KR101430784B1 - Resin composition and absorbent product therefrom - Google Patents
Resin composition and absorbent product therefrom Download PDFInfo
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Abstract
Embodiments of the present invention include a superabsorbent resin (SAP); And a silane-modified olefin resin and an application thereof. The resin composition according to embodiments of the present invention can improve the dispersibility of SAP in the product through physical or chemical interaction between the silane-modified olefin resin and the SAP to increase the content in the product, Can be utilized. In addition, according to the embodiments of the present invention, it is possible to prevent the phenomenon that SAP is separated and desorbed in the product after moisture absorption, thereby providing a product excellent in functionality such as absorbency and excellent in physical properties such as durability .
Description
Embodiments of the present invention relate to a resin composition and an absorbent product formed therefrom, and more particularly to a resin composition capable of increasing the content of a superabsorbent resin in an absorbent body, and to an absorbent material and a product made using the same.
BACKGROUND ART Superabsorbent polymer (hereinafter referred to as SAP) is a functional resin capable of absorbing water several tens to several hundred times its own weight, and is widely used in various fields such as sanitary articles or release agents for chemicals .
Examples of typical SAPs include lightly cross-linked hydrophilic polymers such as crosslinked polyacrylates, neutralizers of starch-acrylonitrile graft polymers, neutralizers of vinyl acetate acrylate copolymers, acrylates of acrylonitrile copolymers Hydrolysates of degradation products and acrylamide copolymers, and the like. Such SAPs can be prepared by aqueous solution polymerization, suspension polymerization, reversed-phase suspension polymerization and the like, and they are currently being variously commercialized, manufactured and sold.
Recently, it is desirable to increase the proportion of water absorbent resin, that is, SAP in the absorber, in accordance with the tendency to make ultra thin and light weight products such as sanitary articles or other control agents. However, conventionally, due to the characteristics of the plastic material itself, it is difficult to sufficiently express the function of the SAP, and application of the absorber containing a high content of SAP is also limited.
In addition, in the manufacturing process of SAP, fine particles of SAP occur as a by-product, and there are also problems in processing the derivatives of such SAP. The SAP derivative has the same composition as SAP, but its size is small and difficult to use. Accordingly, there is an attempt to recycle the fine powder into a manufacturing process or to mix it with pulp or the like, but it is not efficient in terms of time and cost.
A problem to be solved by the embodiments of the present invention is to provide a resin composition capable of expanding the application field of SAP.
Another object to be solved by the embodiments of the present invention is to provide an absorbent article made using the resin composition and an absorbent article including the absorbent article.
According to one embodiment of the present invention, there is provided a superabsorbent resin (SAP); And a silane-modified olefin resin.
An aspect according to another embodiment of the present invention relates to an absorber comprising the resin composition.
Another aspect of the present invention relates to an absorbent article made using the absorbent article.
The resin composition according to embodiments of the present invention can increase the dispersibility of SAP in the product through physical or chemical interaction between the silane-modified olefin resin and SAP. Therefore, according to the embodiments of the present invention, the content of SAP in the product can be increased, and the possibility of utilization of the derivative of SAP, which has been difficult to use conventionally, can be increased. Further, according to the embodiments of the present invention, it is possible to prevent the SAP from being separated and desorbed in the product after moisture absorption. Thus, according to the embodiments of the present invention, it is possible to provide a product excellent in functionality such as absorbency and excellent in physical properties such as durability.
Hereinafter, embodiments of the present invention will be described in more detail. In the following description of the present invention, a detailed description of known general configurations or functions will be omitted.
One embodiment of the present invention provides a resin composition comprising a superabsorbent polymer (SAP) and a silane-modified olefin resin.
That is, the resin composition according to one embodiment of the present invention includes SAP, and the SAP may have a size of a certain level or more, and may include fine particles thereof. Specifically, it may include only one of SAP or its derivatives, or may include a mixture of both. SAP derivatives are by-products in the manufacturing process of SAP, typically SAP particles having an average diameter of less than about 180 탆. In the following description, description of SAP is applied to the derivative of SAP in the same way, and it is assumed that the derivative of SAP is also included as a kind of SAP.
The specific type of superabsorbent resin (SAP) contained in the resin composition according to the embodiments of the present invention is not particularly limited, and materials commonly known in this field can be used. One example of such an SAP is a partially or fully neutralized acidic absorbent resin, i.e., anionic SAP. Anionic SAPs having strong acidity or weak acidity can be resins that act as SAP particles in their neutralized form, and these acidic water absorbent resins generally contain carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid or sulfuric acid residues. Such an acidic water absorbent resin may be a single resin or a resin mixture, or may be a homopolymer or a copolymer.
The acidic water absorbent resin is generally a cross-linked acrylic resin such as a weakly cross-linked polyacrylic acid or the like. The weakly crosslinked acidic resin generally comprises an acidic monomer containing an acyl moiety in the presence of an internal cross-linkable monomer, for example a polyfunctional organic compound, such as acrylic acid or a monomer containing a moiety capable of providing an acid group For example, by polymerizing (meth) acrylamide, alkyl (meth) acrylate or acrylonitrile. The acidic water absorbent resin may contain other copolymerizable monomers known in the art, for example, monoethylenically unsaturated monomers, etc., if the polymer contains certain levels of acidic monomer units. In this case, the content of the acidic monomer may be 50% by weight or more, preferably 70% by weight or more, of the total monomers.
The olefinically unsaturated carboxylic acid and carboxylic acid anhydride monomers that can be used in the acidic water absorbent resin polymerization include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, and the like. As the olefinic unsaturated sulfonic acid monomer, Aliphatic and aromatic vinyl sulfonic acids such as vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylic and methacrylosulfonic acid such as 2- (meth) acrylamide-2-methylpropanesulfonic acid and the like. In addition, monomers having polymerizable unsaturated groups such as olefinic unsaturated amines, olefinically unsaturated phosphoric acid esters, and olefinically unsaturated amides can also be used.
Specific examples of the polymerized acidic water absorbent resin include hydrolysates of starch-acrylonitrile graft copolymer, starch-acrylic acid graft copolymer, polyacrylic acid, vinyl acetate acrylic acid ester copolymer, hydrolyzate of acrylonitrile copolymer, Maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyvinylsulfonic acid, polyvinylphosphonic acid, polyvinylphosphoric acid, polyvinylsulfuric acid, sulfonated polystyrene or polyacrylate And salts thereof. Any one of the above salts or a mixture of two or more of them may be used.
Another example of SAP that can be used as the superabsorbent resin of the present invention, like the above acidic absorbent resin, is a basic absorbent resin, that is, cationic SAP. The cationic SAP, which is strong or weakly basic, may be a resin that acts in its charged form, and the basic water-absorbing resin is present in cationic form and may exist in a basic form, e.g., in the form of a charged amino group. Strongly basic resins may generally be present in the form of hydroxides or bicarbonates. Such a basic water absorbent resin may be a single resin or a resin mixture, or may be a homopolymer or a copolymer.
The basic water absorbent resin may generally be a weakly cross-linked resin such as poly (vinylamine) or poly (dialkylaminoalkyl (meth) acrylamide). Specific examples thereof include weakly crosslinked polyethyleneimine, poly (allylamine), poly (allyl guanidine), poly (dimethyldiallylammonium hydroxide), polystyrene derivatives, and guanidine-modified polystyrene. The weakly crosslinked basic water absorbent resin may contain other copolymerizable monomers as described above in the acidic water absorbent resin, and may be crosslinked using a polyfunctional organic compound.
Specific examples of the basic water absorbent resin include poly (vinylamine), polyethyleneimine, poly (vinyl guanidine), poly (dimethylaminoethylacrylamide) or poly (dimethylaminopropyl methacrylamide) Or a mixture of two or more of them may be used.
The acidic water absorbent resin and the basic water absorbent resin may be used alone or in combination of two or more. When the acidic water absorbent resin and the basic water absorbent resin are mixed together, the composition is chemically unstable, so that the acidic and basic water absorbent resins are not used together .
The polymerization of such a water absorbent resin is generally carried out by a free radical method in the presence of a polyfunctional crosslinkable monomer and is crosslinked to a degree sufficient for the polymer to become insoluble in water and the acid or basic water absorbent resin Is weakly cross-linked. Conventional polymerization initiators used in the art can be used for the production of SAP, and other additives such as dispersants can also be used. Examples of the method for producing such SAP include aqueous solution polymerization, suspension polymerization, reversed-phase suspension polymerization, and the like, and any method commonly used in the art can be used without particular limitation. These SAPs are commercialized, manufactured and sold by various sellers, and SAPs used in the present invention can be purchased and used on the market.
Embodiments of the present invention include a silane-modified olefin resin with SAP as described above. The silane-modified olefin resin may be, for example, an olefin resin having a reactive silyl group represented by the following formula (1). The term " reactive silyl group " as used in embodiments of the present invention means a silyl group having a functional group capable of physically or chemically interacting with SAP, or having a functional group capable of providing such a functional group.
[Chemical Formula 1]
-Si (X) m Y (3-m)
Wherein X represents a reactive functional group bonded to a silicon atom, Y represents a non-reactive functional group bonded to a silicon atom, and m represents an integer of 1 to 3.
The reactive functional group (X) is not particularly limited as long as it can chemically or physically interact with a residue present on the surface of the SAP or can provide such a functional group. Specific examples thereof include a halogen atom, an alkoxy group, A phenoxy group, an acyloxy group, an alkylthio group, an alkyleneoxythio group, or a hydrolyzate of any of the above. In this case, examples of the halogen atom include chlorine (Cl). Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, Examples of the acyloxy group include an acyloxy group having 1 to 12 carbon atoms. Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms. Examples of the alkyleneoxy group include alkyl groups having 1 to 12 carbon atoms And alkylene oxide cations. In embodiments of the present invention, X in the above formula (1) may be preferably alkoxy, specifically, an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms And examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group, preferably a methoxy group or an ethoxy group. The specific kind of the hydrolyzate of the reactive functional group is not particularly limited as long as it is determined depending on the type of the functional group used, and may be, for example, a hydroxy group and the like.
The non-reactive functional group of Formula 1 may be hydrogen, an alkyl group, an aryl group, or an aralkyl group. The alkyl group may be, for example, an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The aryl group in Y may be an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, such as a phenyl group, and the aralkyl group may be an aralkyl group having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, For example, a benzyl group.
In one embodiment of the present invention, the olefin resin may be prepared by copolymerizing, for example, an olefin-based monomer, an unsaturated silane compound capable of providing the silyl group of Formula 1, or an unsaturated silane compound ≪ / RTI > by grafting.
That is, in the embodiments of the present invention, the olefin resin includes a copolymer comprising an olefin monomer and an unsaturated silane compound represented by the following formula (2) in copolymerized form; Or a graft polymer obtained by grafting an unsaturated silane compound represented by the following formula (2) to an olefin resin.
(2)
DSi (X) m Y (3-m)
In Formula 2, D is an ethylenically unsaturated hydrocarbon group or a hydrocarbonoxy group, and X, Y and m are as defined in Formula 1 above.
In embodiments of the present invention, D in Formula 2 may be vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or gamma-methacryloxypropyl, and preferably vinyl.
A specific example of the unsaturated silane compound may be vinylalkoxysilane. For example, the unsaturated silane compound may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxy Silane, vinyltriacetoxysilane, or mixtures thereof.
Further, in embodiments of the present invention, examples of the olefin monomer contained in the olefin resin contained in the copolymer in the form of a copolymer or forming the graft polymer include ethylene, propylene, 1-butene, 1-pentene, 1-butene, 4-methyl-1-butene, 3-methyl-1-butene, 3-methyl- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, -Olefins such as pentene or vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-butadiene and 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene, 2- Halogen-substituted? -Olefins such as roprolene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene or 3,4-dichloro-1-butene, cyclopentene, cyclo Hexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene, and the like, but are not limited thereto.
In embodiments of the present invention, the silane-modified olefin resin may preferably be a graft polymer obtained by grafting the unsaturated silane compound of formula (2) to the olefin resin, wherein the olefin resin is, for example, polyethylene , A polypropylene or an ethylene-vinyl acetate copolymer, preferably polyethylene.
The polyethylene contains not only a homopolymer of ethylene but also at least 50 mol% of ethylene as polymerized units, and also contains an alpha -olefin having 3 or more carbon atoms or other comonomers together as a polymerization unit Coalescence may also be included. The polyethylene may be, for example, one or more of low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, ultralow low density polyethylene or linear low density polyethylene.
In the present invention, preferably, the unsaturated silane compound is grafted with polyethylene, and polyethylene having many side chains can be used. Grafting can be performed more efficiently in polyethylene having many side chains. Polyethylene having a large number of side chains generally has a low density, and a polyethylene having a small side chain generally has a high density. Therefore, in the present invention, it preferred to use a polyethylene of low density and, specifically, a density of 0.85 g / cm 3 to 0.92 g / cm 3, preferably a density of about 0.85 g / cm 3 to 0.90 g / cm 3 of polyethylene Can be used.
Also, the polyethylene may have a melt flow rate (MFR) of about 0.1 g / 10 min to about 50 g / 10 min at 190 캜. When the MFR is in this range, for example, the resin composition of the present invention can exhibit excellent moldability and the like.
The silane-modified olefin resin included in the resin composition according to the embodiments of the present invention may have a silicon content of 50 ppm to 3000 ppm in the copolymer or graft polymer. It is possible to appropriately maintain the reactivity with the SAP without damaging other physical properties of the absorber within the above-mentioned content range.
In the resin composition according to the embodiments of the present invention, the SAP may be contained in an amount exceeding 50 parts by weight based on 100 parts by weight of the total resin composition. Generally, in the prior art, the content of SAP in the absorber was limited to 30% by weight to 40% by weight. However, according to the embodiment of the present invention using the silane-modified olefin resin, Can be included. Also, in the prior art, the SAP fine particles having a small particle size have a low degree of desorption from the absorber, resulting in low utilization. However, when the silane-modified olefin resin is included as in the embodiments of the present invention, It is possible to utilize all the fine particles of SAP particle size by physical and chemical interaction. The above content is only one example of the present invention, which may vary depending on the application to which the product is applied. Unless otherwise specified, unit weight parts in the present specification means weight ratios.
In the resin composition according to embodiments of the present invention, the content of the silane-modified olefin resin may be 50 parts by weight to 300 parts by weight based on 100 parts by weight of the SAP. In this range, SAP It is possible to appropriately maintain the reactivity with
The resin composition according to the embodiments of the present invention may further include additives selected from the group consisting of a polyolefin for additives, an antioxidant, a plasticizer, a colorant, a stabilizer, and a surfactant.
Another embodiment of the present invention relates to an absorbent material, i. E. Absorber, comprising the resin composition. The absorber may comprise the resin composition described above, wherein the silane-modified olefin resin of the resin composition may replace the fiber of the conventional absorber.
The method for producing the absorbent body using the water absorbent resin composition is not particularly limited, and a conventionally used method can be used. Specifically, for example, SAP and a silane-modified olefin resin may be mixed using an extruder or a batch mixer and molded into a sheet or film using T-die or calendaring.
In the case of the conventional absorber, the content of the fiber or pulp is generally higher than that of the absorbent resin. In general, the ratio of the fiber to the absorbent resin is 6: 4. In the case of the absorber according to the embodiments of the present invention, The proportion of the superabsorbent resin (SAP) may be more than 50 parts by weight based on 100 parts by weight of the total absorbent.
In the case of the conventional absorber, the size of the particles from the absorber is less than a certain level, and the degree of desorption is so severe that the utilization of the SAP fine particles is low. However, in the case of the absorber according to the embodiments of the present invention, And it is possible to utilize the fine particles of SAP, which is a small SAP particles having a lower level than the conventional one, because it can prevent desorption after moisture absorption through physical and chemical interaction with SAP.
Therefore, in the case of the absorber prepared using the resin composition according to the embodiments of the present invention, the content of SAP is increased to improve the water absorbability, and the difference between the residues such as the carboxylic acid on the surface of the SAP, especially SAP and the silane modified olefin resin Physical and chemical bonding (Binding) is featured, so that durability can be improved by preventing SAP and the like from absorbing moisture and then being separated and desorbed.
Further, the absorber according to embodiments of the present invention may further include fibers as needed. At this time, the fiber may be at least one selected from the group consisting of pulp, cotton, polyamide fiber, acrylic fiber, polyester fiber, and combinations thereof. .
The absorber according to embodiments of the present invention may be used in any suitable absorbent product. For example, it can be used for various absorbent products such as sanitary articles such as diapers, pants for incontinence, feminine sanitary articles, moisture retaining agents, dehydrating agents, sludge flocculants, disposable bathroom mats, or release agents for various chemicals. For example, in the case of conventional sanitary or sanitary articles, the layers may be laminated in layers, which may consist essentially of a liquid permeable layer, a distribution layer or a transfer layer, an absorbent body, a waterproof layer surrounding them, .
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.
Manufacturing example 1 to 2: Silane Preparation of Modified Olefin Resin
Vinyltrimethoxysilane (VTMS) having a density of 0.87 g / cm 3 and a melt flow rate (MFR) of 190 g / 10 min as shown in Table 1 below, vinyltrimethoxysilane (VTMS), dicumyl peroxide And the mixture was heated to 200 ° C and melt-stirred to prepare a silane-modified olefin resin.
* Reacted Si element content is measured by inductively coupled plasma spectrophotometer (ICP-OES).
Example 1 to 2
100 parts by weight of a crosslinked polyacrylate salt having a particle size of less than 180 μm, 50 parts by weight of the silane-modified olefin resin obtained in Production Examples 1 and 2 and 0.1 part by weight of an antioxidant (Ig1010) Extruded from an extruder of Haake, Germany to prepare a sheet of 0.5 mm. The prepared sheet was dried in a hot air oven for about 1 hour, and water absorption and SAP desorption weight were evaluated.
Comparative Example One
A sheet was produced in the same manner as in Example 1, except that 50 parts by weight of an olefin resin having a density of 0.87 g / cm 3 and an MFR of 5.0 g / 10 min at 190 캜 was used as the olefin resin.
Comparative Example 2
A sheet was produced in the same manner as in Comparative Example 1, except that 50 parts by weight of an olefin resin having a density of 0.93 g / cm < 3 >
Experimental Example 1-2: Property evaluation
1) Water absorption evaluation
The sheets prepared from the resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were allowed to stand in water at 25 캜 for 5 minutes to quantitatively measure the amount of water absorbed to measure the absorption capacity (g / g).
Absorption capacity (g / g) = (absorbed sample weight - initial weight) / initial weight
2) Evaluation of SAP desorption after water absorption
A sheet prepared from the resin compositions obtained in Examples 1 to 2 and Comparative Examples 1 to 2 was stirred in a 1 liter beaker filled with water at 25 DEG C for 5 minutes at 800 rpm and dried in a 100 DEG C oven for 5 hours to change the weight The degree of desorption (%) was measured by quantitative analysis.
Degree of desorption (%) = (initial weight - weight after drying) / initial weight × 100
Referring to Table 2, in the case of the sheet prepared using the resin composition containing the silane-modified olefin resin (Examples 1 and 2), the absorbability of the SAP after the moisture absorption was low, (Comparative Examples 1 and 2) of the sheet prepared using the resin composition containing no silane-modified olefin resin, the absorbability was poor and the degree of desorption of SAP was high.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be appreciated that embodiments are possible. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.
Claims (18)
A copolymer comprising an olefin monomer and an unsaturated silane compound represented by the following formula (2) in copolymerized form; Or a silane-modified olefin resin which is a graft polymer obtained by grafting an unsaturated silane compound represented by the following formula (2) to an olefin resin:
(2)
DSi (X) m Y (3-m)
In Formula 2,
D is an ethylenically unsaturated hydrocarbon group or hydrocarbonoxy group bonded to a silicon atom and X is a halogen atom, an alkoxy group, a phenoxy group, an acyloxy group, an alkylthio group, an alkyleneoxy group or a hydrolyzate of any of the above And,
Y represents hydrogen, an alkyl group, an aryl group or an aralkyl group,
m represents an integer of 1 to 3;
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| US10653149B2 (en) * | 2016-10-20 | 2020-05-19 | Colgate-Palmolive Company | Oral care compositions and methods for anti-attachment polymers and coatings |
| CN106811153B (en) * | 2016-12-28 | 2018-07-10 | 杭州福斯特应用材料股份有限公司 | A kind of photovoltaic module seals the glue that blocks water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100371649B1 (en) | 1994-08-12 | 2003-05-22 | 가오가부시끼가이샤 | Process for producing improved super absorbent polymer |
| US20050239942A1 (en) | 2002-08-23 | 2005-10-27 | Basf Aktiengesellschaft | Superabsorbent polymers and method of manufacturing the same |
| KR20060049215A (en) * | 2004-06-29 | 2006-05-18 | 킴벌리-클라크 월드와이드, 인크. | Biodegradable absorbent material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100371649B1 (en) | 1994-08-12 | 2003-05-22 | 가오가부시끼가이샤 | Process for producing improved super absorbent polymer |
| US20050239942A1 (en) | 2002-08-23 | 2005-10-27 | Basf Aktiengesellschaft | Superabsorbent polymers and method of manufacturing the same |
| KR20060049215A (en) * | 2004-06-29 | 2006-05-18 | 킴벌리-클라크 월드와이드, 인크. | Biodegradable absorbent material |
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