atom of -(CH2)-O-) and the carbon atom of the ring structure.

[0088] In this case, more specifically, the polysaccharide component may include a unit represented by Formula 3 below.

[0089] [Formula 3]

[0090]

[0091] In formula 3, R1 is hydroxyl, amino, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, R3 is hydroxyl, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, and one of L3 and L4 is a single bond, and the other is CHR2, wherein R2 is a hydroxyl group, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, and L5 is an alkylene group or an alkylidene group, but any one of R1 to R3 is an oxygen atom of a bond of the above formula 1 (except the oxygen atom present in the carbonyl group).

[0092] [Formula 4]

[0093]

[0094] In formula 4, X2 is an oxygen atom or NR 11 , where R 11 is a hydrogen atom, an alkyl group or an alkylcarbonyl group, M1 is hydrogen or a metal, and when M1 is a metal, the above O-M1 bond is an ionic bond.

[0095] In Formula 3, when R1 is an amino group, the unit is a glucosamine unit or an N-acetylglucosamine unit. In this case, the amino group may be optionally substituted with one or more substituents. In this case, the substituent may be exemplified by an alkyl group or an alkylcarbonyl group. In this case, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methyl group, wherein such an alkyl group may be linear, branched, or cyclic, and may also be optionally substituted with one or more substituents.

[0096] The functional group in formula 3 is -L5-C(=O)-OH or -L5-C(=O)-O - It may be, for example, a carboxyl group introduced by carboxyalkylation, or a functional group in which the carboxyl group is ionized, and Formula 4 is a functional group introduced by maleation.

[0097] Such functional groups are introduced for forming cross-linking bonds by participating in the above-mentioned self-cross-linking reaction, but not all of the introduced functional groups may participate in the cross-linking reaction, and in this case, some functional groups may remain.

[0098] Here, the fact that either L3 or L4 is a single bond means that either L3 or L4 does not exist. For example, when L3 does not exist, the carbon atoms connected to the left and right sides of L3 in Formula 3 are directly connected, and when L4 does not exist, the carbon atoms connected to the left and right sides of L4 in Formula 3 are directly connected.

[0099] Here, the fact that the other of L3 and L4 is CHR2 means that in Formula 3, either one of L3 and L4 is a carbon atom, and the substituent R2 is substituted on the carbon atom.

[0100] In Formula 3, the fact that any one of R1 to R3 is the oxygen atom of the bond of Formula 1 (except the oxygen atom present in the carbonyl group) means that any one of R1 to R3 is the oxygen atom of the bond of Formula 1 connected to the polysaccharide, wherein the oxygen atom means any one of the leftmost oxygen atom and the rightmost oxygen atom in Formula 1 (if L2 is a single bond, it means the oxygen atom connected to the right of the carbonyl group, and if L2 is not a single bond, it means the oxygen atom of -(CH2)-O-).

[0101] When X2 in Formula 4 is an oxygen atom, it is the case that starch or the like as a polysaccharide is maleated, and when X2 is NR 11 In the case of maleated chitosan or chitin as a polysaccharide. 11 The alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, or a methyl group, and such an alkyl group may be linear, branched or cyclic, and may also be optionally substituted with one or more substituents.

[0102] As described above, the self-crosslinking structure can be achieved by esterification between acidic polysaccharides, especially polysaccharides having carboxyl groups.

[0103] As the acidic polysaccharide, a polysaccharide having carboxyl groups itself, such as CMC (carboxymethyl cellulose), can be used, or a polysaccharide into which carboxyl groups are introduced by a process such as maleation or carboxyalkylation can be used, wherein in order to achieve the above-mentioned degree of substitution and effective self-crosslinking, a polysaccharide into which carboxyl groups are introduced by a denaturation process can be used.

[0104] The method for introducing carboxyl groups into polysaccharides is not particularly limited. For example, to introduce functional groups such as Formula 4, a so-called maleation process can be performed. Such a process is a process in which a polysaccharide is reacted with an unsaturated dicarboxylic acid or an anhydride thereof to replace the hydroxyl groups present in the unit body of the polymer with functional groups, wherein examples of dicarboxylic acids or anhydrides thereof can be exemplified by maleic acid or maleic anhydride, etc., but are not limited thereto, and salts of maleic acid can also be used. Methods for performing maleation processes are known.

[0105] The carboxyalkylation process can be carried out by reacting the polysaccharide with an alkanoic acid or a halogenated alkanoic acid or a salt of an alkanoic acid or a halogenated alkanoic acid. As is known, an alkanoic acid is an aliphatic acid derived from an alkane, and a halogenated alkanoic acid is an alkanoic acid in which at least one of the hydrogen atoms of the alkanoic acid is replaced by a halogen atom (e.g., chlorine, fluorine, or bromine). In this specification, the alkanoic acid, halogenated alkanoic acid, salt of an alkanoic acid, and / or salt of a halogenated alkanoic acid used in the carboxyalkylation process may be referred to as a treating agent.

[0106] As the alkanoic acid or halogenated alkanoic acid used as the treating agent, an alkanoic acid or halogenated alkanoic acid having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms can be used, and acetic acid or chloroacetic acid can be typically used.

[0107] In addition, the halogenated alkanoic acid or the salt of the alkanoic acid may be an alkali metal salt or alkaline earth metal salt of a halogenated alkanoic acid or an alkanoic acid having the same number of carbon atoms as above.

[0108] By reacting the treating agent with the polysaccharide under appropriate conditions, acidic groups (carboxyl groups) can be introduced into the polysaccharide.

[0109] The process of introducing the acidic group can be performed according to a known method, and if necessary, an additional process may be performed or the conditions of the process may be adjusted for efficient performance of the carboxyalkylation process.

[0110] For example, the above process can be carried out in a mixture in which the treatment agent and the hydroxide are dispersed in a solvent. Here, as the solvent, for example, an aqueous solvent such as water can be used. Here, as the water, tap water, distilled water, deionized water, purified water, etc. can be used. Here, as the hydroxide, ammonium hydroxide or a metal hydroxide can be used, and as the metal hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be used, but are not limited thereto.

[0111] It is contemplated that in the reaction of the mixture, for example, a gelatinization reaction of the polysaccharide is first performed in the mixture, followed by introduction of carboxyl groups by the treating agent.

[0112] For example, when the torque of the reactor in which the mixture is present after gelatinization reaches a certain level, the reaction can be carried out. In this way, the introduction of appropriate carboxyl groups is carried out.

[0113] For example, if the mixture is mixed in a mixer capable of mixing the components by rotation, such as an internal mixer, gelatinization proceeds. During gelatinization, the load caused by gelatinization generates heat energy within the reactor, causing an increase in torque and temperature. Typically, a section occurs in which the torque and temperature within the reactor increase to a certain level and then remain constant. The point at which this section occurs is generally considered to be the point at which gelatinization is complete. By maintaining the torque at an appropriate level at and / or after the point in time when gelatinization is complete, such as to achieve the desired degree of substitution, a polysaccharide capable of effectively self-crosslinking can be obtained.

[0114] In an example, the lower limit of the torque in the reactor after gelatinization completion time point and / or gelatinization completion time point can be 5Nm, 5.5Nm, 7Nm, 7.5Nm or 8Nm or so, and its upper limit can be 20Nm, 19Nm, 18Nm, 16Nm, 15Nm, 14Nm, 13Nm, 12Nm, 11Nm, 10Nm or 9Nm or so.This torque can be greater than or equal to or greater than any one in the above-mentioned lower limit, or be less than or equal to or less than any one in the above-mentioned upper limit, or be less than or equal to or less than any one in the above-mentioned upper limit simultaneously greater than or equal to or greater than any one in the scope of the above-mentioned lower limit.By torque being maintained in the above scope, the excessive evaporation of solvent can be prevented, and processability can be stably kept, while the substitution efficiency of carboxyl is maintained in the desired scope.

[0115] In order to maintain the torque as above, the ratio of the solvent in the mixture can be controlled. For example, the lower limit of the ratio of the solvent in the mixture can be about 0.45 times, 0.5 times, 0.6 times, or 0.7 times of the weight of the polysaccharide present in the mixture, and its upper limit can be about 0.75 times, 0.74 times, 0.73 times, or 0.72 times of the weight of the polysaccharide present in the mixture. The ratio can be greater than or equal to, or greater than any one of the above-mentioned lower limits, or less than or equal to, or less than any one of the above-mentioned upper limits, or less than or equal to, or less than any one of the above-mentioned upper limits while being greater than or equal to, or greater than the scope of any one of the above-mentioned lower limits. By keeping the ratio of the solvent in the above range, excessive evaporation of the solvent can be prevented, and the torque that can stably maintain processability can be maintained while the substitution efficiency of the carboxyl group is maintained in the desired range.

[0116] In the above reaction process, it may be appropriate to use only the above aqueous solvent (e.g., water) as a solvent. Generally, as a solvent for carboxyalkylation, in addition to aqueous solvents, alcohols, ketones, 1,4-diols, However, when such a solvent is used, the reaction may not proceed as desired.

[0117] In some embodiments, the mixture can be substantially free of solvent except aqueous solvent (for example, water).At this moment, the fact that it is substantially free of solvent can mean such situation: the upper limit of the content of the solvent except aqueous solvent (for example, water) in mixture is 10 weight %, 9 weight %, 8 weight %, 7 weight %, 6 weight %, 5 weight %, 4 weight %, 3 weight %, 2 weight %, 1 weight %, 0.5 weight %, 0.1 weight %, 0.05 weight %, 0.01 weight %, 0.005 weight % or 0.001 weight % or so, and its lower limit is 0 weight % or so.This ratio can be less than any one in the above-mentioned upper limit, or being less than or equal to or less than any one in the above-mentioned upper limit simultaneously being greater than or equal to or greater than in the scope of any one in the above-mentioned lower limit.

[0118] The ratio of hydroxide to treating agent in the mixture can also be controlled.

[0119] For example, the lower limit of the ratio of hydroxide in the mixture can be about 0.5 equivalents, 0.6 equivalents, or 0.7 equivalents, and its upper limit can be about 1.5 equivalents, 1.15 equivalents, 1.1 equivalents, 1 equivalent, 0.9 equivalents, or 0.8 equivalents. This equivalent can be less than or equal to or less than any one of the above-mentioned upper limits, or in the range of being less than or equal to or less than any one of the above-mentioned upper limits while being greater than or equal to or greater than any one of the above-mentioned lower limits. Here, this equivalent can be obtained by formula A / B, wherein A is the molar number of hydroxide present in the mixture, and B is the value calculated according to C / 162.14, wherein C is the weight (unit: g) of polysaccharide in the mixture. Here, 162.14 is the molar mass (g / mol) of anhydroglucose unit. Typically, polysaccharide comprises anhydroglucose unit or its derivatives, or has a unit of similar molar mass. Therefore, in the present application, if the amount of polysaccharide used to obtain the above equivalent weight is representatively applied by formula C / 162.14, then by specifying the equivalent weight within the above range according to such application, the reaction can be carried out according to the purpose. By keeping the amount of the hydroxide used within the above range, the reaction efficiency and processability can be stably maintained, while the substitution efficiency of the carboxyl group can be kept within the desired range, and unnecessary side reactions can be suppressed.

[0120] In addition, the lower limit of the ratio of treatment agent in the mixture can be about 0.5 equivalent, 0.6 equivalent or 0.7 equivalent, and its upper limit can be about 1.5 equivalent, 1.15 equivalent, 1.1 equivalent, 1 equivalent, 0.9 equivalent or 0.8 equivalent.This equivalent can be less than or equal to or less than any one in the above-mentioned upper limit, or is less than or equal to or less than any one in the above-mentioned upper limit simultaneously in the scope of more than or equal to or greater than any one in the above-mentioned lower limit.Here, this equivalent can obtain by formula D / B, and wherein D is the molar number of the treatment agent existing in the mixture, and B is identical with the formula for calculating hydroxide equivalent.By the usage amount of treatment agent being remained in the above scope, reaction efficiency and processability can be stably kept, simultaneously the substitution efficiency of carboxyl is remained in the scope of expectation, and unnecessary side reaction etc. can be suppressed.

[0121] The lower limit of the ratio (A / B) of the mole number (A) of hydroxide and the mole number (D) of treating agent in the mixture can be about 0.5,0.6,0.7,0.8,0.9 or 0.95, and its upper limit can be about 1.5,1.4,1.3,1.2,1.1 or 1.05.This ratio can be less than or equal to or less than any one in the above-mentioned upper limit, or be less than or equal to or less than any one in the above-mentioned upper limit while being greater than or equal to or greater than the scope of any one in the above-mentioned lower limit.By keeping above ratio, can obtain the polysaccharide that can stabilize self-crosslinking while the substitution efficiency of carboxyl is maintained in the desired range, can stably keep reaction efficiency and processability, and can suppress unnecessary side reaction etc.

[0122] In the above reaction, the mixture can be present in the reactor where the reaction occurs at a predetermined ratio. For example, based on the total volume of the reactor, the lower limit of the ratio of the volume of the mixture in the reactor can be about 70%, 75%, 76% or 77%, and its upper limit can be about 95%, 94%, 93% or 92%. The ratio can be less than or equal to, or less than any one of the above-mentioned upper limits, or in a range of less than or equal to, or less than any one of the above-mentioned upper limits and greater than or equal to, or greater than any one of the above-mentioned lower limits. By maintaining the above ratio, the torque in the reactor can be stably maintained, the polysaccharide capable of stable self-crosslinking can be obtained while the substitution efficiency of the carboxyl group is maintained within the desired range, the reaction efficiency and processability can be stably maintained, and unnecessary side reactions can be suppressed.

[0123] In the above reaction, the temperature in the reactor at the time point of gelatinization completion and / or after the time point can also be maintained at a certain level. For example, the lower limit of the temperature can be about 90°C, 92°C, 94°C, or 96°C, and the upper limit thereof can be about 110°C, 105°C, 100°C, 99°C, 98°C, or 97°C. The temperature can be less than or equal to, or less than any one of the above-mentioned upper limits, or in a range of less than or equal to, or less than any one of the above-mentioned upper limits and greater than or equal to, or greater than any one of the above-mentioned lower limits. By maintaining the above temperature, the torque in the reactor can be stably maintained, a polysaccharide capable of stable self-crosslinking can be obtained while maintaining the substitution efficiency of the carboxyl group within the desired range, reaction efficiency and processability can be stably maintained, and unnecessary side reactions can be suppressed.

[0124] As described above, carboxyalkylation can be carried out using a reactor that can mix the mixture by rotation. There is no particular limitation on the specific type of reactor, and for example, internal mixers such as a twin-roll mixer, a Banbury mixer, and an intermix mixer can be used. Torque and temperature can also be measured by sensors installed on such mixers.

[0125] Incorporation time is not particularly limited, and it can be controlled to realize the gelatinization and the carboxyalkylation level of expectation.For example, the lower limit of incorporation time can be about 5 minutes, 7 minutes, 9 minutes or 10 minutes, and its upper limit can be about 60 minutes, 55 minutes, 50 minutes, 45 minutes, 40 minutes, 35 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 14 minutes, 13 minutes, 12 minutes, 11 minutes or 10 minutes.This incorporation time can be less than or equal to or less than any one in the above-mentioned upper limit, or is less than or equal to or less than any one in the above-mentioned upper limit simultaneously in the scope of being greater than or equal to or greater than any one in the above-mentioned lower limit.

[0126] The rotating speed of mixing can be controlled, to keep the torque and / or temperature of expectation.The lower limit of this rotating speed can be such as 30rpm, 35rpm, 40rpm, 45rpm or 50rpm or so, and its upper limit can be 100rpm, 95rpm, 90rpm, 85rpm, 80rpm, 75rpm, 70rpm, 65rpm, 60rpm, 55rpm or 50rpm or so.This rotating speed can be less than or equal to or less than any one in the above-mentioned upper limit, or be less than or equal to or less than any one in the above-mentioned upper limit simultaneously greater than or equal to or greater than the scope of any one in the above-mentioned lower limit.

[0127] Through the above process, carboxyalkylation proceeds, and the desired polysaccharide can be obtained.

[0128] The self-crosslinking process may also be performed immediately after the carboxyl groups are introduced into the polysaccharide by the reaction, and if necessary, after the polysaccharide is recovered once, the self-crosslinking process may be performed.

[0129] Here, the recovery of the polysaccharide may include a process of dissolving a reactant produced by the reaction in water and precipitating it using an organic solvent such as alcohol, and various methods may be applied besides this.

[0130] After the acidic polysaccharide is obtained in the above manner, it can be self-crosslinked. The method for self-crosslinking is not particularly limited, but for efficient self-crosslinking, it can be performed by dispersing the acidic polysaccharide in a solvent and then maintaining the pH within a predetermined range.

[0131] In the above process, the above-mentioned aqueous solvent such as water may also be used as a solvent, and tap water, distilled water, deionized water, pure water, or the like may be used as water.

[0132] In some embodiments, the present invention relates to a method for the preparation of the present invention that is suitable for use in conjunction with water-based solvents (for example, water) or the like. In some embodiments, the present invention relates to a method for preparing the present invention that is suitable for use in conjunction with water-based solvents (for example, water) or the like. In some embodiments, the present invention relates to a method for preparing the present invention that is suitable for use in conjunction with water-based solvents (for example, water) or the like. In some embodiments, the present invention relates to a method for preparing the present invention that is suitable for use in conjunction with water-based solvents (for example, water) or the like. In some embodiments, the present invention relates to a method for preparing the present invention that is suitable for use in conjunction with water-based solvents (for example, water) or the like.

[0133] The amount of the solvent used in the above process can be 5 to 15 times the weight of the polysaccharide used. The dissolution of the polysaccharide in the solvent can be carried out at room temperature and normal pressure, but is not limited thereto.

[0134] Self-crosslinking can be performed by dissolving the polysaccharide in a solvent and maintaining the pH at a constant level. If necessary, an additional process that can promote self-crosslinking, such as a stirring process, can also be performed.

[0135] The lower limit of the pH maintained in the above process can be about 4, 4.5, 5, 5.5 or 6, and the upper limit can be about 10, 9.5, 9, 8.5, 8, 7.5, 7 or 6.5. The pH can be less than or equal to, or less than any one of the above upper limits, or less than or equal to, or less than any one of the above upper limits while being greater than or equal to, or greater than any one of the above lower limits. By maintaining this pH range, the desired self-crosslinking can be effectively performed.

[0136] The method for maintaining the pH within the above range is not particularly limited. If the pH within the above range is achieved by adding an acidic polysaccharide, self-crosslinking can proceed in this state. If the desired pH is not achieved, the pH can be adjusted by adding an appropriate acid or base in consideration of the desired pH. In this case, for example, hydroxides used in carboxyalkylation can be used as bases, and hydrochloric acid, sulfuric acid, etc. can be used as acids, but are not limited thereto.

[0137] During the above reaction process, a catalyst can be added as needed. For example, an ester catalyst that promotes the reaction of carboxyl and hydroxyl groups can be added. As such a catalyst, 4-methylaminopyridine, magnesium acetate, tetra-n-butyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide and / or N-methylimidazole can be used, but are not limited thereto. The catalyst can be added in a catalytic amount, for example, relative to 1 mole of polysaccharide applied to the reaction, it can be used at a ratio within the range of 0.1 mol to 5 mol. The lower limit of the catalyst usage ratio can be about 0.1 mol, 0.5 mol, 1 mol, or 2 mol, and the upper limit thereof can be about 5 mol, 4.5 mol, 4 mol, or 3.5 mol. The ratio can be less than or equal to, or less than any one of the above upper limits, or less than or equal to, or less than any one of the above upper limits while being greater than or equal to, or greater than any one of the above lower limits.

[0138] If necessary, the reaction can also be carried out in the presence of a heat stabilizer. Suitable heat stabilizers include organic or inorganic phosphorus compounds, such as phosphoric acid, organic esters of phosphoric acid, phosphorous acid, or organic esters of phosphorous acid. For example, phosphoric acid, alkyl phosphates, or aryl phosphates known commercially as heat stabilizers can be used.

[0139] Furthermore, if necessary, the reaction can also be carried out in the presence of additives such as a thickener, a plasticizer, a storage stabilizer and / or an antioxidant.

[0140] Cross-linking reaction can be carried out at a predetermined temperature. For example, the lower limit of the temperature for the reaction can be about 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, and its upper limit can be about 300°C, 280°C, 260°C, 240°C, 220°C, 200°C, 180°C, 160°C, 140°C, 130°C, 125°C or 125°C. The temperature can be less than or equal to or less than any one of the above-mentioned upper limits, or in a range of less than or equal to or less than any one of the above-mentioned upper limits and greater than or equal to or greater than any one of the above-mentioned lower limits. Such reaction temperature can be achieved by methods such as hot air supply, infrared irradiation, microwave irradiation or ultraviolet irradiation.

[0141] The time that reaction is carried out is not particularly limited.For example, the lower limit of the reaction times can be 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes or about 120 minutes, and its upper limit can be 500 minutes, 480 minutes, 460 minutes, 440 minutes, 420 minutes, 400 minutes, 380 minutes, 360 minutes, 340 minutes, 320 minutes, 300 minutes, 280 minutes, 260 minutes, 240 minutes, 220 minutes, 200 minutes or about 180 minutes.The time can be less than or equal to or less than any one in the above-mentioned upper limit, or being less than or equal to or less than any one in the above-mentioned upper limit simultaneously being greater than or equal to or greater than the scope of any one in the above-mentioned lower limit.

[0142] The desired self-crosslinked polysaccharide component can be obtained by the above method.

[0143] In addition to the self-crosslinked polysaccharide component, the polymer material may also contain a crosslinking agent that reacts with the polysaccharide component. Such a reaction can be introduced by reacting the self-crosslinked polysaccharide component with the crosslinking agent. That is, the polymer material of the present application can be provided in a state in which two or more polysaccharide molecules are crosslinked by the above-mentioned self-crosslinking and then further crosslinked by applying a crosslinking agent. The introduction of this further crosslinking serves to increase the gel strength of the self-crosslinked polysaccharide component and improve the absorption capacity under pressure (AUP) and / or saline flow conductivity.

[0144] Alternatively, an additional crosslinking agent may be introduced, for example, by treating the self-crosslinked polysaccharide component, such as by grinding it into a powder, and reacting the surface of the powder with the crosslinking agent. In this case, the polymer material may include the self-crosslinked polysaccharide component in the form of particles and the crosslinking agent bound to the surface of the particles. In this case, the size of the particles is not particularly limited, and the particles can be controlled to an appropriate size depending on the intended use.

[0145] Such a cross-linking agent may have two or more functional groups capable of reacting with the functional groups (hydroxyl, amino or carboxyl groups, etc.) of the polysaccharide component. The cross-linking agent may have 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, or 2 to 3, or 2, or 3 functional groups capable of reacting with the functional groups (hydroxyl, amino or carboxyl groups, etc.) of the polysaccharide component.

[0146] As the type of applicable crosslinking agent, one or more selected from polyfunctional epoxy compounds, epoxysilane compounds, aminosilane compounds, epichlorohydrin, aldehyde compounds such as formaldehyde or glutaraldehyde, acid chlorides, carbonates, diamines, diols, carbon disulfide, phosphorus oxychloride, divinylbenzene, organic acids and organic acid anhydrides can be used.

[0147] In order to achieve efficient cross-linking and ensure desired physical properties, it may be advantageous to use a specific type of cross-linking agent.

[0148] In one example, as the cross-linking agent, an organic acid having two or more carboxyl groups, or an anhydride of the organic acid, or an organic compound having two or more aldehyde groups (formyl groups or aldehyde groups) may be used.

[0149] The organic acid, the anhydride of the organic acid or the organic compound may consist only of carbon, oxygen and hydrogen.

[0150] The type of organic acid that can be used as a crosslinking agent is not particularly limited, but an organic acid having a molecular weight of about 90 g / mol to 300 g / mol, or about 100 g / mol to 250 g / mol can be used. The organic acid can have 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, or 2 to 3, or 2, or 3 carboxyl groups.

[0151] Examples of such organic acids include, but are not limited to, citric acid, succinic acid, pimelic acid, and adipic acid.

[0152] An organic acid or an anhydride thereof can be used as a cross-linking agent.

[0153] The type of organic compound having two or more aldehyde groups that can be used as a crosslinking agent is not particularly limited, but an organic compound having a molar mass of about 90 g / mol to 200 g / mol, or about 90 g / mol to 150 g / mol can be used. The organic compound can have 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, or 2 to 3, or 2, or 3 aldehyde groups.

[0154] Examples of such organic compounds include glutaraldehyde, but are not limited thereto.

[0155] In one example, oxidized polysaccharides (including oxidized disaccharides) can be used as cross-linking agents. In this case, the definition of polysaccharide is as described above. When the polysaccharide component is oxidized, the hydroxyl groups contained in the polysaccharide are first converted into carbonyl groups to form aldehyde groups, and as further oxidation proceeds, carboxyl groups can be generated. Since aldehyde groups or carboxyl groups can participate in cross-linking reactions, they can be used as cross-linking agents. Methods for oxidizing polysaccharides are known.

[0156] Examples of suitable oxidized polysaccharides include oxidized starch, oxidized dextrin, oxidized chitosan, oxidized chitin, oxidized sucrose and / or oxidized maltose, but are not limited thereto.

[0157] As the oxidized polysaccharide, for example, a component having a molar mass within a predetermined range and having 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, or 2 to 3, or 2, or 3 aldehyde groups (formyl or aldehyde groups) and / or carboxyl groups can be used.

[0158] In another example, the lower limit of the ratio of aldehyde groups and / or carboxyl groups per mole of oxidized polysaccharide in the oxidized polysaccharide may be about 0.01 mol, 0.05 mol, 0.1 mol, 0.15 mol, 0.2 mol, 0.25 mol, or 0.3 mol, and the upper limit thereof may be about 0.9 mol, 0.85 mol, 0.8 mol, 0.75 mol, 0.7 mol, 0.65 mol, 0.6 mol, 0.55 mol, 0.5 mol, 0.45 mol, 0.4 mol, 0.35 mol, or 0.3 mol. The molar ratio of aldehyde groups and / or carboxyl groups per mole of oxidized polysaccharide may be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within the range of less than or equal to, or less than any of the above upper limits and greater than or equal to, or greater than any of the above lower limits. The ratio may be determined by the amount of the oxidized polysaccharide. 1 H NMR analysis. That is, because the carboxyl and / or aldehyde groups present in the polysaccharide can be determined by 1 H NMR analysis is quantitative, so the ratio can be determined. 1 The method of quantitatively analyzing functional groups by H NMR analysis is known.

[0159] The molar mass of the oxidized polysaccharide may have a lower limit of about 100 g / mol, 150 g / mol, 200 g / mol, 250 g / mol, or 300 g / mol, and an upper limit thereof may be about 1000 g / mol, 950 g / mol, 900 g / mol, 850 g / mol, 800 g / mol, 750 g / mol, 700 g / mol, 650 g / mol, 600 g / mol, 550 g / mol, 500 g / mol, 450 g / mol, 400 g / mol, or 350 g / mol. The molar mass may be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within a range of less than or equal to, or less than any of the above upper limits while greater than or equal to, or greater than any of the above lower limits. Typically, disaccharides in the polysaccharide exhibit molar masses within the above ranges.

[0160] The polymer material treated with such a crosslinking agent can meet the desired absorption characteristics and biodegradability while exhibiting appropriate gel strength.

[0161] In the polymer material, the weight ratio of the crosslinking agent relative to 100 parts by weight of the self-crosslinked polysaccharide component can have a lower limit of about 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or about 5 parts by weight, and an upper limit thereof can be about 20 parts by weight, 18 parts by weight, 16 parts by weight, 14 parts by weight, 12 parts by weight, 10 parts by weight, 8 parts by weight, or about 6 parts by weight. The ratio can be greater than or equal to, or greater than any of the above lower limits, or less than or equal to, or less than any of the above upper limits, or within the range of less than or equal to, or less than any of the above upper limits while greater than or equal to, or greater than any of the above lower limits. Typically, the disaccharides in the polysaccharide exhibit a molar mass within the above range.

[0162] At such a ratio, the polymer material can meet the desired absorption characteristics and biodegradability while exhibiting appropriate gel strength.

[0163] The polymer material may include the polysaccharide component as described above (the polysaccharide component that is self-crosslinked and combined with a crosslinking agent), and may further include other components if necessary.

[0164] In one example, the lower limit of the ratio of the polysaccharide component (the polysaccharide component that is self-crosslinked and combined with the crosslinking agent) in the polymer material can be about 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, 92% by weight, 94% by weight, 96% by weight, or 98% by weight, and the upper limit thereof can be about 100% by weight, 98% by weight, 96% by weight, 94% by weight, 92% by weight, or 90% by weight. The ratio can be less than any of the above upper limits, or within a range of less than or equal to, or less than, any of the above upper limits and greater than or equal to, or greater than any of the above lower limits.

[0165] The ratio of the polysaccharide component in the polymer material is not particularly limited, but the higher the ratio, the greater the biodegradability of the polymer material. However, in conventional absorbent materials using polysaccharide components, excessively increasing the polysaccharide component ratio, in view of biodegradability, can lead to a decrease in absorption capacity. However, in the present application, the desired absorption capacity can be stably achieved while maintaining a high polysaccharide component ratio.

[0166] Since polymer materials simultaneously exhibit excellent absorbability and biodegradability, they can be used in various applications.

[0167] For example, the polymer material can be used as a sanitary product such as a diaper or sanitary napkin, or as an absorbent material for other applications requiring absorption. If necessary, the polymer material can be further cross-linked, surface treated, or physically ground to improve its efficiency as a sanitary product or absorbent material.

[0168] Therefore, the present application relates to absorbent materials or hygiene products (such as diapers, sanitary napkins, etc.) comprising said polymer material.

[0169] A specific method of forming an absorbent material or a sanitary product by applying the polymer material is not particularly limited, and for example, a method of forming an absorbent material or a sanitary product by applying an existing SAP may be used in the same manner.

[0170] Beneficial effects

[0171] The present application can provide a polymer material having excellent biodegradability and absorption capacity and uses thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0172] Figures 1 to 3 The material obtained in the preparation example 1 H NMR spectrum. DETAILED DESCRIPTION

[0173] Hereinafter, the present application will be described in detail below through Examples and Comparative Examples, but the scope of the present application is not limited to the following Examples.

[0174] 1. Assessment of Centrifuge Retention Capacity (CRC)

[0175] Centrifugal retention capacity (CRC) is measured according to EDANA (European Disposables and Nonwovens Association) WSP 241.3. The polymeric material of the acquisition of about 0.2g (WO) is placed in nonwoven bag, sealing, then immersed in normal saline solution. As normal saline solution, working concentration is the NaCl aqueous solution of 0.9 % by weight. Kept this state about 30 minutes, used centrifuge under the condition of 250G, from bag, remove water 3 minutes, and measure the quality (g, W of bag).

[0176] The same operation was performed on the same nonwoven bag without the polymer material, and the mass (g, W1) was measured.

[0177] CRC(g / g) is calculated by substituting the measurement results into the following equation A.

[0178] The evaluation was performed under constant temperature and humidity conditions (23±1° C., relative humidity: 50±10%).

[0179] [Equation A]

[0180] CRC(g / g)={[W2(g)-W1(g)] / W0(g)}-1

[0181] 2. Assessment of Absorption Capacity Under Pressure (AUP)

[0182] According to the standard measurement of EDANA (European Disposables and Nonwovens Association) WSP 242.3, the absorption capacity under pressure (AUP, 0.7psi) of polymeric material is measured. 400 mesh stainless steel wire mesh is installed on the bottom of the plastic cylinder that internal diameter is about 60mm. Under the condition of 23 ± 2 ℃ temperature and 50% relative humidity, about 0.90g (W0) of polymeric material is evenly sprayed on the wire mesh, and the piston that can further evenly apply about 0.7psi load is installed thereon, to make measuring device. As piston, use the piston that external diameter is slightly less than 60mm, described piston is installed so that it can move up and down and can not form gap with the inner wall of cylinder. The weight (unit: g) (W3) of measuring device is measured.

[0183] A glass filter with a diameter of approximately 90 mm and a thickness of approximately 5 mm was placed inside a culture dish with a diameter of approximately 150 mm. A physiological saline solution (0.9% by weight sodium chloride solution) was applied to the same height as the upper surface of the glass filter. A piece of filter paper with a diameter of approximately 90 mm was placed on top of the filter paper. A measuring device was placed on the filter paper and allowed to absorb the physiological saline solution under a load of 0.7 psi for 1 hour. After 1 hour, the measuring device was raised and the weight (g) was measured.

[0184] The absorption capacity under pressure (AUP) (g / g) was calculated by substituting each measured weight into the following equation B.

[0185] [Equation B]

[0186] AUP(g / g)=[W4(g)-W3(g)] / W0(g)

[0187] 3. Measurement of biodegradability

[0188] The degree of biodegradability was measured using the method specified in the ISO 14855-1 (2005) standard. This standard is a method for measuring the aerobic biodegradability of plastic materials under composting conditions. It is a method for calculating the biodegradability of polymeric materials by quantifying the amount of carbon dioxide released by microorganisms that metabolize the material. When the polymeric material is subjected to composting conditions according to the standard, the degree of biodegradability is measured for six months and the degree of biodegradability is calculated as the ratio of the material's theoretical carbon dioxide production to its actual carbon dioxide production. The theoretical carbon dioxide production and degree of biodegradability are calculated according to the following equations C and D, respectively.

[0189] [Equation C]

[0190] Theoretical carbon dioxide generation (ThCO2, g / container) = M T O T ×C T O T ×(44 / 12)

[0191] In Equation C, M T O T is the amount (g) of the total dry solid content of the test material (polymer material) added to the compost at the beginning of the measurement, and C T O T It means the ratio (g / g) of organic carbon contained in the total dry solid content of the test material.

[0192] [Equation D]

[0193] Degree of biodegradability (%) = [{(CO2) T-(CO2) B} / ThCO2]×100

[0194] In equation D, (CO2) T is the cumulative amount of carbon dioxide generated from the compost container containing the test material (g / container), (CO2) B is the average value of the cumulative amount of carbon dioxide generated from the inoculum source container (g / container), and ThCO2 is the theoretical carbon dioxide generation amount confirmed in Equation C above.

[0195] 4. Molecular Weight Measurement of Polysaccharide Components

[0196] The molecular weight (weight average molecular weight, unit: g / mol) of the polysaccharide component was evaluated in the following manner.

[0197] (1) Preparation of mobile phase

[0198] Mobile phase A was prepared by filtering 1000 mL of a 150 mM NaNO 3 aqueous solution containing 0.02 wt % NaN 3 using a solvent purification system (Millipore Millisolve Kit, MilliporeSigma).

[0199] (2) Preparation of sample solution

[0200] The sample to be measured was collected in an amount of 25 mg and mixed with 5 mL of a 150 mM NaNO 3 aqueous solution containing 0.02 wt % NaN 3 , and then a sample solution was prepared by heating the mixture at 80° C. for 20 hours, and then filtered with a 0.4 μm nylon syringe filter.

[0201] (3) GPC (gel permeation chromatography) / MALS (multi-angle light scattering) conditions

[0202] The molecular weight was evaluated using the sample solution and mobile phase A in the following manner.

[0203] Measuring instrument: Agilent GPC (Agilent 1200 series, USA)

[0204] Stationary phase: Connecting Shodex OH-Pak 804 column and Shodex OH-Pak 80 column Mobile phase: A; 0.02% NaN3, 150mM NaNO3 aqueous solution = 100 (volume / volume%)

[0205] Flow rate: 0.4 mL / min

[0206] Stationary phase temperature: 25°C

[0207] Injection volume: 100 μL (filtered through 0.45 μm)

[0208] Analysis time: 120 minutes

[0209] Preparation Example 1.

[0210] A polysaccharide (modified chitosan) (Compound A) containing a modified monosaccharide unit of the following formula A was prepared in the following manner. The modified monosaccharide unit of the following formula A is a monosaccharide unit into which a maleic acid group is introduced.

[0211] [Formula A]

[0212]

[0213] 15g chitosan and 300mL DMSO (dimethyl sulfoxide) are added in 500mL RBF (round-bottom flask), and stirred at 65 ℃ for 30 minutes to carry out gelatinization.In the chitosan through gelatinization, add about 30g maleic anhydride, and react about 3 hours at 65 ℃.After reaction is completed, the temperature is cooled to about room temperature (about 25 ℃), and acetone is added thereto to produce precipitate.Reclaim precipitate, and in 40 ℃ vacuum drying oven, dry one day, to obtain solid target product (Compound A).

[0214] The degree of substitution of the obtained target product (compound A) can be determined by 1 H NMR analysis was performed. 1 H NMR analysis was performed at room temperature (approximately 25°C). 1 H NMR spectroscopy was performed, as described 1 The H NMR spectrometer consisted of a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. 1 For H NMR analysis, a Bruker Avance Neo instrument was used.

[0215] 50 mg of the obtained solid target product (Compound A) and 200 mg of a 30% DCl solution in D2O were mixed and stirred at 50°C for about 1 hour to initiate a hydrolysis reaction, and the mixture was allowed to proceed. 1 H NMR analysis.

[0216] pass 1 H NMR analysis was used to determine the degree of substitution of maleic acid groups in chitosan. Figure 1 The target product 1 H NMR spectrum. Figure 1Peaks were identified at 6.3 ppm and 5.8 ppm corresponding to the vinyl groups of maleic acid groups, which confirmed that maleic acid groups had been introduced into chitosan. Based on the integral ratio of the peaks, the degree of substitution of maleic acid groups (-OCOCH=CHCOOH) in maleated chitosan was determined, and the degree of substitution obtained in this manner was approximately 0.94.

[0217] Preparation Example 2.

[0218] A polysaccharide (modified starch) (compound B) containing a modified monosaccharide unit of the following formula B was prepared in the following manner. The modified monosaccharide unit of the following formula B is a monosaccharide unit into which a maleic acid group is introduced.

[0219] [Formula B]

[0220]

[0221] 15g starch and 50mL DMSO (dimethyl sulfoxide) are added in 500mL RBF (round-bottom flask), and stirred at 65 ℃ for 2 hours to carry out gelatinization. As starch, potato starch is used. About 30g maleic anhydride is added to the gelatinized starch, and reacted at 65 ℃ for about 3 hours. After the reaction is completed, the temperature is cooled to room temperature, and acetone is added thereto to produce precipitation. The precipitate is reclaimed and dried in a vacuum drying oven at 40 ℃ for one day to obtain a solid target product (Compound B).

[0222] 50 mg of the obtained solid target product (Compound B) was mixed with 200 mg of a 30% DCl solution in D2O and stirred at 50°C for about 1 hour to initiate a hydrolysis reaction, which was then allowed to proceed. 1 H NMR analysis.

[0223] In the same manner as in Preparation Example 1, 1 The degree of substitution of the target product (Compound B) was determined by H NMR analysis, and as a result, the degree of substitution was approximately 0.8. Figure 2 The target product 1 H NMR analysis results.

[0224] Preparation Example 3.

[0225] Oxidized polysaccharides (oxidized disaccharides) (oxidized maltose) were prepared in the following manner. 20 g of maltose was dissolved in 100 mL of distilled water in a 500 mL RBF (round bottom flask). Light was blocked with foil, and about 0.5 to 0.75 equivalents of NaIO4 were introduced thereto, and stirred at room temperature (about 25°C) for about 24 hours. Barium acetate was further introduced thereto, and stirred, and the solution filtered through a filter was then dried to obtain oxidized maltose. Figure 3The target product (oxidized maltose) 1 H NMR analysis results. The extent of aldehyde formation in oxidized maltose can be examined by 1 The results of H NMR analysis were confirmed. 1 In the H NMR analysis result, the integral value of the peak (corresponding to the peak of aldehyde group) identified in the range of 8.0ppm to 8.5ppm is set to 1, and the integral value of other peaks is set based on this. Afterwards, the integral value of the peak identified in the range of 3.0ppm to 4.0ppm is divided by 14 to confirm the value. The peak identified in the range of 3.0ppm to 4.0ppm is the peak of the ring structure derived from oxidized polysaccharide (oxidized maltose), and therefore 14 is a value related to the number of hydrogen atoms present in the ring structure and the value obtained by dividing the integral value by 14. Therefore, by comparing the integral value of the peak (corresponding to the peak of aldehyde group) identified in the range of 8.0ppm to 8.5ppm and the integral value of the peak identified in the range of 3.0ppm to 4.0ppm divided by 14, the ratio of aldehyde group contained in oxidized maltose can be determined. As a result determined in this way, oxidized maltose contains about 0.3 mole of aldehyde group per mole.

[0226] Example 1

[0227] The self-crosslinked polysaccharide component was prepared by self-crosslinking CMC (carboxymethyl cellulose). When an aqueous solution having a concentration of 1 wt % was prepared using CMC, CMC having an aqueous solution having a viscosity of about 1600 cP to 1700 cP and a degree of substitution (DS) of about 0.7 to 0.8 was used as CMC (carboxymethyl cellulose). Here, the viscosity of the aqueous solution was measured using a Brookfield viscometer-DV2T apparatus, wherein a V-74 rotor was selected as the rotor, the speed was set to 50 rpm, and the measurement temperature was set to 25°C. In addition, the degree of substitution (DS) is the degree of substitution of the carboxyl groups present in the CMC, which was determined by the conditions based on Preparation Examples 1 and 2. 1 H NMR analysis results were obtained. 20 g of CMC was dissolved in 800 mL of distilled water, spread thinly on a tray, and then dried in an oven at approximately 40°C. The pH of the CMC and distilled water mixture was adjusted to approximately 10.5 by adding approximately 1N aqueous NaOH. After drying, the CMC was heated at 120°C for 3 hours to produce a self-crosslinked polysaccharide component. The polysaccharide component was then pulverized and classified to obtain a material with a particle size of approximately 300 to 600 μm.

[0228] The material obtained is carried out to surface crosslinking.Use by the compound (oxidized maltose) of 0.18g Preparation Example 3 and 0.018g AlCl3 being dissolved in the surface crosslinking solution prepared in the solution of 0.6g acetone and 0.6g water and carry out surface crosslinking.3.6g is crushed and classified into the material that particle size is about 300 μm to 600 μm and is placed on aluminum tray, and crosslinking solution is sprayed evenly.Described mixture is mixed, until crosslinking agent is fully mixed, then at 120 ℃, heat 30 minutes, to obtain the polymer material comprising the crosslinking agent through self-crosslinking polysaccharide component and this component.As required, the material obtained is further crushed and classified.

[0229] Example 2.

[0230] A polymer material was prepared in the same manner as in Example 1, except that CMC having a viscosity of approximately 9,000 to 10,000 cP in an aqueous solution containing 1% by weight of CMC and a degree of substitution (DS) of 0.65 to 0.75 was used. The methods for measuring the viscosity and degree of substitution were the same as in Example 1.

[0231] Example 3.

[0232] A polymer material was prepared in the same manner as in Example 1, except that the target product of Preparation Example 1 (Compound A) was used instead of CMC.

[0233] Example 4.

[0234] A polymer material was prepared in the same manner as in Example 1, except that the target product of Preparation Example 2 (Compound B) was used instead of CMC.

[0235] Comparative Example 1

[0236] A polymer material was prepared in the same manner as in Example 4, but without performing a surface cross-linking process after self-cross-linking.

[0237] The results of physical property measurements of the polymer materials are shown in Table 1 below.

[0238] [Table 1]

[0239]

Claims

1. A polymer material comprising: a self-crosslinked polysaccharide component; and A cross-linking agent is associated with the self-cross-linked polysaccharide component. 2 . The polymer material of claim 1 , wherein the self-crosslinked polysaccharide component is in the form of particles, and the crosslinking agent is bound to the surface of the particles.

3. The polymeric material according to claim 1, having a centrifuge retention capacity according to EDANA (European Disposables and Nonwovens Association) method WSP 241.3 of 10 g / g or more.

4. The polymeric material according to claim 1, having an Absorption Capacity under Pressure at 0.7 psi according to EDANA (European Disposables and Nonwovens Association) method WSP 242.3 of 3 g / g or more. The polymer material according to claim 1 , having a biodegradability of 50% or more. The polymer material according to claim 1 , wherein the polysaccharide is an acidic polysaccharide having a degree of substitution ranging from 0.4 to 2.

5.

7. The polymer material of claim 1 , wherein the self-crosslinked polysaccharide component comprises polymer chains comprising monosaccharide units linked by glycosidic bonds, and bonds of the following formula 1 linking the polymer chains: [Formula 1] In formula 1, X1 is an oxygen atom or NR 11 , where R 11 is a hydrogen atom, an alkyl group or an alkylcarbonyl group, and L1 is an alkylene group, an alkylidene group or a bond of the following formula 2, and L2 is represented by a single bond or -(CH2)-O-: [Formula 2] 8 . The polymer material according to claim 7 , wherein the monosaccharide unit has a ring structure including carbon atoms and oxygen atoms as ring-constituting atoms, and the bond of Formula 1 is directly connected to the carbon atom of the ring structure or is connected via a methylene group.

9. The polymer material according to claim 1, wherein the polysaccharide component comprises a unit represented by the following formula 3: [Formula 3] In formula 3, R1 is hydroxyl, amino, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, R3 is hydroxyl, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, and one of L3 and L4 is a single bond, and the other is CHR2, wherein R2 is a hydroxyl group, -L5-C(=O)-OH, -L5-C(=O)-O - , or a functional group of the following formula 4, and L5 is an alkylene group or an alkylidene group, but any one of R1 to R3 is an oxygen atom of a bond of the above formula 1 (except the oxygen atom present in the carbonyl group): [Formula 4] In formula 4, X2 is an oxygen atom or NR 11 , where R 11 is a hydrogen atom, an alkyl group or an alkylcarbonyl group, M1 is hydrogen or a metal, and when M1 is a metal, the above O-M1 bond is an ionic bond.

10. The polymer material of claim 1, wherein the crosslinking agent is one or more selected from the group consisting of a multifunctional epoxy compound, an epoxysilane compound, an aminosilane compound, epichlorohydrin, formaldehyde, glutaraldehyde, sucrose oxide, an acid chloride, a carbonate, a diamine, a diol, carbon disulfide, phosphorus oxychloride, divinylbenzene, an organic acid, and an organic anhydride. 11 . The polymer material according to claim 1 , wherein the cross-linking agent is an organic acid having two or more carboxyl groups, an anhydride of the organic acid, or an organic compound having two or more aldehyde groups.

12. The polymeric material of claim 1, wherein the cross-linking agent is an oxidized polysaccharide. 13 . The polymer material according to claim 1 , wherein the cross-linking agent is one or more selected from the group consisting of oxidized starch, oxidized dextrin, oxidized chitosan, oxidized chitin, oxidized sucrose, and oxidized maltose.

14. The polymeric material of claim 12, wherein the oxidized polysaccharide comprises aldehyde groups in the range of 0.01 to 0.9 moles per mole.

15. The polymer material according to claim 12, wherein the molar mass of the oxidized polysaccharide is in the range of 100 g / mol to 1000 g / mol. The polymer material according to claim 1 , comprising 0.01 to 20 parts by weight of the cross-linking agent relative to 100 parts by weight of the self-cross-linked polysaccharide component.

17. An absorbent material comprising the polymer material according to any one of claims 1 to 16.

18. A hygiene article comprising the polymeric material according to any one of claims 1 to 16.

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