particulate superabsorbent polymer, its production method, and absorbent article

专利摘要:
particulate superabsorbent polymer having an increased capacity. the present invention relates to a superabsorbent polymer and particulate superabsorbent polymer comprising a monomer and a crosslinker composition in which the particulate superabsorbent polymer has an increase in centrifugal retention capacity of 2g / g or more, as stated herein, in the augmentation test centrifugal holding capacity. the present invention further relates to a superabsorbent polymer comprising a crosslinker composition comprising a silane compound comprising at least one vinyl group, or an allyl group attached to a silicon atom, and at least one si-o bond. the present invention further relates to an absorbent article which includes such particulate superabsorbent polymers.
公开号:BR112012028192B1
申请号:R112012028192
申请日:2011-04-29
公开日:2020-04-07
发明作者:L Bergman David Jr；Tian Gonglu；Shi Yaru
申请人:Evonik Stockhausen Llc；
IPC主号:

专利说明:

Invention Patent Descriptive Report for PARTICULATED SUPERABSORBENT POLYMER, ITS PRODUCTION METHOD, AND ABSORBENT ARTICLE.
BACKGROUND [0001] The present invention relates to a superabsorbent polymer and particulate superabsorbent polymer. A superabsorbent polymer is a partially cross-linked neutralized polymer, including cross-linked polyacrylic acids or cross-linked acrylic starch graft polymers, which is capable of absorbing large amounts of aqueous liquids and body fluids, such as urine or blood, with swelling and the formation of hydrogels , and to retain the aqueous liquids under a certain pressure according to the general definition of superabsorbent polymer. The superabsorbent polymer can be formed into particles, generally referred to as particulate superabsorbent polymer, comprising the particulate superabsorbent polymer which can be post-treated with surface crosslinking, surface treatment, and other treatment, to form particulate superabsorbent polymer. The acronym SAP can be used in place of superabsorbent polymer, and particles thereof. A primary use of superabsorbent polymer and particulate superabsorbent polymer is in sanitary articles, such as baby diapers, incontinence products, or sanitary napkins. Comprehensive survival of superabsorbent polymers, and their use and production, is given in F.
L. Buchholz and A. T. Graham (editors) in Modern superabsorbent polymer Technology, Wiley-VCR, New York, 1998.
[0002] Superabsorbent polymers can be prepared by initially polymerizing unsaturated carboxylic acids or derivatives thereof, such as acrylic acid, alkali metal (eg sodium and / or potassium), or ammonium salts of acrylic acid, alkyl acrylates , and the like, in the presence of relatively small amounts
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2/61 of an internal crosslinker, such as di- or polyfunctional monomers which can include N, N'-methylenebisacrylamide, trimethylolpropane triacrylate, ethylene glycol di (meth) acrylate, or trialylamine. The di- or poly-functional monomer materials can serve as covalent internal crosslinking agents to lightly crosslink the polymer chains, thereby making them insoluble in water, still swellable in water. These lightly cross-linked superabsorbent polymers contain a multiplicity of carboxyl groups attached to the polymer support. These carboxyl groups generate an osmotic actuation force for the absorption of body fluids by the network of cross-linked polymer.
[0003] In addition to covalent internal crosslinking agents, internal ionic crosslinking agents have been used to prepare superabsorbent polymers as well. Internal ionic crosslinking agents are generally coordination compounds comprising polyvalent metal cations, such as Al ³⁺ and Ca ²⁺ , as disclosed in United States Patent No. 6,716,929 and United States Patent No. 7,285,614. The superabsorbent polymers disclosed in these patents have a slow rate of absorption due to the presence of ionic cross-links. In this context, the slow rate can be measured by Vortex Testing, and the slow rate particulate superabsorbent polymer generally has a vortex time of 180 s or more.
[0004] Superabsorbent polymers and particulate superabsorbent polymers, useful as absorbents in absorbent articles, such as disposable diapers, need to have adequately high sorption capacity, as well as, adequately, high gel resistance. The sorption capacity needs to be high enough to enable the absorbent polymer to absorb significant amounts of the aqueous body fluids found during the use of article 870190130737, of 12/09/2019, p. 6/74
3/61 sorbent. Gel resistance refers to the tendency of swollen polymer particles to deform under an applied tension, and needs to be such that the particles do not deform and fill the capillary voids in the absorbent member or article to an unacceptable degree, so-called gel, thereby inhibiting the rate of fluid entry, or the distribution of fluid by the limb or article. Once the gel block occurs, it substantially prevents the distribution of fluids to relatively dry zones or regions in the absorbent article, and leakage of the absorbent article can occur before the superabsorbent polymer particulate in the absorbent article is fully saturated, or before the fluid can diffuse or pass the blocking particles in the rest of the absorbent article. [0005] Another property of these particulate superabsorbent polymers is that which is called Gel Bed Permeability. The gel permeability of the particulate superabsorbent polymer is a measure of how quickly the liquid flows through the swollen particulate superabsorbent polymer mass. In general, the permeability of the gel of a zone, or layer, comprising swollen particulate superabsorbent polymer can be increased by increasing the cross-linking density of the polymer gel, thereby increasing the strength of the gel. Particulate superabsorbent polymers with relatively high gel permeability can be produced by increasing the level of internal crosslinking, which increases the strength of the swollen gel, but this typically also undesirably reduces the absorbent capacity of the gel, as described above.
[0006] In the past decade, significant investments have been made to improve the performance of such particulate superabsorbent polymers, for example, to provide higher absorbent capacity by volume, to improve fluid distribution
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4/61 through all particulate superabsorbent polymers, and to reduce the so-called gel blocking of particulate superabsorbent polymers. One area of focus was to modify the surface of particulate superabsorbent polymers such that the optimal gel permeability was achieved without significantly compromising the absorbent capacity.
[0007] The current trend in absorbent articles, including diapers, is towards even thinner core constructions having a reduced or zero cellulose fiber content, or fluff content, and an increased content of particulate superabsorbent polymers. As the diaper cores become thinner, the particulate superabsorbent polymer must have properties that have historically been supplied by the fluff pulp. Since reducing the fiber content between the superabsorbent polymers increases the risk of gel blocking, there is a need to provide thinner cores without much or any fibers, which do not suffer from gel blocking.
[0008] Consequently, there is still a need to improve the absorbent capacity and gel strength of the particulate superabsorbent polymer at the same time.
SUMMARY [0009] The present invention includes numerous embodiments, some of which are included here. One embodiment of the present invention is a particulate superabsorbent polymer comprising a monomer and a crosslinker composition comprising an internal crosslinking agent in which the particulate superabsorbent polymer has an Increase in Centrifugal Holding Capacity (CRCI) of 2g / g or more, of 2g / g ga 50g / g, 2g / ga 40g / g, 3g / ga 30g / g, or 3g / ga 15g / g, as placed here, in the Centrifugal Retention Capacity Increase Test.
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[00010] Another embodiment of the present invention includes a superabsorbent polymer including an internal cross-linking composition that contains a silane compound comprising at least one vinyl group, or allyl group directly attached to a silicon atom, and at least one Si bond. -O. The silane compound can be selected from one of the following:
(Rd — Si — fO --- R2] ^v 'ml'2'n (M j (I);
R4
Si 'y (
2 m
R5 (II);
or
RiR4
I1 Y
Si'óSi
I ^x I
R5
(III) in which
Ri represents C2 to C3 alkenyl,
R2 represents H, C1 to C4 alkyl, C2 to C5 alkenyl, C6 to C8 aryl, C2 to C5 carbonyl,
R3 represents H, C1 to C4 alkyl, C6 to C8 aryl,
R4 and R5 independently represent H, C1 to C4 alkyl,
C6 to C8 aryl, m represents an integer from 1 to 3, preferably 1 to 2, n represents an integer from 1 to 3, preferably 2 to 3, l represents an integer from 0 to 2, preferably 0 to 1, m + n + l = 4, x represents an integer greater than 1, and
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6/61 y represents an integer of 0, or greater than 0.
[00011] In one aspect, the silane compound can be selected from vinyltriisopropenoxy silane, vinyltriacetoxy silane, vinyltrimethoxysilane, vinyl triethoxysilane, dietoxymethyl vinyl silane, and polysiloxane comprising at least two vinyl groups.
[00012] In a further aspect, the superabsorbent polymer of the present invention can additionally comprise a second internal crosslinker. The second internal crosslinker can be selected from the group of polyethylene glycol monoalyl ether acrylate, trimethylol propane ethoxylated triacrylate, and polyethylene glycol diacrylate.
[00013] Another embodiment of the present invention is a particulate superabsorbent polymer comprising a superabsorbent polymer comprising at least one monomer, an internal crosslinking composition containing a silane compound comprising at least one vinyl group, or allyl group directly attached to a silicon atom , and at least one Si-O bond, a salt-forming cation, and a surface cross-linking agent, in which the monomer is selected from an ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid and hydride, salts or derivatives thereof in the superabsorbent polymer. In another aspect, the internal cross-linking composition is 0.001 wt% to 5 wt% based on the monomer.
[00014] Another embodiment of the present invention is a method for producing a particulate superabsorbent polymer, in which the method comprises the steps of preparing a superabsorbent polymer, polymerizing the components of the superabsorbent polymer in a hydrogel, preparing the particulate superabsorbent polymer, surface treatment of the particulate superabsorbent polymer to produce particulate superabsorbent polymer. Numerous other aspects of embodiments, features and advantages of this
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7/61 invention will appear from the following detailed description, accompanying drawings and claims. In the interest of brevity and awareness, any ranges of values placed in this specification include all values within the range, and are to be built in support of claims that cite any sub-ranges having endpoints that are real number values within the specified range in question.
[00015] These and other aspects, advantages and salient features of the present invention will become apparent from the following detailed description, the accompanying drawings and the attached claims.
BRIEF DESCRIPTION OF THE FIGURES [00016] The foregoing and other characteristics, aspects and advantages of the present invention will become apparent with respect to the following description, appended claims, and accompanying drawings where:
figure 1 is a graph showing an increase in absorption capacity over time;
figure 2 contains CRC vs. graphs. swelling time for particulate SAP pre-product of the present invention;
figure 3 contains CRC vs. graphs. swelling time for particulate SAP composition of the present invention;
figure 4 contains CRC vs. graphs. swelling time for the prior art particulate SAP composition;
figure 5 is a side view of the test apparatus employed for the Swell Gel Bed Permeability Tste;
Figure 6 is a cross-sectional side view of a cylinder / bowl assembly used in the Free Swell Gel Bed Permeability Test apparatus shown in Figure 5;
figure 7 is a top view of a plunger used
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8/61 in the Free Swollen Gel Bed Permeability Test apparatus shown in figure 5; and figure 8 is a side view of the test apparatus used for the Load Absorbance Test.
DEFINITIONS [00017] It should be noted that, when used in the present disclosure, the terms comprise, comprising and other derivatives from the main term comprise are intended to be open-ended terms that specify the presence of any features cited, elements, integers, steps, or components, and are not intended to limit the presence or addition of one or more other characteristics, elements, steps, integers, components, or groups thereof.
[00018] The term absorbent article, as used herein, refers to devices that absorb and contain bodily exudates, and, more specifically, refers to devices that are placed against or in proximity to the user's body to absorb and contain the various exudates discharged from the body. Absorbent items may include diapers, training pants, adult incontinence underwear, feminine hygiene products, breast pads, care cloths, bibs, wound cover products, and the like. Absorbent articles may additionally include floor cleaning articles, food industry articles, and the like. As used herein, the term bodily fluids or bodily exudates include, but are not limited to, urine, blood, vaginal discharges, breast milk, sweat, and fecal matter.
[00019] The term Centrifugal Retention Capacity (CRC), as used here, refers to the ability of the particulate superabsorbent polymer to retain liquid in it after being saturated and subjected to centrifugation under controlled conditions, and is quoted in grams of liquid.
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9/61 liquid retained in gram weight of the sample (g / g). The CRC test can be conducted at a test temperature designated for a test time period, known as CRC (test temperature, test time). As used herein, the term test temperature refers to the temperature of the test solution in which the particulate superabsorbent polymer sample is wet. The term test time refers to the period of time that the particulate superabsorbent polymer sample is wetted in a test solution. For example, CRC (rt, 0.5 hour) refers to a CRC with an ambient temperature test temperature (rt, 23 ° C) and a test time of 0.5 hour.
[00020] The term Increase in Centrifugal Retention Capacity (CRCI) or Increase in CRC or Increase in Capacity is defined as the increase by at least 2g / g in the CRC that occurs and is calculated as the difference between a second CRC and a first CRC. As used herein, the term first CRC or initial CRC generally refers to CRC (rt, 0.5 hour), although another CRC value may be used. The second CRC can be tested at room temperature or higher, preferably from 23 ° C to 50 ° C, for at least 1 hour, preferably from 2 hours to 24 hours. CRC Increase is measured according to the CRC Increase Test Method described here below.
[00021] The term Centrifugal Retention Capacity Increase Rate or CRCIR, as used herein, refers to the increase in CRC per hour (g / g / hour) and is measured according to the Centrifugal Holding Capacity described here below.
[00022] The terms crosslinking, crosslinking, crosslinking, or crosslinking, as used herein, refer to any means to effectively make polymers normally soluble in substantial water
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10/61 insoluble in water, but swelling. Such a crosslinking medium can include, for example, physical entanglement, crystalline domains, covalent bonds, ionic complexes and associations, hydrophilic associations such as hydrogen bonding, hydrophobic associations, or Van der Waals forces.
[00023] The term internal crosslinker, as used herein, refers to the use of a crosslinker in the monomer solution to form the polymer.
[00024] The term Darcy is a unit of permeability CGS. A Darcy is the permeability of a solid through which a cubic centimeter of fluid, having a viscosity of one centipoise, will flow in one second through a section one centimeter thick and one square centimeter in cross section, if the pressure difference between the two sides of the solid is an atmosphere. Reporting that the permeability presents the same units as area; since there is no SI permeability unit, square meters are used. A Darcy is equal to 0.98692 x 10 ^-12 m ² or 0.98692 x 10 ^-8 cm ² .
[00025] The term diaper, as used herein, refers to an absorbent article generally used by children and incontinent people on the lower torso to wrap around the user's waist and legs, and which is specifically adapted to receive and contain urinary discharge and fecal. As used herein, the term diaper also includes pants.
[00026] The term available, as used herein, refers to absorbent articles that are not intended to be intended to be washed or, otherwise, restored or reused as an absorbent article after a single step. Examples of such absorbent articles available include, but are not limited to, absorbent personal care articles, absorbent health / medical articles, and
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11/61 household / industrial absorbent articles.
[00027] The term dry particulate superabsorbent polymer, as used herein, generally refers to the composition of superabsorbent polymer having less than 10% moisture.
[00028] The term hydrolyzable bonds, as used herein, refers to bonds that can be broken by coming into contact with water, such as anhydrous bonds.
[00029] The term mass average particle size of a given sample of particles of superabsorbent polymer composition is defined as the particle size, which divides the sample in half on a mass basis, that is, half of the sample by weight it has a particle size larger than the mass average particle size, and half of the sample per mass has a particle size smaller than the mass average particle size. Thus, for example, the mass average particle size of a sample of particles of superabsorbent polymer composition is 2 pm if half of the sample by weight is measured as more than 2 pm.
[00030] The terms particle, particulate, and the like, when used with the term superabsorbent polymer, refer to the form of discrete units. The units may comprise flakes, fibers, agglomerates, granules, powders, spheres, pulverized materials, or the like, as well as combinations thereof. The particles can have any desired shape: for example, cubic, rod-like polyhedra, spherical or semi-spherical, round or semi-round, angular, irregular, etc. Shapes having a high aspect ratio, similar to needles, flakes, and fibers, are also contemplated for inclusion here. The terms particle or particulate may also include an agglomeration comprising more than one individual particulate, particulate, or the like. Additionally, a particle, particulate, or any
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12/61 desired agglomeration of these, may be composed of more than one type of material.
[00031] The terms particulate superabsorbent polymer refer to the discrete form of superabsorbent polymer, comprising the particulate superabsorbent polymer which can have a particle size of less than 1000 pm, or from 150 pm to 850 pm.
[00032] The term polymer includes, but is not limited to, homopolymers, copolymers, for example, block, graft, random, and alternating copolymers, terpolymers, etc., and mixtures and modifications thereof. In addition, unless otherwise specifically limited, the term polymer should include all possible configurational isomers of the material. These configurations include, but are not limited to, isotactic, syndiotactic and atactic symmetries.
[00033] The term polyolefin, as used herein, generally includes, but is not limited to, materials such as polyethylene, polypropylene, polyisobutylene, polystyrene, ethylene vinyl acetate copolymer, and the like, homopolymers, copolymers, terpolymers, etc. , of these, and mixtures and modifications of these. The term polyolefin should include all possible structures of these, which include, but are not limited to, isotactic, synodiotactic, and random symmetries. Copolymers include atactic and block copolymers.
[00034] The term polysiloxane, as used herein, refers to polymerized siloxanes consisting of an inorganic silicon-oxygen support (...- Si-O-Si-O-Si-O -...) with organic side groups attached to silicon atoms, which are four-coordinated. In addition, unless otherwise specifically limited, the term polysiloxane should include polymers comprising two of more siloxane repeat units.
[00035] The term superabsorbent polymer, as used herein,
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13/61 refers to water-insoluble organic or inorganic materials, swellable in water, including superabsorbent polymers and particulate superabsorbent polymer capable of, under the most favorable conditions, absorbing at least 10 times its weight, or at least 15 times its weight, or at least 25 times its weight in an aqueous solution containing 0.9 weight percent sodium chloride.
[00036] The term superabsorbent polymer pre-product, as used herein, refers to a material that is produced by conducting all the steps to produce a superabsorbent polymer as described herein, up to and including drying of the material, and coarse grinding in a crusher.
[00037] The term surface crosslinking, as used herein, refers to the level of functional crosslinking in the vicinity of the surface of the superabsorbent polymer particle, which is generally higher than the level of functional crosslinking within the superabsorbent polymer particle. As used here, surface describes the outermost opposite boundaries of the particle.
[00038] The term thermoplastic, as used herein, describes a material that softens when exposed to heat, and which substantially returns to an unmolested condition when cooled to room temperature.
[00039] The term% by weight or% by weight, as used herein, and referring to the components of the superabsorbent polymer composition, is to be interpreted as based on the weight of the dry particulate superabsorbent polymer, unless otherwise specified herein. .
[00040] These terms can be defined with additional language in the remaining portions of the specification.
DETAILED DESCRIPTION [00041] While typical aspects of implementation and / or con
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14/61 cretizations were placed for the purpose of illustration, this Detailed Description and accompanying drawings should not be considered to be limiting the scope of the invention. Consequently, various modifications, adaptations and alternatives can occur to a person skilled in the art without departing from the spirit and scope of the present invention. By means of a hypothetical illustrative example, a disclosure in this specification of a range from 1 to 5 must be considered to support claims to any of the following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and 4- 5.
[00042] The present invention is directed to a particulate superabsorbent polymer having an Increased Centrifugal Retention Capacity (CRCI). The increased capacity means that the particulate superabsorbent polymer has high gel resistance and high absorption capacity at the same time. An idealized increase in the absorption capacity is illustrated in figure 1 showing a particulate superabsorbent polymer having low absorption capacity initially and increased capacity over the swelling time.
[00043] One embodiment of the present invention includes a particulate superabsorbent polymer comprising a monomer and an internal crosslinking agent comprising the particulate superabsorbent polymer has a CRCI of 2 g / g or more, 2 g / g to 50 g / g, or 2 g / g to 40 g / g, or 3 g / g to 30 g / g, as placed here in the CRCI Test. In another aspect, the CRCI may be dependent on the test time.
[00044] The CRC Increase Rate of the particulate superabsorbent polymer of the present invention can be in the range of 0.4 g / g / hour to 10 g / g / hour, or 0.6 g / 'g / hour at 8 g / g / hour. The test time can be in the range of 2 hours to 24 hours, or 2 hours to 16 hours. The test temperature can be in the range of 23 ° C to 50 ° C, preferably, or 23 ° C (room temperature) or 37 ° C (body temperature). Like
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15/61 same test time, CRC at body temperature (CRC (bt)) is at least 2 g / g, or 2 g / g at 20g / g higher than CRC at room temperature (CRC (ta) ).
[00045] The particulate superabsorbent polymer having the CRCI of the present invention can be prepared by using a silane compound as the internal crosslinking agent. The silane compound comprises at least one carbon-carbon double bond and at least one Si-O bond.
[00046] Another embodiment of the present invention includes a superabsorbent polymer including an internal crosslinking composition containing a silane compound comprising at least one vinyl group or allyl group directly attached to a silicon atom, and at least one Si-O bond. The silane compound can be selected from one of the following:
R4 (I);

m
x
Si 'y
R3) '2-m
R5 (II); or
Laugh

R4
Si 'y
R5 (III) in which
R1 represents C2 to C3 alkenyl,
R2 represents H, C1 to C4 alkyl, C2 to C5 alkenyl, C6 to C8 aryl, C2 to C5 carbonyl,
R3 represents H, C1 to C4 alkyl, C6 to C8 aryl,
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16/61
R4 and R5 independently represent H, C1 to C4 alkyl, C6 to C8 aryl, m represents an integer from 1 to 3, preferably 1 to 2, n represents an integer from 1 to 3, preferably 2 to 3, l represents an integer from 0 to 2, preferably 0 to 1, m + n + l = 4, x represents an integer greater than 1, and y represents an integer of 0, or greater than 0.
[00047] Illustrative of silanes, having at least one vinyl group or allyl group directly attached to a silicon atom and a SiO bond, which can be used to provide the structure in formula (I) above includes: vinylalkoxysilanes such as vinyltrimethoxysilane, methylvinyltrimethoxysilane , vinyltriethoxysilane, methylvinyltriethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, and vinyltris (2-methoxyethoxy) silane; vinylacethoxysilanes, such as vinylmethyldiacethoxysilane, vinylethylacethoxysilane and vinyltriacetoxy silane; allylalkoxysilanes such as allyl trimethoxysilane, allyl methyldimethoxysilane, and allyl trimethoxysilane; divinylalkoxysilanes and divinylacetoxysilanes such as divinyldimethoxysilane, divinyldiethoxysilane and divinyldiacethoxysilane; diallylalkoxysilanes and diallyl ethoxysilanes such as diallyldimethoxysilane, diallyldiethoxysilane and diallyldiacethoxysilane; as well as other similar ethylenically unsaturated silane monomers containing one or more hydrolyzable groups. As will be appreciated by a person skilled in the art given the present disclosure, the use of compounds such as vinyltrichlorosilane in water or alcohol can provide structures in formula (I) above in which, for example, the group R1 may be a group vinyl. It is also possible that more complex structures can be formed, for example, by reacting vinyl silane with polyethylene glycol.
[00048] Illustrative of polysiloxanes, having at least one vinyl group or allyl group directly attached to a silicon atom, which can
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17/61 can be used to provide the structure in formula (II) or (III) above, include the polymers and copolymers of silanes having the structure in formula (I). Preferred examples include, but are not limited to, polysiloxane comprising vinyl and methoxy groups (commercially available from Evonik Degussa Corporation, under the trade name Dynasylan® 6490), polysiloxane comprising vinyl and ethoxy groups (commercially available from Evonik Degussa Corporation, under the trade name Dynasylan® 6498), vinylmethylsiloxane homopolymers, vinylmethylsiloxane copolymers, finished vinyl siloxane homopolymers, and finished vinyl siloxane copolymers. However, it is contemplated that a wide range of polysiloxanes having vinyl functional groups that provide the desired effects, are effective crosslinking agents according to the present invention.
[00049] In another embodiment, the superabsorbent polymer may include a second internal crosslinker which may comprise polyethylene glycol monoallyl ether acrylate, propane ethoxylated trimethylol triacrylate, and / or polyethylene glycol diacrylate.
[00050] Another embodiment of the particulate superabsorbent polymer of the present invention comprises a process for preparing a particulate superabsorbent polymer, having a CRCI of 2 g / g to 50 g / g, by polymerizing at least one monomer, selected from an ethylenically carboxylic acid. unsaturated, ethylenically unsaturated carboxylic acid and hydride, salts or derivatives thereof, based on the superabsorbent polymer, and an internal crosslinking composition of 0.001 weight percent to 5 weight percent based on the monomer, where the internal crosslinking composition includes a first and second internal crosslinking composition comprising one of the crosslinking compositions comprising a silane compound, having at least one vinyl group or an allyl group directly attached to a silicon atom, and at least one Si-O bond,
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18/61 in a hydrogel, preparation of particulate superabsorbent polymer from the superabsorbent polymer, and treatment of the superabsorbent polymer particles with surface additives including a surface crosslinking agent.
[00051] Another embodiment of the present invention is an absorbent article, such as diapers, training pants, incontinence products, other personal care or health care garments, including medical garments, or the like, comprising the particulate superabsorbent polymer of the present invention.
[00052] The term superabsorbent polymer, as used herein, refers to water-soluble, water-swellable organic or inorganic materials, including superabsorbent polymers and superabsorbent polymer compositions capable, under the most favorable conditions, of absorbing at least 10 times their weight, or at least 15 times its weight, or at least 25 times its weight in an aqueous solution containing 0.9 weight percent sodium chloride. A particulate superabsorbent polymer is a superabsorbent polymer that has been granulated into particles such as, for example, particles within the range 150 to 850 pm.
[00053] A superabsorbent polymer, as placed in the embodiments of the present invention, is obtained by the initial polymerization of 55 weight percent to 99.9 weight percent of the polymeric unsaturated acid group superabsorbent polymer containing monomer. A suitable monomer includes any of those containing carboxyl groups, such as acrylic acid, methacrylic acid, or acid
2-acrylamido-2-methylpropanesulfonic, or mixtures thereof. It is desirable for at least 50 weight percent, and most desirable for at least 75 weight percent of the acid groups to be carboxyl groups.
[00054] Acid groups are neutralized to the extent of at least
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19/61 minus 25 mol%, that is, the acid groups are desirably present as sodium, potassium and ammonium salts. In some respects, the degree of neutralization can be at least 50 mol%, or it can be at least 60 mol%. In some respects, it is desirable to use polymers obtained by polymerization of acrylic acid or methacrylic acid, the carboxyl groups of which are neutralized to the extent of 50 mol to 80 mol%, in the presence of internal crosslinking agents.
[00055] In some respects, the suitable monomer that can be copolymerized with the ethylenically unsaturated monomer may include, but is not limited to, acrylamide, methacrylamide, hydroxyethyl acrylate, dimethylaminoalkyl (meta) -acrylate, (meth) acrylates, ethoxylamide, dimethylaminoamide or acrylamidopropyltrimethylammonium chloride. Such a monomer can be present in a range of 0% to 40% by weight of the polymerized comonomer.
[00056] The superabsorbent polymer includes crosslinking points comprising the superabsorbent polymer which can be crosslinked with an internal crosslinking agent. Suitable internal crosslinking agents in this embodiment can include, but are not limited to, a first internal crosslinking agent, which contains a silane compound comprising at least one vinyl group or an allyl group directly attached to a silicon atom, and at least one bond Si-O. Examples of internal silane crosslinkers suitable for
present invention are placed with their chemical structure in Table 1. TABLE 1 Chemical Chemical structure
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20/61
TABLE 1 Chemical Chemical structure Vinyltri-isopropenoxy silane O- Si - o ^^^ kk Vinyltriacetoxy silane O OCCH3 II o _ — 1 ii ^ Si - occh ₃ OCCH3 II ³ O Vinyltrimethoxysilane och ₃ Si --- OCH3 OCH3 Vinyltriethoxysilane çç ) CH ₂ CH3 Ü --- OCH2CH3) CH ₂ CH3 Dietoxymethylvinyl silane çÇ CH ₂ CH ₃ Ü --- OCH2CH3 3H3
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21/61
TABLE 1 Chemical Chemical structure Dynasylan® 6490(vinyl siloxane reaction oligomer, functional methoxy) —F — Si — A—'n cch ₃ Dynasylan® 6498(vinyl siloxane concentrate, oligomeric siloxane, functional ethoxy) Ç ü - Cj— 'n) CH ₂ CH ₃ Vinylmethyl polysiloxane ( Ji --- C -) -'n3H3 [00057] The superabsorven polymer! of the present invention can
include an additional or a second internal crosslinking agent, which can be used in conjunction with the internal silane crosslinker. The additional or second internal cross-linking compositions generally include at least two ethylenically unsaturated double bonds, or an ethylenically unsaturated double bond, and a functional group that is reactive to the acidic groups of the polymerizable unsaturated acidic group containing monomer, or several functional groups that are reactive for acid groups they can be used as the internal crosslinking component, and is desirably present during the polymerization of the polymerizable unsaturated acid group containing a monomer. Second internal cross-linking agents can include, but are not limited to, aliphatic unsaturated amides, such as methylenebisacryl- or -methacrylamide or ethylenebisacrylamide; aliphatic esters of polyols or alkoxylated polyols with ethylenically insane acids
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Buttered di (meta) acrylates or butanediol or ethylene glycol tri (meta) acrylates, polyglycols or trimethylolpropane; trimethylolpropane di- and triacrylate esters that can be oxyalkylated, desirably ethoxylated, with 1 to 30 moles of alkylene oxide; acrylate and methacrylate esters of glycerol and pentaerythritol and glycerol and pentaerythritol oxyethylated with desirably 1 to 30 moles of ethylene oxide; allyl compounds, such as allyl (meta) acrylate, alkoxylated ally (meta) acrylate reacted with desirably 1 to 30 moles of ethylene oxide, trialyl cyanurate, trialyl isocyanurate, maleic acid diallyl ester, polyallyl esters, tetraalyloxyethane, trialylamine, tetraalylatylenine , diols, polyols, hydroxy allyl or acrylate compounds and allyl esters of phosphoric acid or phosphorous acid; and monomers that are capable of cross-linking, such as N-methylol compounds of unsaturated amides, such as methacrylamide or acrylamide, and the ethers derived therefrom. Internal ionic crosslinkers, such as multivalent metal salts, can also be employed. The additional or second internal crosslinkers can be selected from polyethylene glycol monoalyl ether acrylate, propane trimethylol ethoxylated triacrylate, or polyethylene glycol diacrylate. Mixtures of the mentioned internal crosslinking agents can also be employed.
[00058] The content of the internal crosslinkers of internal silanes and second internal crosslinking agents is 0.001 percent by weight to 5 percent by weight, or 0.1 percent by weight to 3%, based on the total amount of the polymerizable unsaturated acid group. containing monomer. The superabsorbent polymer can include 9: 1 to 1: 9, or 7: 1: to 1: 7, of the internal crosslinker composition comprising silane and the second internal crosslinker.
[00059] In some respects, primers can be used to initiate free radical polymerization. Suitable initiators include, but are not limited to, azo or peroxo compounds, systems
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23/61 redox or ultraviolet initiators, sensitizers, and / or radiation. [00060] After polymerization, the superabsorbent polymer is generally formed into particles of superabsorbent polymer, or particulate superabsorbent polymer. While the superabsorbent polymer particles can be used by way of example of the physical form of the superabsorbent polymer composition, the invention is not limited to this form, and is applicable to other forms, such as fibers, foams, films, beads, rods , and the like. The particulate superabsorbent polymer of the present invention generally includes particle sizes ranging from 50 to 1000 pm, or 150 to 850 pm. The present invention can include at least 40 weight percent of the particles having a particle size of 300 pm to 600 pm, at least 50 weight percent of the particles having a particle size of 300 pm to 600 pm, or at least 60 percent by weight of the particles having a particle size of 300 pm to 600 pm, as measured by classification through a United States standard 30 mesh sieve, and retained in a United States standard 50 mesh sieve. In addition, the size distribution of the particulate superabsorbent polymer of the present invention can include less than 30 weight percent particles having a size greater than 600 pm, and less than 30 weight percent particles having a size of less than than 300 pm, as measured using, for example, a Model B RO-TAP® Mechanical Sieve Oscillator available from WS Tyler, Inc., Mentor Ohio.
[00061] In one embodiment, the particulate superabsorbent polymer can then be treated on the surface with additional chemicals and treatments, as placed here. In particular, the surface of the particulate superabsorbent polymer can be cross-linked, generally referred to as the cross-linked surface, by the addition of a surface cross-linking agent and heat treatment. In general, reticu
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Surface bonding is a process that is believed to increase the crosslink density of the polymer matrix in the vicinity of the surface of the particulate superabsorbent polymer with respect to the crosslink density of the interior of the particle.
[00062] Desirable surface crosslinking agents can include chemicals with one or more functional groups that are reactive to the pendant groups on the polymer chains, typically acid groups. Surface crosslinking agents can include compounds that comprise at least two functional groups that can react with functional groups of a polymer structure in a condensation reaction (condensation crosslinker), in an addition reaction or in a ring opening reaction . These compounds can include condensation crosslinkers such as, for example, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan acid fatty esters, trimethylolpropane, pentaerythritol, polyvinyl alcohol, sorbitol, 1,3-dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolan-2-one (propylene carbonate), 4,5dimethyl-1, 3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4metill-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, as well as 1,3dioxolan-2-one. The amount of the surface crosslinking agent can be present in an amount of 0.01 weight percent to 5 weight percent of the dry particulate superabsorbent polymer, and as much as 0.1 weight percent to 3 weight percent, and so on. as from 0.1 weight percent to 1 weight percent, based on the weight of the dry particulate superabsorbent polymer.
[00063] After the particulate superabsorbent polymer has been brought into contact with the surface crosslinker, or with the fluid with
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25/61 comprising the surface crosslinker, the treated particulate superabsorbent polymer is heat treated, which may include heating the coated particulate superabsorbent polymer to a temperature of 50 to 300 ° C, or 75 to 275 ° C, or 150 to 250 ° C, so that the outer region of the polymer structures is more strongly cross-linked, compared to the inner region (ie, surface cross-linking). The duration of the heat treatment is limited by the risk that the desired property profile of the polymer structures will be destroyed as a result of the heat effect.
[00064] In a particular aspect of surface crosslinking, the particulate superabsorbent polymer is coated or treated on the surface with an alkylene carbonate, followed by heating to affect the surface crosslinking, which can improve the surface crosslinking density and characteristics resistance of the superabsorbent polymer particle gel. More specifically, the surface crosslinking agent is coated on the superabsorbent polymer particulate by mixing the particulate superabsorbent polymer with an aqueous alcoholic solution of the alkylene carbonate surface crosslinking agent. The amount of alcohol in the aqueous alcoholic solution can be determined by the solubility of the alkylene carbonate, and is kept as low as possible for various reasons, for example, for protection against explosions. Suitable alcohols are methanol, isopropanol, ethanol, butanol, or butyl glycol, as well as mixtures of these alcohols. In some respects, the solvent is desirably water, which is typically used in an amount of 0.3 weight percent to 5.0 weight percent, based on the weight of the dry particulate superabsorbent polymer.
[00065] In other respects, the alkylene carbonate surface crosslinking agent is dissolved in water without any alcohol. In still other aspects, the carbonate surface crosslinking agent
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26/61 of alkylene can be applied from a powder mixture, for example, with an inorganic carrier material, such as silicon dioxide (SiO2) or in a vapor state by sublimation of the alkylene carbonate.
[00066] To achieve the desired surface crosslinking properties, alkylene carbonate must be constantly distributed in the particulate superabsorbent polymer. For this purpose, mixing is carried out in suitable mixers known in the art, such as fluidized bed mixers, paddle mixers, rotary drum mixers, or double wear mixers. It is also possible to coat the particulate superabsorbent polymer during one of the process steps in the production of the particulate superabsorbent polymer. In a particular aspect, a suitable process for this proposal is the reverse suspension polymerization process.
[00067] The heat treatment, which follows the coating treatment of the particulate superabsorbent polymer, can be carried out as follows. In general, the heat treatment is at a temperature of from 100 ° C to 300 ° C. Lower temperatures are possible if highly reactive epoxy crosslinking agents are used. However, if alkylene carbonates are used, then the heat treatment is suitably at a temperature of from 150 ° C to 250 ° C. In this particular aspect, the treatment temperature depends on the down time and the type of alkylene carbonate. For example, at a temperature of 150 ° C, heat treatment is carried out for an hour or longer. In contrast, at a temperature of 250 ° C, a few minutes (for example, from 0.5 minutes to 5 minutes) are sufficient to achieve the desired surface crosslinking properties. Heat treatment can be carried out in conventional dryers or ovens known in the art.
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27/61 [00068] In addition to surface crosslinking, the particulate superabsorbent polymer can be additionally treated on the surface with other chemical compositions. In some respects, the particulate superabsorbent polymer composition of the present invention can be surface treated from 0 weight percent to 5 weight percent, and from 0.001 weight percent to 5 weight percent, or 0.01 weight percent at 0.5 weight percent of the dry particulate superabsorbent polymer of a polymeric coating, such as a thermoplastic coating, or a cationic coating, or a combination of thermoplastic coating and a cationic coating. In some particular aspects, the polymeric coating desirably is a polymer that can be in a solid, emulsion, suspension, colloidal, or solubilized state, or combinations thereof. Polymeric coatings suitable for this invention may include, but are not limited to, a thermoplastic coating having a thermoplastic melting temperature comprising the polymeric coating that is applied to the particle surface coinciding with, or followed by a temperature of the treated superabsorbent polymer particle at the thermoplastic melting temperature.
[00069] Examples of thermoplastic polymers include polyolefin, polyethylene, polyester, polyamide, polyurethane, polybutadiene styrene, linear low density polyethylene (LLDPE), ethylene acrylic acid copolymer (EAA), ethylene alkyl methacrylate (EMA) copolymer, polypropylene (polypropylene) PP), maleat polypropylene, ethylene vinyl acetate (EVA) copolymer, polyester, polyamide, and mixtures of all polyolefin families, such as mixtures of PP, EVA, EMA, EEA, EBA, HDPE, MDPE, LDPE, LLDPE , and / or VLDPE, can also be advantageously employed. The term polyolefin, as used herein, is defined above. In particular, polypropylene maleate Petition 870190130737, of 12/09/2019, p. 31/74
28/61 is a preferred thermoplastic polymer for use in the present invention. A thermoplastic polymer can be functionalized to have additional benefits, such as water solubility or dispersibility. [00070] The polymeric coatings of this invention can also include a cationic polymer. A cationic polymer, as used herein, refers to a polymer or mixture of polymers comprising a functional group or groups having the potential to become positively charged ions after ionization in an aqueous solution. Functional groups suitable for a cationic polymer include, but are not limited to, primary, secondary or tertiary amino groups, imino groups, imido groups, starch groups, and quaternary ammonia groups. Examples of synthetic cationic polymers include the salts or partial salts of poly (vinyl amines), poly (allylamines), poly (ethylene imine), poly (amino propanol vinyl ethers), poly (acrylamidopropyl trimethyl ammonium chloride), poly (diallyldimethyl chloride) ammonia). Examples of naturally based cationic polymers include partially deacetylated chitin, chitosan, and chitosan salts. Synthetic polypeptides, such as polyasparagines, polylysines, polyglutamines, and polyarginines, are also suitable cationic polymers.
[00071] The particulate superabsorbent polymer compositions according to the invention can be surface treated from 0.01% to 2 weight percent, or from 0.01 weight percent to 1 weight percent based on the composition of superabsorbent polymer dries out of a water-insoluble inorganic metal compound. The water-insoluble inorganic metal compound may include a cation selected from aluminum, titanium, calcium, or iron, and an anion selected from phosphate, borate, or chromate. An example of a water-insoluble inorganic metal compound includes aluminum phosphate. The inorganic metal compound can have a mass average particle size of less than 2 pm, and can have a particle size
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Mass average 29/61 of less than 1 pm.
[00072] The inorganic metal compound can be applied in dry physical form to the surface of the particulate superabsorbent polymer composition. For this, the particulate superabsorbent polymer composition can be intimately mixed with the finely divided inorganic metal compound. The finely divided inorganic metal compound is usually added, at room temperature, to the superabsorbent polymer particles, and mixed until a homogeneous mixture is present. For this purpose, mixing is carried out in suitable mixers known in the art, such as fluidized bed mixers, paddle mixers, rotary drum mixers, or dual use mixers. The mixing of the particulate superabsorbent polymer compositions with the finely divided water-insoluble inorganic metal compound can occur before or after any surface crosslinking, for example, during the application of the surface crosslinking agent.
[00073] Alternatively, a suspension of finely divided water-insoluble inorganic metal compound can be prepared and applied to a particulate water-absorbing polymer. The suspension is applied, for example, by spraying. Useful dispersion medium for preparing the suspension includes water, organic solvents, such as alcohols, for example, methanol, ethanol, isopropanol, ketones, for example, acetone, methyl ethyl ketone, or mixtures of water with the aforementioned organic solvents. Other useful dispersion media include dispersion aids, surfactants, colloidal protectors, viscosity modifiers, and other auxiliaries to assist in preparing the suspension. The suspension can be applied in conventional reaction mixers, or mixing and drying systems, as described above, at a temperature in the ambient temperature range less than the boiling point of the dispersion medium, pre
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30/61 at room temperature. It is appropriate to combine the application of the suspension with a surface crosslinking step by dispersing the finely divided water-insoluble metal salt in the surface crosslinking agent solution. Alternatively, the suspension can also be applied before or after the surface crosslinking step. The application of the slurry can be followed by a drying step.
[00074] In some respects, the particulate superabsorbent polymer compositions according to the invention may include from 0 weight percent to 5 weight percent, or, in the alternative form, from 0.01 weight percent to 3 weight percent weight of dry particulate superabsorbent silica polymer. Examples of silica include steam silica, precipitated silica, silicon dioxide, silicic acid, and silicates. In some particular aspects, microscopic non-crystalline silicon dioxide is desirable. In some respects, the particle diameter of the inorganic powder can be 1,000 pm or less, such as 100 pm, or less.
[00075] In some respects, particulate superabsorbent polymer compositions may also include from 0% to 30 weight percent dry particulate superabsorbent polymer, such as 0.1 weight percent to 5 weight percent water-soluble polymers at weight basis of dry particulate superabsorbent polymer, such as partially or completely hydrolyzed polyvinyl acetate, polyvinylpyrrolidone, starch or starch derivatives, polyglycols, polyethylene oxides, polypropylene oxides, or polyacrylic acid.
[00076] In some respects, additional surface additives may optionally be employed with the particulate superabsorbent polymer, including odor-binding substances, such as cyclodextrins, zeolites, inorganic or organic salts, and similar materials; anti-mass additives, flow modifying agents, surfactants, viscosity modifiers, and the like. In addition,
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31/61 surface can be used, which perform various roles during surface modifications. For example, a simple additive can be a surfactant, viscosity modifier, and can react to crosslink polymer chains.
[00077] In some respects, the particulate superabsorbent polymer of the present invention can be, after a heat treatment step, treated with water so that the superabsorbent polymer composition has a water content of up to 10 weight percent of the superabsorbent polymer. dry particulate. This water can be added, with one or more of the top surface additives, to the particulate superabsorbent polymer.
[00078] The superabsorbent polymer according to the invention can be desirably prepared by two methods. The composition can be prepared continuously or discontinuously in a large-scale industrial manner, after cross-linking according to the invention being carried out accordingly.
[00079] According to the method, the partially neutralized monomer, such as acrylic acid, is converted to a gel by free radical polymerization in an aqueous solution in the presence of crosslinking agents and any additional components, and the gel is comminuted, dried, ground, and sieved to the desired particle size. This polymerization can be carried out continuously or discontinuously. For the present invention, the size of the high capacity particulate superabsorbent polymer is dependent on manufacturing processes including grinding and screening. It is well known to those skilled in the art that the particle size distribution of the superabsorbent polymer particles resembles a normal distribution, or a bell-shaped curve. It is also known that for various reasons, the normal particle size distribution can be tilted in any direction.
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[00080] According to another method, reverse suspension and emulsion polymerization can also be used to prepare the products according to the invention. According to these processes, a partially neutralized aqueous monomer solution, such as acrylic acid, is dispersed in a hydrophobic organic solvent with the aid of protective colloids and / or emulsifiers, and polymerization is initiated by free radical initiators. The internal cross-linking agents can either be dissolved in the monomer solution, and are measured together with it, or are added separately and optionally during polymerization. The addition of water-soluble polymer as the graft base optionally occurs via the monomer solution, or by direct introduction into the oil phase. The water is then removed azeotropically from the mixture, and the polymer is filtered and optionally dried. Internal crosslinking can be carried out by polymerizing a polyfunctional crosslinking agent dissolved in the monomer solution and / or by reacting suitable crosslinking agents with functional groups of the polymer during the polymerization steps.
[00081] The result of these methods is a superabsorbent polymer, or a superabsorbent polymer pre-product. A superabsorbent polymer pre-product, as used herein, is produced by repeating all the steps for producing superabsorbent, up to and including drying the material, and grinding coarse materials in a grinder, and removing particles larger than 850 pm, and less than 150 pm.
[00082] The particulate superabsorbent polymer of the present invention exhibits certain characteristics, or properties, as measured by Centrifugal Holding Capacity (CRC), Centrifugal Holding Capacity Increasing (CRCI), Centrifugal Holding Capacity Increasing Rate (CRCIR), Absorbance Under Load at 0.9 psi
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33/61 (AUL (0.9psi)), and Gel Bed Permeability (GBP). The Vortex Time measures the speed of the particulate superabsorbent polymer in saline absorption solution, and is expressed in seconds.
[00083] The resulting CRC is quoted as grams of liquid retained in gram weight of the sample (g / g), and can be 20g / g to 60g / g, 25g / g to 55g / g, or 27g / g to 50g / g.
[00084] CRCI is quoted as grams of liquid retained in gram weight of the sample (g / g), and can be from 2g / g to 50g / g, or from 3g / g to 40g / g.
[00085] The Centrifugal Retention Capacity Increase Rate Test (CRCIR) measures the Centrifugal Retention Capacity Increase Rate by time difference between the CRC Test (initial) and the CRC Test (second), and is measured in terms of g / g / hour. The CRC Increase Rate can be 0.4 to 10g / g / hour, or 0.5 to 5g / g / hour.
[00086] Absorbance Under Load at 0.9 psi (AUL (0.9psi)) can vary from 12 g / g to 30 g / g, or from 15 g / g to 25 g / g.
[00087] Permeability is a measure of the effective connectivity of a porous structure, be it a fiber mat, or a foam board or, in this case, particulate superabsorbent polymer, and can be specified in terms of the void fraction, and extent of connectivity of the particulate superabsorbent polymer. Gel permeability is a property of the particle mass as a whole, and is related to the particle size distribution, particle shape, and open pore connectivity between the particles, shear modulus, and surface modification of the swollen gel. In practical terms, the gel permeability of the particulate superabsorbent polymer is a measure of how quickly the liquid flows through the mass of swollen particles. The low gel permeability indicates that the liquid cannot readily flow through the
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34/61 particulate superabsorbent polymer, which is generally referred to as gel blocking, and that any forced flow of liquid (such as a second application of urine during diapering) must take an alternating path (for example, diaper leakage). Gel Bed Permeability (GBP) can range from 10 Darcy to 300 Darcy, or from 10 Darcy to 200 Darcy.
[00088] The vortex time for the particulate superabsorbent polymer and the particulate superabsorbent polymer composition can be from 20 to 180 s, or from 60 to 130 s, or from 70 to 125 s.
[00089] As shown in fig 1, it is an objective of the present invention to increase the absorption capacity over time comprising such particulate superabsorbent polymers which can offer the advantage of high gel resistance in the short term and high absorption capacity in the long term.
[00090] Figure 2 reveals CRC (ta) and CRC (bt) of a particulate superabsorbent polymer comprising 0.5% Dynasylan® 6490. It shows that the CRC of the particulate superabsorbent polymer increases with time or at room temperature or temperature of the body. In addition, it shows that CRC at body temperature is higher than CRC at room temperature at any specific time. In addition, it shows that CRC increases at body temperature than at room temperature.
[00091] Figure 3 shows CRC (t.a) and CRC (bt) of a particulate superabsorbent polymer with a cross-linked surface comprising 0.5% Dynasylan® 6490 as an internal crosslinker. It shows that CRC increases with time or at room temperature or body temperature. In addition, it demonstrates that CRC at body temperature is higher than CRC at room temperature at any specific time. In addition, it shows that CRC increases faster at body temperature than at room temperature.
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35/61 [00092] Figure 4, Prior Art, shows the CRC (t.a) and CRC (bt) of a particulate superabsorbent polymer with a cross-linked surface comprising only conventional internal crosslinker. It shows that CRC was essentially constant over time or at different temperatures.
[00093] The particulate superabsorbent polymer, according to the present invention, can be used in many absorbent articles, including sanitary towels, diapers, or wound coverings, and they have the property that they quickly absorb large amounts of menstrual blood, urine , or other bodily fluids. Since the agents according to the invention retain the absorbed liquids even under pressure, and are also capable of delivering additional liquid within the construction in the swollen state, they are most desirably employed in higher concentrations with respect to the hydrophilic fiber material, such as as fluff, when compared to current conventional superabsorbent compositions. They are also suitable for use as a homogeneous superabsorbent layer without retaining fluff within the diaper construction, as a result of which particularly thin articles are possible. Polymers are, moreover, suitable for use in hygiene articles (incontinence products) for adults.
[00094] Absorbent articles, similar to diapers, may include (a) a liquid-permeable top sheet; (b) a liquid-permeable backsheet; (c) a core positioned between (a) and (b), and comprising from 10% to 100%, or from 50 percent by weight to 100%, by weight of the particulate superabsorbent polymer, and from 0% to 90% by weight hydrophilic fiber material; (d) optionally a layer of tissue directly positioned above and below said core (c); and (e) optionally, an acquisition layer positioned between (a) and (c).
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36/61
PROCEDURE TESTS
Water content
Centrifugal Retention Capacity Test (CRC).
[00095] The CRC Test measures the ability of the superabsorbent polymer to retain liquid in it after being saturated and subjected to centrifugation under controlled conditions. The resulting holding capacity is referred to as grams of liquid retained in gram weight of the sample, (g / g). The sample to be tested is prepared from particles that are pre-classified through a United States standard 30 mesh sieve and retained in a United States standard 50 mesh sieve. As a result, the particulate superabsorbent polymer sample comprises particles sized in the range of 300 to 600 pm. The particles can be pre-sieved by hand, or automatically.
[00096] Retention capacity is measured by placing 0.2 gram of the pre-classified sample of particulate superabsorbent polymer in a water-permeable bag that will contain the sample, while a test solution (0.9 percent by weight of sodium chloride in distilled water) is to be freely absorbed by the sample. A heat sealable tea bag material, such as that available from Dexter Corporation (having a business location in Windsor Locks, Connecticut, U.S.A.) as a model 1234T designation heat seal filter works well for many applications. The bag is formed by folding a 13cm by 8cm (5 inch by 3 inch) sample of the bag material in half, and heat sealing two of the open edges to form a 6cm by 8cm (2.5 inch) rectangular bag by 3 inches). Heat seals are 1 cm (0.25 inch) inside the edge of the material. After the sample is placed in the pouch, the remaining open edge of the pouch is also heat sealed. Empty bags are also produced to serve
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37/61 as controls. Three samples are prepared for each particulate superabsorbent polymer to be tested.
[00097] The sealed bags are submerged in a container containing the test solution at a designated test temperature, making sure that the bags are kept down until they are completely moistened. After wetting, the samples remain in the solution for a designated test period, during which time they are removed from the solution and temporarily set on a flat, non-absorbent surface.
[00098] The wet bags are then placed in the basket comprising the wet bags that are separated from each other, and are placed on the outer circumferential edge of the basket, comprising the basket which is of a suitable centrifuge capable of subjecting the samples to a g-force of 350. A suitable centrifuge is a CLAY ADAMS DYNAC II, model # 0103, having a water collection basket, a digital rpm meter, and a machined drain basket adapted to retain and drain the flat bag samples. Where multiple samples are centrifuged, samples are placed in opposite positions within the centrifuge to balance the basket when rotating. The bags (including the wet empty bags) are centrifuged at 1,600 rpm (for example, to reach a 350 g target force with a force variance of 240 to 360 g, for 3 minutes. The G force is defined as a unit of inertial force in a body that is subjected to rapid acceleration or gravity, equal to 9.7 m / s ² (32 ft / s ² ) at sea level.The bags are removed and weighed, with the empty bags (controls) being weighed first, followed by the bags containing the samples of superabsorbent polymer , exPetition 870190130737, of 12/09/2019, page 41/74
38/61 rush as grams of fluid per gram of superabsorbent polymer. More particularly, the holding capacity is determined by the following equation:
CRC = [sample / bag after centrifuge - empty bag after centrifuge dry sample weight] / dry sample weight [00099] The three samples are tested and the results are classified to determine the CRC of the particulate superabsorbent polymer.
[000100] CRC (rt, 0.5 hour) is measured with a test temperature of 23 ° C (room temperature) and a test time of 0.5 hour.
[000101] CRC (rt, 5 hour) is measured with a test temperature of 23 ° C (room temperature) and a test time of 5 hours.
[000102] CRC (rt, 16 hours) is measured with a test temperature of 23 ° C (room temperature) and a test time of 16 hours.
[000103] CRC (bt, 0.5 hour) is measured with a test temperature of 37 ° C (body temperature) and a test time of 0.5 hour.
[000104] CRC (bt, 5 hours) is measured with a test temperature of 37 ° C (body temperature) and a test time of 5 hours.
Centrifugal Retention Capacity Increase Test (CRCI) [000105] The Centrifugal Retention Capacity Increase Test (CRCI) measures the increase in CRC that occurs and is calculated as the difference between the second CRC Test and the first CRC Test. CRC (ta, 0.5 hour, and is determined by the following equation:
[000106] CRC increase = second CRC - (CRC (t.a, 0.5 hour). [000107] For example, CRCI's in the present invention are determined by the following equations:
[000108] At room temperature, CRCI (t.a) = CRC (t.a, 5 hours) .CRC (t.a, 0.5 hours).
[000109] At body temperature, CRCI (bt) = CRC (bt, 5 hours) .CRC (bt, 0.5 hours).
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39/61 [000110] CRCI (t.a) and CRCI (bt) are collectively referred to as CRCI.
Centrifugal Retention Capacity Increase Rate Test (CRCIR) [000111] CRCIR measures the ability of the particulate superabsorbent polymer to gain additional CRC over time when contacted with a liquid. It is tested by measuring the CRC and at a test temperature designated for two different test times. The second test time is at least one hour longer than the first test time. The resulting CRCIR is quoted as grams of additional liquid retained in gram weight of the sample per hour (g / g / hour).
[000112] For example, the CRCIR in the present invention is determined by the following equations:
[000113] At room temperature: CRCIR (ta) = [CRC (ta, 5 hours) - (CRC (ta, 0.5 hours)] / 4.5 [000114] At body temperature: CRCIR (bt) = [ CRC (bt, 5 hours) (CRC (bt, 0.5 hours)] /4.5 [000115] CRCIR (ta) and CRCIR (bt) are collectively referred to as CRCIR.
Swell-Free Gel Bed Permeability Test (FSGBP) [000116] As used herein, the Swell-Free Gel Bed Permeability Test, also referred to as the Gel-Bed Permeability (GBP) Under Swell Pressure Test at 0 psi, it determines the permeability of a swollen bed of particulate superabsorbent polymer (for example, such as the surface-treated particulate superabsorbent polymer before being treated on the surface), under what is commonly referred to as free swelling conditions. The term free swelling means that
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40/61 particulate superabsorbent polymers are allowed to swell without a restriction load after absorbing the test solution, as will be described. An apparatus suitable for conducting the Gel Bed Permeability Test is shown in figures 5, 6, and 7, and is generally indicated as 500. The 528 test apparatus set comprises a sample container, generally indicated at 530, and a plunger, generally indicated at 536. The plunger comprises a shaft 538 having a cylinder bore drilled below the longitudinal axis and a head 550 positioned at the bottom of the shaft. The shaft bore 562 has a diameter of 16 mm. The plunger head is attached to the shaft, as by adhesion. Twelve holes 544 are drilled in the radial axis of the shaft, three positioned throughout 90 degrees having diameters of 6.4 mm. The 538 shaft is machined from a LEXAN rod or equivalent material, and has an outer diameter of 2.2 cm and an inner diameter of 16 mm.
[000117] The plunger head 550 has a concentric inner ring with seven holes 560 and an outer ring with 14 holes 554, all holes having a diameter of 8.8 mm, as well as a 16 mm hole aligned with the shaft. The plunger head 550 is machined from a LEXAN rod or equivalent material, and has a height of approximately 16 mm, and a diameter dimensioned such that it rests inside the cylinder 534 with minimal wall clearance, but still slides freely. The total length of the plunger head 550 and shaft 538 is 8.25 cm, but can be machined at the top of the shaft to obtain the desired mass of the plunger 536. The plunger 536 comprises a 100 564 mesh stainless steel screen that it is biaxially stretched and tightened to the lower end of the plunger 536. The sieve is fixed to the plunger head 550 using an appropriate solvent that causes the sieve to be securely adhered to the plunger head 550. Care must be taken to avoid
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41/61 excessive solvent migration in the open portions of the sieve and reduction of the open area for liquid flow. Weld-on 4 acrylic solvent from IPS Corporation (having a business location in Gardena, California, USA) is a suitable solvent.
[000118] Sample container 530 comprises a cylinder 534 and a 400 566 mesh stainless steel sieve which is biaxially stretched and fixed to the lower end of the cylinder 534. The sieve is fixed to the cylinder using a solvent that makes the sieve adhere securely to the cylinder. Care must be taken to avoid excessive solvent migration in the terminal portions of the sieve and to reduce the open area for liquid flow. Acrylic solvent Weld-on 4 from IPS Corporation is a suitable solvent. A sample of particulate superabsorbent polymer, indicated as 568 in figure 2, is supported on the 566 sieve inside the cylinder 534 during testing.
[000119] Cylinder 534 can be drilled from a transparent LEXAN rod, or equivalent material, or can be cut from a LEXAN tube, or equivalent material, and has an internal diameter of 6 cm (for example, a cross-sectional area of 28.27 cm ² ), a wall thickness of 0.5 cm and a height of approximately 7.95 cm. A step is machined to the outside diameter of cylinder 534 such that a region 534a with an outside diameter of 66 mm exists for the bottom 31 mm of cylinder 534. An o-ring 540 that adjusts the diameter of region 534a can be placed on top of the step.
[000120] Annular weight 548 features a perforated counter hole
2.2 cm in diameter and 1.3 cm deep, so that it slides freely on the 538 axis. The annular weight also has a 16 mm hole 548a. The ring weight 548 can be produced from stainless steel or other suitable corrosion resistant materials in the presence of the test solution, which is 0.9 percent by weight of
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42/61 sodium chloride in distilled water. The combined weight of the plunger 536 and annular weight 548 equals approximately 596 grams (g), which corresponds to a pressure applied to the sample 568 of 0.3 pounds per square inch (psi), or 2.07 kPa (20.7 dynes / cm ² ), a sample area of 28.27 cm ² remains.
[000121] When the test solution flows through the test apparatus during the test, as described below, the sample container 530 generally sits in a container 600. The proposal of the reservoir is to divert liquid that floods the top of the sample container 530 and diverts the flooded liquid to a separate collection device 601. The reservoir can be positioned above a scale 602 with a beaker 603 resting on it to collect saline solution that passes through the swollen sample 568.
[000122] To conduct the Gel Bed Permeability Test under conditions of free swelling, the plunger 536, with the weight 548 seated in it, is placed in an empty sample container 530 and the height from the top of the weight 548 the bottom of the sample container 530 is measured using a suitable measurement accurate to 0.01 mm. The strength of the thickness measurement applied during measurement should be as low as possible, preferably less than 0.74 Newtons. It is important to measure the height of each combination of empty sample container 530, plunger 536, and weight 548 and maintain the track from which plunger 536 and weight 548 is used when using a multiple tester. The same plunger 536 and weight 548 should be used for measurement when the sample 568 is later swelled after saturation. It is also desirable that the base that the sample cup 530 is resting on is level, and the upper surface of the weight 548 is parallel to the bottom surface of the sample cup 530.
[000123] The sample to be tested is prepared from superab polymer
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43/61 particulate sorbent that is pre-sieved through the United States standard 30 mesh sieve, and retained in the United States standard 50 mesh sieve. As a result, the test sample comprises particles sized in the range of 300 to 600 pm. The particulate superabsorbent polymer can be pre-screened with, for example, a RO-TAP Model B Mechanical Sieve Oscillator available from W. S. Tyler, Inc., Mentor Ohio. The screening is conducted for 10 minutes. Approximately 2.0 grams of the sample is placed in the 530 sample container and spread constantly on the bottom of the sample container. The container, with 2.0 grams of sample in it, without the plunger 536 and weight 548 in it, is then submerged in the 0.9% saline solution for a period of 60 minutes to saturate the sample and allow the sample to swell free of any restraining loads. During saturation, the sample cup 530 is seated on a mesh located in the liquid reservoir so that the sample cup 530 is raised slightly above the bottom of the liquid reservoir. The mesh does not inhibit the flow of saline into the sample cup 530. A suitable mesh can be obtained as part number 7308 from Eagle Supply and Plastic, having a place of business in Appleton, Wisconsin, USA Saline does not fully cover the particles of superabsorbent polymer composition, as evidenced by a perfectly flat saline surface in the test cell. Also, the depth of the saline is not allowed to fall below that of the surface within the cell is defined only by the swollen particulate superabsorbent polymer, preferably than saline.
[000124] At the end of this period, the plunger assembly 536 and weight 548 is placed in the saturated sample 568 in the sample container 530 and then the sample container 530, plunger 536, weight 548, and sample 568, are removed of the solution. After removal and before
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44/61 measured, the sample container 530, plunger 536, weight 548, and sample 568 are to remain in the remainder for 30 seconds on a suitable large flat grid non-deformable plate of uniform thickness. The thickness of the saturated sample 568 is determined by re-measuring the height from the top of the weight 548 to the bottom of the sample container 530, using the same thickness measurement used previously provided that the zero point is unchanged from the measurement of initial height. Sample container 530, plunger 536, weight 548, and sample 568, can be placed on a large, flat grid non-deformable plate of uniform thickness that will prevent the liquid in the sample container from being released on a flat surface due to the strain of surface. The plate has a total dimension of 7.6 cm by 7.6 cm, and each grid has a cell size dimension of 1.59 cm long by 1.59 cm wide by 1.12 cm deep. A suitable large flat grid non-deformable plate material is a parabolic diffuser panel, catalog number 1624K27, available from McMaster Carr Supply Company, having a business location in Chicago, Illinois, USA, which can then be cut at correct dimensions. This large flat mesh non-deformable plate must also be present when measuring the height of the initial empty set. The height measurement should be made as soon as practicable after the thickness measurement is engaged. The height measurement obtained from the measurement of the empty sample container 530, plunger 536, and weight 548, is subtracted from the height measurement obtained after sample saturation 568. The resulting value is the thickness, or height H of the swollen sample.
[000125] The permeability measurement is initiated by distributing a flow of the 0.9% saline solution in the sample container 530 with the saturated sample 568, plunger 536, and weight 548, inside. The flow rate of the test solution in the container is adjusted to make
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45/61 that saline overflows on top of cylinder 534, thereby resulting in a consistent head pressure equal to the height of sample container 530. The test solution can be added by any suitable means that is sufficient to ensure a small but consistent amount of overflow from the top of the cylinder, such as a 604 metering pump. The overflow liquid is diverted in a separate collection device 601. The amount of solution that passes through the sample 568, versus time, is measured gravimetrically using the 602 scale and 603 beaker. Data points from the 602 scale are collected every second for at least sixty seconds once the overflow has started. Data collection can be done manually or with data collection software. The flow rate, Q, through the swollen sample 568, is determined in units of grams / second (g / s) by a linear minimum square adjustment of fluid that passes through the sample 568 (in grams) versus time (in seconds).
[000126] The permeability in cm ² is obtained by the following equation: K = [Q * H * p] / [A * p * P] where K = Permeability (cm ² ), Q = flow rate (g / s) , H = swollen sample height (cm), μ = liquid viscosity (poise) (approximately one centipoise for the test solution used with this Test), A = cross-sectional area for liquid flow (28.27 cm ² for the sample container used with this Test), p = density of the liquid (g / cm ³ ) (approximately one g / cm ³ , for the test solution used with this Test) and P = hydrostatic pressure (dynes / cm ² ) (normally approximately 0.779 KPa (7.797 dynes / cm ² ). Hydrostatic pressure is calculated from P = p * g * h, where p = density of the liquid (g / cm ³ ), g = gravitational acceleration, nominally 981 cm / s ² , eh = fluid height, for example, 7.95 cm for The Gel Bed Permeability Test described here.
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46/61 [000127] A minimum of two samples are tested and the results are classified to determine the Gel Bed Permeability of the sample.
Absorbency Under Load Test (AUL (0.9psi)) [000128] The Absorbance Under Load Test (AUL) measures the ability of the particulate superabsorbent polymer to absorb a 0.9 weight percent solution of sodium chloride in distilled water at temperature environment (test solution), while the material is under a load of 0.9. The AUL test device consists of:
• a set of AUL including a cylinder, a piston of
4.4 g, and a standard weight of 317 gm. The components of this set are described in further detail below.
• a flat rounded square plastic tray that is large enough to allow the glass frits to sit on the bottom without contact with the tray walls. A plastic tray that is 9 by 9 (22.9cm x 22.9cm), with a depth of 0.5 to 1 (1.3cm to 2.5cm), is commonly used for this test method.
• a 12.5 cm diameter sintered glass frit with a 'C' porosity (25-50 microns). This frit is prepared in advance by equilibrating in saline (sodium chloride 0.9% in distilled water, by weight). In addition to being washed with at least two portions of fresh saline, the frit must be immersed in saline for at least 12 hours before AUL measurements.
• Whatman Grade 1 filter paper circles 12.5 cm in diameter.
• a supply of saline (sodium chloride 0.9% in distilled water, by weight).
[000129] Referring to figure 8, cylinder 412 of the AUL 400 assembly used to contain particulate superabsorbent polymer 410 is produced from a plastic tube with a thermoplastic inner diameter of one
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47/61 inch (2.54cm) lightly machined to be safe from concentricity. After machining, a 400 414 stainless steel wire mesh fabric is fixed to the bottom of the cylinder 412 by heating the steel wire fabric 414 in a flame to red heat, after which the cylinder 412 is held in the wire fabric of steel until cooled. A soldering iron can be used to weld the seal if it is unsuccessful, or if it breaks. Care must be taken to maintain a smooth, flat bottom and not to distort the inside of cylinder 412.
[000130] The 4.4 g (416) piston is made of one-inch solid material (eg PLEXIGLAS®), and is machined to fit closely without connection to cylinder 412.
[000131] A standard weight of 317 gm 418 is used to provide a restraining load of 0.9 psi (62,053 dyne / cm ² ). The weight is a cylindrical stainless steel weight of 2.5 cm (1 inch) in diameter, which is machined to fit closely without connection to the cylinder.
[000132] Unless otherwise specified, a sample 410 corresponding to a layer of at least 0.16 g (300 gsm.) Of particulate superabsorbent polymer is used to test the AUL. Sample 410 is taken from the particulate superabsorbent polymer which is pre-sieved through the United States standard # 30 mesh and retained in the United States standard # 50 mesh. Superabsorbent polymer composition particles can be pre-screened with, for example, a RO-TAP ^® Model B Mechanical Sieve Oscillator, available from WS Tyler, Inc., Mentor Ohio. The screening is conducted for 10 minutes.
[000133] The inside of the cylinder 412 is cleaned with an anti-aesthetic fabric before placing the particles of particulate superabsorbent polymer 410 in the cylinder 412.
[000134] The desired quantity of the sieved particulate superabsorbent polymer sample 410 (0.16 g) is weighed on a
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48/61 weight, and constantly distributed on wire fabric 414 at the bottom of cylinder 412. The weight of the particulate superabsorbent polymer at the bottom of the cylinder is recorded as 'SA,' for use in calculating the AUL described below. Care is taken to be safe in the particulate superabsorbent polymer adhered to the cylinder wall. After carefully placing the 4.4 g 412 piston and 317 g 418 weight into the particulate superabsorbent polymer 410 in the cylinder 412, the AUL 400 assembly including the cylinder, piston, weight, and superabsorbent particulate polymer is weighed, and the weight is recorded as 'A' weight.
[000135] The sintered glass frit 424 (described above) is placed in plastic tray 420, with saline 422 added at a level equal to that of the top surface of glass frit 424. A simple circle of filter paper 426 is placed gently on the glass frit 424, and the AUL 400 set with the particulate superabsorbent polymer 410 is then placed on top of the filter paper 426. The AUL 400 set is then allowed to remain on top of the 426 filter paper for a one-hour test period, paying attention to keeping the saline level in the tray constant.
[000136] At the end of the one-hour test period, the AUL device is then weighed, with this value recorded as 'B' weight. [000137] AUL (0.9 psi) is calculated as follows:
AUL (0.9 psi) = (B-A) / SA comprising
A = AUL Unit Weight with dry SAP
B = AUL Unit Weight with SAP after 60 minutes of absorption
SA = Actual SAP weight [000138] A minimum of two tests are performed and the results are classified to determine the AUL value under load of 0.9 psi. The samples are tested at 23 ° C and 50% relative humidity.
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Vortex time [000139] General Description: Vortex tests measure the amount of time in seconds required for 2 grams of a particulate superabsorbent polymer to close a vortex created by shaking 50 milliliters of saline at 600 revolutions per minute on a plate magnetic stirrer. The time it takes for the vortex to close is an indication of the rate of free swelling absorption of the particulate superabsorbent polymer.
EQUIPMENT AND MATERIALS
1. Beaker, 100 milliliters
2. Programmable magnetic stirrer, capable of delivering 600 revolutions per minute (such as the one commercially available from PMC Industries as Dataplate®. Model # 721).
3. Magnetic stirring bar without rings, 7.9 mm 32 times mm, Teflon. TM. covered (such as that commercially available from Baxter Diagnostics, under the trade name S / PRIM single brand package step stir bars with removable pivot ring).
4. Stopwatch
5. Accurate balance at +/- 0.01 gram
6. Saline solution, 0.87 w / w percent, Blood Bank Saline available from Baxter Diagnostics (considered here to be the equivalent of 0.9 weight percent saline)
7. Weighing the paper
8. Environment with standard atmosphere condition: Temperature = 23 ° C +/- 1 ° C and Relative Humidity = 50% + / - 2%.
TEST PROCEDURE
1. Measure 50g +/- 0.01 gram of saline solution in the 100 milliliter beaker.
2. Place the magnetic stir bar in the beaker.
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3. Program the magnetic stirring plate at 600 revolutions per minute.
4. Place the beaker in the center of the magnetic stirring plate such that the magnetic stirring bar is activated. The bottom of the vortex should be near the top of the stir bar.
5. Weigh 2g +/- 0.01 gram of the particulate superabsorbent polymer to be tested on the weighing paper.
[000140] NOTE: The particulate superabsorbent polymer is tested as received (ie, as it would be in an absorbent compound such as that described here). No screening for a specific particle size is done, although the particle size is known to have an effect on this test.
6. While the saline solution is being stirred, the rapidly poor particulate superabsorbent polymer is tested in the saline solution and starts the timer. The particulate superabsorbent polymer to be tested should be added to the saline solution between the center of the vortex and the side of the beaker.
7. Stop the timer when the surface of the saline solution becomes plaque and record the time.
8. Time, recorded in seconds, is recorded as the Vortex Time.
EXAMPLES [000141] The following comparative examples and examples of superabsorbent polymer and particulate superabsorbent polymer of the present invention, and a pre-product thereof, are provided to illustrate the present invention and not to limit the scope of the claims. Unless otherwise stated elsewhere, percentages are by weight.
SAP pre-product [000142] A superabsorbent polymer of the present invention can
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51/61 be produced as follows. In a polyethylene container equipped with a stirrer and cooling coils, 482 grams of 50% NaOH and 821 grams of distilled water were added and cooled to 20 ° C. 207 grams of glacial acrylic acid was then added to the caustic solution, and the solution again cooled to 20 ° C. Specific amount of internal crosslinkers according to Tables 2 to 3 for Comparative Examples 1 to 7 and Examples 1 to 18, and 413 grams of glacial acrylic acid were added to the first solution, followed by cooling to 4-6 ° C. Nitrogen was bubbled through the monomer solution for 10 minutes. The cooling coils have been removed from the container. To the monomer solution was added 20 g of 1 wt% aqueous solution of H ₂ O ₂ , 30 g of 2 wt% aqueous solution of sodium persulfate, and 18 g of 0.5 wt% aqueous solution of sodium erythorbate to initiate the polymerization reaction. The stirrer was stopped and the initiated monomer was allowed to polymerize for 20 minutes.
[000143] A particulate superabsorbent polymer can be prepared as follows. The resulting hydrogel was cut and extruded with a commercial Hobart 4M6 extruder, followed by drying in a Procter & Schwartz Model 062 air-forced oven at 175 ° C for 12 minutes with upward flow and 6 minutes with downward air flow in a tray. perforated 20-inch X 40-inch metal at a final product moisture level of less than 5 percent by weight. The dry particulate superabsorbent polymer was coarsely ground in a Prodeva Model 315-S grinder, ground in a 666-F three-stage cylinder mill and sieved with a Minox MTS 600DS3V to remove superabsorbent polymer particles larger than 850 pm and smaller than 150 pm.
Comparative examples 1 to 6 [000144] According to Table 2 for Comparative Examples 1
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52/61 to 6, the internal crosslinkers and silicon compounds were added to the monomer solution in the SAP SuperProduct superabsorbent polymer to prepare particulate superabsorbent polymers from Comparative Examples 1-6.
[000145] Comparative Examples 1 to 5 demonstrate that silane or silicate compounds without carbon-carbon double bond are not effective internal crosslinkers for particulate superabsorbent polymers based on polyacrylate. In addition, CRC Increase was not seen in these comparative examples of particulate superabsorbent polymer.
[000146] Comparative Example 6 demonstrates that 3-trimethoxysili propyl methacrylate is an effective crosslinker for superabsorbent polymers. But the CRC Increase was not seen in this case. The crosslinking formed by 3-trimethoxysil propyl methacrylate is likely to be adequate over time. The chemical structure of 3-trimethoxysil propyl methacrylate is shown below.

Table 2 - Comparative Examples 1-6 of particulate superabsorbent polymer
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Sample Second internal crosslinker Silane crosslinker CRC (t.a,0.5 hours) CRC (t.a,16 hours) CE 1 0.4% A * none 47.3 47.8 CE 2 0.4% A 1% sodium methyl silicate 48.9 50.2 EC 3 0.4% A 1% methyltrimethoxy silane 49.7 50.8 CE 4 0.4% A 1% tetraethoxy orthosilicate 51.9 52.4 EC 5 0.4% A 1% tetra-acetoxy silicate 51.8 52.4 EC 6 0.4% A 0.5% 3-trimethoxysilipropyl methacrylate 25.2 26.0 * Reticulated or A: polyethylene glycol monoalylether acrylate,
Comparative Example 7 and Examples 1 to 13 [000147] According to Table 3 for Comparative Example 7 and Examples 1 to 13, conventional crosslinker (s) and / or silicon crosslinker (s) were added to the solution of monomer of the superabsorbent polymer of the SAP Pre-Product to prepare particulate superabsorbent polymers.
[000148] The results in Table 3 indicate that the CRC of the particulate superabsorbent polymer of Examples 1 to 13 increases with time or at room temperature or at body temperature. In addition, the CRC increases with increasing test temperature. In addition, CRC increases more quickly at body temperature than at room temperature.
[000149] In comparison, comparative example 7 of the sample (CE 7) of the particulate superabsorbent polymer, which comprises only conventional internal crosslinker, shows CRC essentially constant from the particulate superabsorbent polymer over time, or at different temperatures.
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Table 3 - Comparative Example 7 and Examples 1-13 of particulate superabsorbent polymer
Ex Second internal crosslinker Silane or siloxane crosslinker CRC (t.a,0.5 hour) CRC (t.a,5 hours) CRC (bt,0.5 hour) CRC (bt,5 hours) EC 7 0.5% A *, and 0.25% C *** none 43 43.9 43.4 42.7 Ex 1 none 1% Dynasylan® 6490 27.1 41.3 39.1 78.3 Ex 2 0.4% A vinyltriisopropenoxy silane 1% 30.5 37.9 36.2 47.7 Ex 3 0.4% A vinyltriacetoxy silane 1% 27.4 34.7 33.9 45.2 Ex 4 0.4% A vinyltrimethoxy silane 1% 20.6 27.2 26.2 40.9 Ex 5 0.4% A vinyltriethoxy silane 1% 20.5 28.8 27.8 43.5 Ex 6 0.4% A dietoxymethylvinyl silane 40.4 50.1 49.3 52.3 Ex 7 0.4% A 1% Dynasylan® 6498 39.6 45.2 44.6 49.4 Ex 8 0.4% A 0.5% Dynasylan® 6490 26.1 33.7 32.6 44.4 Ex 9 0.4% A 0.375% Dynasylan® 6490 30.2 35.5 33.5 43.1 Ex 10 0.2% A, and 0.1% B ** 0.5% Dynasylan® 6490 26.1 33.6 32.4 41.3 Ex 11 0.2% A, and 0.1% C 0.25% Dynasylan® 6490 41.4 48.2 46.2 56.3 Ex 12 0.2% A, and 0.1% C 0.375% Dynasylan® 6490 35.2 42.2 40.2 52.2 Ex 13 0.2% A, and 0.1% C 0.5% Dynasylan® 6490 31.1 38.9 35.3 48.6
54/61 * Crosslinker A: polyethylene glycol monoalylether acrylate, ®
** Crosslinker B: ethoxylated trimethylol propane triacrylate (SARTOMER 454 product) *** Crosslinker C: polyethylene glycol 300 diacrylate
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Comparative example 8 [000150] Comparative example 8 of a particulate superabsorbent polymer can be prepared as follows. 100g of the product obtained from Comparative Example 7 was mixed uniformly with 0.5% Sipernat® 22s (commercially available from Evonik-Degussa Corporation), followed by uniform spray application of a solution containing 1 weight percent ethylene carbonate and 4 weight percent of water using a finely atomized spray, while the particulate superabsorbent polymer is fluidized in air. The coated particulate superabsorbent polymer was then heated to 185 ° C for 55 minutes in a convection oven. The product was cooled and sieved to remove particles greater than 850 pm and less than 150 pm.
[000151] Examples 14-19 of a particulate superabsorbent polymer according to the present invention can be prepared as follows.
Example 14 [000152] 100g of particulate superabsorbent polymer obtained from
Example 12 was mixed uniformly with 0.5% Sipernat® 22s, followed by the application of uniform spraying of a solution containing 1 weight percent ethylene carbonate and 4 weight percent water using a finely atomized spray, while the particles of SAP are fluidized in air. The coated particulate superabsorbent polymer was then heated to 185 ° C for 55 minutes in a convection oven. The particulate superabsorbent polymer was cooled and sieved to remove particles greater than 850 pm and less than 150 pm.
Example 15 [000153] Similar to Example 14, except the particulate superabsorbent polymer of Example 13 was used as the base polymer and the poly
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56/61 mere coated particulate superabsorbent was heated for 40 minutes at 185 ° C.
Example 16 [000154] 100 g of particulate superabsorbent polymer obtained from
Example 12 was mixed uniformly with 0.5 weight percent of Sipernat ^® 22s, followed by the application of uniform spraying of a solution containing 1 weight percent ethylene carbonate, 200 ppm malty polypropylene, and 4 weight percent water using a finely atomized spray, while the particulate superabsorbent polymer is fluidized in air. The coated particulate superabsorbent polymer was then heated to 185 ° C for 55 minutes in a convection oven. The particulate superabsorbent polymer was cooled and sieved to remove particles greater than 850 pm and less than 150 pm.
Example 17 [000155] 100 g of particulate superabsorbent polymer obtained from
Example 12 was mixed uniformly with 0.5% Sipernat® 22, followed by the application of uniform spraying of a solution containing 1 weight percent ethylene carbonate, 200 ppm malty polypropylene, 0.25 weight percent aluminum phosphate , and 4 weight percent water using a finely atomized spray, while SAP particles are fluidized in air. The coated particulate superabsorbent polymer was then heated to 185 ° C for 55 minutes in a convection oven. The particulate superabsorbent polymer was cooled and sieved to remove particles greater than 850 pm and less than 150pm.
Example 18 [000156] 100 g of particulate superabsorbent polymer obtained from
Example 17 was coated with a solution containing 0.2 weight percent polyvinylamine (Lupamin® 9025), 0.1% PEG-8000, and 3
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57/61 weight percent of water using a finely atomized spray, while the particulate superabsorbent polymer is fluidized in air. The coated particulate superabsorbent polymer was relaxed at room temperature overnight and sieved to remove particles greater than 850 pm and less than 150 pm.
Example 19 [000157] 100 g of the particulate superabsorbent polymer obtained from
Example 12 was coated with a solution containing 1 weight percent ethylene carbonate, 1% aluminum sulfate, 200 ppm malty polypropylene, and 4 weight percent water using a finely atomized spray, while SAP particles are fluidized in air. The coated particulate superabsorbent polymer was then heated to 185 ° C for 55 minutes in a convection oven. The particulate superabsorbent polymer was cooled and sieved to remove particles greater than 850 pm and less than 150 pm.
[000158] Table 4 summarizes the results for particulate superabsorbent polymer. As we can see from Table 4, the CRC (ta, 0.5 hour), CRC (ta, 5 hours), CRC (bt, 0.5 hour), and CRC (bt, 5 hours) of the particulate superabsorbent polymer of the Examples 14 to 19 increase with time or at room temperature, or at body temperature. In addition, the CRC increases with increasing test temperature. In addition, CRC increases more quickly at body temperature than at room temperature.
[000159] In comparison, the particulate superabsorbent polymer of Comparative Example 8 which comprises only conventional internal crosslinker shows CRC essentially constant over time, or at different temperatures.
Table 4
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Ex CRC(r.t., 0.5 hour) CRC(r.t., 5 hours) CRC(bt, 0.5 hour) CRC(bt, 5 hours) AUL(0.9 psi) GBP EC 8 35.5 36.9 36.5 35.9 12.9 23 Ex14 29.0 34.3 33.5 41.2 17.3 54 Ex 15 27.9 34.5 33 41.9 15.8 49 Ex 16 26.8 30.5 30.5 d34.9 19.2 90 Ex 17 26.3 30.2 29.9 34.8 18.9 100 Ex 18 25.6 29.7 29.2 34.1 18.4 118 Ex 19 27.1 31.2 31.2 36.5 19.9 69
[000160] Table 5 shows the CRCI, CRCIR, and vortex time values for CE7-8 and examples 1-19 of the particulate superabsorbent polymer.
Table 5
Ex CRCI (t.a)(g / g) CRCI (bt)(g / g) CRCIR (t.a)(g / g / hour) CRCIR (bt)(g / g / hour) Time tovortex (sec) EC 7 0.9 -0.3 0.20 -0.16 87 EC 8 1.4 0.4 0.31 -0.13 85 Ex 1 14.2 51.2 3.15 8.70 105 Ex 2 7.4 17.2 1.65 2.56 115 Ex 3 7.3 17.8 1.62 2.53 at Ex 4 6.6 20.3 1.47 3.27 at Ex 5 8.3 23.0 1.84 3.49 at Ex 6 9.7 11.9 2.16 0.66 97 Ex 7 5.6 9.8 1.25 1.06 85 Ex 8 7.6 18.3 1.68 2.61 120 Ex 9 5.3 12.9 1.17 2.14 85 Ex 10 7.5 15.2 1.66 1.99 112 Ex 11 6.8 14.9 1.51 2.24 84 Ex 12 7.0 17.0 1.56 2.67 91 Ex 13 7.8 17.5 1.73 2.96 113 Ex 14 5.3 12.2 1.18 1.71 96 Ex 15 6.6 14.0 1.47 1.98 107 Ex 16 3.8 8.1 0.84 0.99 95 Ex 17 3.9 8.5 0.87 1.09 103 Ex 18 4.1 8.4 0.90 1.07 87 Ex 19 4.1 9.4 0.92 1.18 85 [000161] As shown in Table 5, CRCIR ( t.a) and CRCIR
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59/61 (bt) of the particulate superabsorbent polymer of Examples 1 to 19 are higher than 0.4 g / g / hour, while the rates of increase of the comparative particulate superabsorbent polymer of Comparative Examples 7 and 8 are lower than than 0.4 g / g / hour. As shown in Table 5, the particulate superabsorbent polymer of the present invention has a Vortex time comparable to the conventional particulate superabsorbent polymer.
Example 20 [000162] To further illustrate that the present increase in capacity of particulate superabsorbent polymer had an improved ability to absorb, retain and distribute liquids in absorbent articles, laboratory diaper cores containing the present increase in capacity of particulate superabsorbent polymer were prepared and compared to laboratory diaper cores containing a conventional SAP. In particular, the following diaper cores have been prepared:
core A — 60% conventional comparative particulate superabsorbent polymer (as in EC 8), and 40% fluff pulp, by weight;
core B — 60% particulate superabsorbent polymer with increased capacity of the present invention (as in Ex 14), and 40% fluff pulp, by weight.
[000163] Hand sheets (laboratory diaper cores) were prepared using standard air hand-held sheet equipment. The resulting hand sheet compounds were 25.4 cm wide by 43.2 cm long.
[000164] Manual sheets were produced using the following procedure. A sheet of the forming tissue was placed at the bottom of the first. Then, the particulate superabsorbent polymer and the fluff were each divided into equal portions (that is, 6 portions of fluff and
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60/61 portions of particulate materials). Each portion of fluff and portion of particulate superabsorbent polymer were alternately introduced at the top of the first, allowing compressed air to mix fluff and particulate materials, while the vacuum removes the material through the forming chamber and into the forming fabric. This process was continued until the last portion of fluff was consumed, forming a substantially uniform distribution of fluff and particulate materials. These absorbent compounds produced had a base weight of 500 gsm. Following the formation of the web, another layer of the above forming fabric was placed on top of the formed compound. The resulting hand sheet compound was compressed to reach the desired density of approximately 0.26 g / cc prior to testing, using, for example, a CARVER PRESS model # 4531 (available from Carver, Inc., having a business location in Wabash, Indiana USA). Following the preparation and densification of the manual sheet, the samples were cut in circles of 7.6 cm x 7.6 cm for core testing.
[000165] Fluid Inlet, as used in Table 6, was tested according to the Fluid Intake Assessment Test described in United States Patent No. 7,073,373 and Core Retention Capacity, as used in Table 6 , was tested according to the Liquid Saturation Retention Capacity Test described in United States Patent No. 7,073,373, except that the diaper cores were immersed in the test liquid at 37 ° C for 5 hours. Table 6 contains the test results. The Fluid Intake Assessment Test including figures. 4 and 5, and the Liquid Saturation Retention Capacity Test including figure 3, as set forth in United States Patent No. 7,073,373, are incorporated by reference in the present application.
Table 6
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61/61
Code SAP Insult Quantity (g) 1 and ^the fluid inlet Time (sec) 2nd Fluid Entry and Time (sec) Code A EC 8 16.0 20.8 12.3 Code B Ex 14 16.0 19.3 9.8
Table 6 -continuation-
Code 3rd Fluid and Time Entry (sec) 4th Fluid and Time Entry (sec) Core Retention Capacity (g / g) Code A 24.2 44.1 23.8 Code B 17.2 32.4 25.6
[000166] The data presented in Table 6 demonstrate that a diaper core of the present invention shows an improved fluid entry time and an increased core holding capacity. The practical result of these improved properties is a core having an improved ability to prevent jet leakage, and to maintain dryness.
[000167] Notwithstanding that the numerical ranges and parameters that place the broad scope of the invention are approximations, the numerical values placed in the specific examples are reported as precisely as possible. Other than in the operating examples, or where otherwise indicated, all numbers that express quantities of ingredients, reaction conditions, and so placed, used in the specification and claims, are to be understood as being modified in all the examples by the term
Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements.

权利要求:
Claims (9)
[1]
1. Particulate superabsorbent polymer, characterized by the fact that it comprises a polymerized monomer selected from an ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, salts or derivatives thereof, and an internal crosslinking agent comprising an internal crosslinking agent, in which the particulate superabsorbent polymer has an Increase in Centrifugal Retention Capacity of 2g / g or more, as placed here in the Centrifugal Retention Capacity Increase Test;
the internal cross-linking agent comprising a silane compound comprising at least one carbon-carbon double bond and at least one Si-O bond;
said silane compound being selected from vinyltriisopropenoxy silane, vinyltriacethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dietoxymethylvinyl silane, and polysiloxane comprising at least two vinyl groups;
the internal cross-linking composition being from 0.001% to 5% by weight, based on the monomer; and at least 60% by weight of the particles having a particle size of 300 pm to 600 pm, as measured by classification through a United States standard 30 mesh sieve, and retained in a United States standard 50 mesh sieve. .
[2]
2. Particulate superabsorbent polymer, according to claim 1, characterized by the fact that it also comprises a second internal crosslinker.
[3]
3. Particulate superabsorbent polymer, according to claim 1 or 2, characterized by the fact that it has an Increase in Centrifugal Retention Capacity from 2g / g to 50g / g.
Petition 870190130737, of 12/09/2019, p. 66/74
2/4
[4]
4. Particulate superabsorbent polymer according to any one of claims 1 to 3, characterized in that the polymerized monomer has a neutralization of at least 50 mol%.
[5]
5. Particulate superabsorbent polymer according to any one of claims 1 to 4, characterized by the fact that it has a Centrifugal Retention Capacity Increase Rate of 0.4g / g / hour to 10g / g / hour, as stated here , in the Centrifugal Retention Capacity Increase Rate Test.
[6]
6. Particulate superabsorbent polymer according to any one of claims 1 to 5, characterized by the fact that it has a Centrifugal Holding Capacity measured at the body temperature (CRC (bt)), and a Centrifugal Holding Capacity measured at room temperature (CRC (ta)) comprising CRC (bt), and CRC (ta) has the same test time and CRC (bt) is 2g / g and 20g / g higher than CRC (ta).
[7]
7. Method for the production of a particulate superabsorbent polymer, characterized by the fact that it comprises the steps of:
(a) preparing a superabsorbent polymer by the polymerization process of at least one monomer selected from an ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, salts or derivatives thereof, based on the superabsorbent polymer, and 0.001% by weight at 5 % by weight of an internal crosslinking agent comprising a silane compound comprising at least one vinyl group, or allyl group directly attached to a silicon atom and at least one Si-O bond, said silane compound being selected from vinilltriisopropenoxy silane, vinilltriacetoxysilane, vinilltrimethoxysilane, vinilltriethoxysilane, dietoxymethylvinyl silane and polysiloxane with at least two groups of vinyl;
Petition 870190130737, of 12/09/2019, p. 67/74
3/4 (b) polymerization of the components of (a) in a hydrogel;
(c) preparing the particulate superabsorbent polymer from the superabsorbent polymer;
(d) treatment of the superabsorbent polymer particles with surface additives including a surface crosslinking agent based on the particulate superabsorbent polymer, in which said superabsorbent polymer has an Increase in Centrifugal Retention Capacity of 2g / ga 50g / g as placed here in Centrifugal Retention Capacity Increase Test; and at least 60% by weight of the particles having a particle size of 300 pm to 600 pm, as measured by classification through a United States standard 30 mesh sieve, and retained in a United States standard 50 mesh sieve. .
[8]
8. Absorbent article, characterized by the fact that it comprises:
(a) a liquid-permeable topsheet;
(b) a liquid-permeable backsheet;
(c) a core positioned between (a) and (b);
said core comprising 10% to 100% by weight of the particulate superabsorbent polymer according to any one of the preceding claims, and 0% to 90% by weight of hydrophilic fiber material;
(d) optionally, a layer of tissue directly positioned above and below said core (c); and (e) optionally, an acquisition layer positioned between (a) and (c), the particulate superabsorbent polymer comprising a monomer selected from an ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride.
Petition 870190130737, of 12/09/2019, p. 68/74
4/4 rado, salts or derivatives thereof, and an internal crosslinking agent in which the superabsorbent polymer has an Increase in Centrifugal Retention Capacity of 2g / g or more, as stated here, in the Centrifugal Retention Capacity Increase Test; and at least 60% by weight of the particles having a particle size of 300 pm to 600 pm, as measured by classification through a United States standard 30 mesh sieve, and retained in a United States standard 50 mesh sieve. .
[9]
9. Absorbent article, according to claim 8, characterized by the fact that the particulate superabsorbent polymer has an Increase in Centrifugal Retention Capacity of 2g / g and 50g / g, as stated here, in the Centrifugal Retention Capacity Increase Test .

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-04-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-08-04| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA CORPORATION (US) |

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2020-08-25| B25D| Requested change of name of applicant approved|Owner name: EVONIK CORPORATION (US) |

优先权:

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申请号 | 申请日 | 专利标题

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US12/775,984|US8304369B2|2010-05-07|2010-05-07|Superabsorbent polymer having a capacity increase|

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PCT/US2011/034504|WO2011139883A1|2010-05-07|2011-04-29|Particulate superabsorbent polymer having a capacity increase|

---