JP2019116636A - Superabsorbent polymer comprising crosslinking agent - Google Patents

Abstract

To provide a particulate superabsorbent polymer composition.SOLUTION: There are provided: a crosslinking agent which is a reaction product selected from (i) a saturated amine and/or a saturated polyamine and an ethylenically unsaturated glycidyl compound and/or an ethylenically unsaturated polyglycidyl compound, (ii) an ethylenically unsaturated amine and/or an ethylenically unsaturated polyamine and a saturated glycidyl compound and/or a saturated polyglycidyl compound or (iii) an ethylenically unsaturated amine and/or an ethylenically unsaturated polyamine and an ethylenically unsaturated glycidyl compound and/or an ethylenically unsaturated polyglycidyl compound; and a particulate superabsorbent polymer composition comprising a surface crosslinking agent applied to a particle surface. There is further provided an absorbent article containing such a particulate superabsorbent polymer composition.SELECTED DRAWING: Figure 1

Description

  The present invention is directed to superabsorbent polymers, particulate superabsorbent polymer compositions, and methods of making such products, as well as absorbent articles comprising such products. Examples of superabsorbent polymers, according to the general definition of superabsorbent polymers, can absorb large amounts of aqueous liquids and fluids, such as urine or blood, and can swell to form a hydrogel, and Included are crosslinked partially neutralized polymers, including crosslinked polyacrylic acid or crosslinked starch-acrylic acid graft polymers, capable of holding an aqueous liquid under pressure. The superabsorbent polymer may be shaped into particles generally referred to as particulate superabsorbent polymers, which are post-treated with surface cross-linking, surface treatment, and other treatments to produce particulate superabsorbents. It may form a polymer composition. Instead of superabsorbent polymers, superabsorbent polymer compositions, and particles thereof, the acronym SAP may be used. The primary use of superabsorbent polymers and superabsorbent polymer compositions is hygiene articles, such as baby diapers, incontinence products, or sanitary napkins. An extensive survey of superabsorbent polymers, and their use and manufacture, is described in F.S. L. Buchholz and A. T. Graham (Editor) "Modern Superabsorbent Polymer Technology", Wiley-VCR, New York, 1998.

  The superabsorbent polymer is first treated with a caustic such as hydroxylation of unsaturated carboxylic acids or their derivatives, such as acrylic acid, alkali metal (eg sodium and / or potassium) salts of acrylic acid, or ammonium salts, alkyl acrylates etc. It may be prepared by neutralization in the presence of sodium and then polymerizing the product with relatively small amounts of internal or monomeric crosslinking agents, such as difunctional or polyfunctional monomers. The bifunctional or multifunctional monomeric material serves as a covalent internal crosslinker, and lightly crosslinks the polymer chains, thereby making it water insoluble but water swellable. These lightly crosslinked superabsorbent polymers contain multiple carboxyl groups attached to the polymer backbone. These carboxyl groups, by virtue of the cross-linked polymer network, provide the osmotic driving force to absorb body fluids.

In addition to covalent internal crosslinking agents, ionic internal crosslinking agents have been utilized to prepare superabsorbent polymers. The ion binding internal crosslinking agent is generally a polyvalent metal cation such as Al ³⁺ as disclosed in US Pat. No. 6,716,929 and US Pat. No. 7,285,614. , And a coordination compound containing Ca ²⁺ . The superabsorbent polymers disclosed in these patents have slow absorption rates due to the presence of ionic crosslinks. In this context, the rate of absorption may be measured by the Vortex test.

  Superabsorbent polymers useful as absorbents in absorbent articles, such as disposable diapers, need to have sufficiently high absorption capacity and sufficiently high gel strength. The absorbent capacity needs to be high enough so that the absorbent polymer can absorb the significant amount of aqueous body fluid generated during use of the absorbent article. Gel strength refers to the tendency of expanded polymer particles to deform under applied stress, causing the particles to deform under pressure, filling the capillary void space of the absorbent member or article, to an unacceptable degree. It is necessary to cause so-called gel blocking and thereby not to impede the rate of fluid absorption or fluid distribution by the component or article. Once gel-blocking has occurred, the distribution of the fluid to the relatively dry area or areas in the absorbent article may be substantially impeded and sufficiently before the absorbent polymer particles in the absorbent article are completely saturated. Leakage from the absorbent article can occur before the fluid can diffuse or wick into the remaining absorbent article through the "blocked" particles or into the rest of the absorbent article.

  U.S. Pat. No. 6,087,450 is directed to providing internal crosslinkers, superabsorbent polymers crosslinked by them, and methods of making them. These superabsorbent polymers are characterized by an internal crosslinking characterized by opening the epoxide ring by reacting a glycidyl compound with an unsaturated amine such as allylamine to form a hydroxyl group that is optionally available for subsequent ethoxylation. By using the agent it is suitable for superabsorbents or other technical applications of the construction of the diaper. According to the invention, other reaction pathways for producing crosslinkers; for example, amines may also be reacted with unsaturated glycidyl compounds such as (meth) allyl glycidyl ether or glycidyl (meth) acrylates.

  The properties of superabsorbents, in particular the absorption of their liquids under pressure, can be improved by surface crosslinking. During surface crosslinking, the carboxyl groups of the polymer molecules crosslink with the crosslinker at the surface of the superabsorbent particles at elevated temperatures. Among them, polyvalent metal salts, glycidyl compounds, polyols, polyepoxides, polyamines, alkylene carbonates and polyethylene glycols are used as crosslinking agents.

  It is an object of the present invention to provide superabsorbent polymers with improved permeability, as determined by the Gel Bed Permeability Test described herein, and methods of making the same. .

The present invention includes a number of embodiments, some of which are included herein. One embodiment of the present invention is a particulate superabsorbent polymer composition:
a) a polymerizable monomer, wherein the monomer is selected from unsaturated acid group-containing monomers, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof;
b) an internal crosslinking agent composition,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound, or (ii) ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and saturated glycidyl Compound and / or saturated polyglycidyl compound, or (iii) reaction of one selected from ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound An internal crosslinker composition which is a product;
Here, components a) and b) are polymerized and granulated to form a particulate superabsorbent polymer having particle surfaces, wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm. And c) 0.01 to 5% by weight of the surface crosslinker applied to the particle surface, based on the weight of the dried superabsorbent polymer composition;
Contains and
The particulate superabsorbent polymer composition comprises a centrifugal retention capacity of 20 g / g to 40 g / g as determined by the Centrifuge Retention Capacity Test as described herein, and a gel bed as described herein. Have a gel bed permeability of at least 5 Darcy or more as determined by the Gel Bed Permeability Test
It is a particulate superabsorbent polymer composition.

Another embodiment of the present invention is a method of making a particulate superabsorbent polymer composition:
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Superabsorbent polymer by polymerizing from 0.001% by weight to 1% by weight of an internal crosslinker composition which is the reaction product of an unsaturated glycidyl compound and / or a product selected from ethylenically unsaturated polyglycidyl compounds To prepare;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm;
d) surface crosslinking the particulate superabsorbent polymer with 0.001 to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface crosslinker applied to the particle surface; and e) heat treating the surface crosslinked particulate superabsorbent polymer of step e) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form a surface crosslinked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
It is a method of making a particulate superabsorbent polymer composition.

Another embodiment of the present invention is a method of making a particulate superabsorbent polymer composition:
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Superabsorbent polymer by polymerizing from 0.001% by weight to 1% by weight of an internal crosslinker composition which is the reaction product of an unsaturated glycidyl compound and / or a product selected from ethylenically unsaturated polyglycidyl compounds To prepare;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer, wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 850 μm;
d) 0.01 to 5% by weight of the insoluble inorganic powder of the surface-crosslinked particulate superabsorbent polymer of step c), based on the weight of the dried superabsorbent polymer composition powder, and / or the dried superabsorbent Surface treating with 0.01 to 5% by weight of polyvalent metal salt based on the weight of the polymer composition powder;
e) Surface cross-linking the particulate superabsorbent polymer with 0.001% to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition, of a surface crosslinker applied to the particle surface; And f) heat treating the surface-crosslinked particulate superabsorbent polymer of step d) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form a surface cross-linked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Process for the production of particulate superabsorbent polymer compositions.

Another embodiment of the present invention is an absorbent article:
(A) liquid-permeable top sheet;
(B) liquid impermeable back sheet;
(C) a core disposed between (a) and (b), wherein the core is 10% to 100% by weight particulate superabsorbent polymer composition, and 0% to 90% by weight hydrophilic Core materials, including cores;
(D) an optional tissue layer disposed directly above and below the core (c);
(E) including an optional capture layer disposed between (a) and (c),
The particulate superabsorbent polymer composition is
i) a monomer selected from an ethylenically unsaturated carboxylic acid, an anhydride of an ethylenically unsaturated carboxylic acid, a salt, or a derivative thereof;
ii) an internal crosslinking agent composition,
(Α) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Β) Ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and saturated glycidyl compounds and / or saturated polyglycidyl compounds, or (γ) ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and ethylenicity An internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
iii) 0.001 to 5% by weight, based on the weight of the dried superabsorbent polymer composition, of a surface crosslinker applied to the particle surface;
Contains and
The particulate superabsorbent polymer composition comprises a centrifugal retention capacity of 20 g / g to 40 g / g as determined by the Centrifuge Retention Capacity Test as described herein, and a gel bed as described herein. Have a gel bed permeability of at least 5 Darcy or more as determined by the Gel Bed Permeability Test
Absorbent article.

  Many aspects of other embodiments, features, and advantages of the present invention are set forth in the following detailed description, the accompanying drawings, and the claims. For the sake of brevity and simplicity, the range of values provided herein takes into account all values within that range, and describes every subrange having endpoints that are real values within that particular range. It is to be understood as supporting a claim of 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 appended claims.

The foregoing and other features, aspects, and advantages of the present invention will be better understood with regard to the following description, appended claims, and accompanying drawings.
FIG. 1 is a side view of a test apparatus used for free expansion gel bed permeability testing. FIG. 2 is a cross-sectional side view of a cylinder / cup assembly used in the free-standing gel bed permeability testing device shown in FIG. FIG. 2 is a top view of a plunger used in the free-standing gel bed permeability testing device shown in FIG. 1; It is a side view of the test apparatus used for the load absorption test (Absorbency Under Load Test).

<< definition >>
As used in this disclosure, the terms "comprises", "comprising", and other derivatives of the word "comprise" refer to any of the described features, elements, integers, steps, and Or intended to be an open-ended term identifying the presence of a component, and intended to exclude the presence or addition of one or more other features, elements, integers, steps, components, or combinations thereof It should be noted that it is not

  As used herein, the term "about" which modifies the amount of components used in the composition of the invention or in the method of the invention is a typical measurement, for example, as used in the preparation of concentrates or use solutions. And through liquid processing procedures; through inadvertent errors in these procedures; through differences in the preparation, source, or purity of the raw materials used in the manufacture of the composition or practice of the process; It means a change of a certain quantity. The term also includes different amounts due to different equilibrium conditions of the composition resulting from the particular initial mixture. Whether modified by the term "about" or not, the claims include equivalent amounts.

  As used herein, the term "absorbent article" refers to a device that absorbs and contains body fluids or body exudates, and more specifically, placed on or in close proximity to the body of the wearer, from the body By means is a device that absorbs and contains the various fluids or exudates that are released. Absorbent articles include diapers, training pants, adult incontinence underwear, feminine hygiene products, chest pads, care mats, chest pads, traumatic bandage products and the like. The absorbent articles further include floor cleaning articles, food industry articles and the like.

  As used herein, the term "centrifuge retention volume (CRC)" refers to the ability of particulate superabsorbent polymer to retain liquid therein after saturation and centrifugation under controlled conditions. Stated as grams of liquid held per gram mass of sample (g / g), as measured in the Centrifuge Retention Volume Test described in the document.

  As used herein, the terms "crosslinked", "crosslink", "crosslinker", or "crosslinking" refer to materials that are normally water soluble, effectively Mean any means that makes it substantially water insoluble but expandable. Such cross-linking means include, for example, physical entanglement, crystalline domains, covalent bonds, ionic complexes and ionic associations, hydrophilic associations such as hydrogen bonds, hydrophobic associations, or van der Waals forces.

  As used herein, the terms "internal crosslinker" or "monomeric crosslinker" refer to the use of the crosslinker in a solution of monomers that form a polymer.

The term "Darcy" is a unit of permeability of the Gaussian unit system (CGS). A Darcy means that a fluid with a viscosity of 1 centipoise at 1 cubic centimeter passes through a portion with a thickness of 1 centimeter and a cross section of 1 cm ² centimeters when the pressure difference between two sides of a solid is 1 atm. Flowing, solid permeability. Since there is no SI unit of permeability and square meters are used, it can be seen that permeability has the same units as the area. One Darcy is equal to 0.98692 × 10 ⁻¹² m ² or 0.98692 × 10 ⁻⁸ cm ² .

  As used herein, the term "diaper" is generally worn by infants and incontinent persons on the lower torso so as to surround the waist and legs of the wearer, and in particular receives and contains urine and feces. Means an absorbent article suitable for

  The term "disposable" as used herein means an absorbent article that is not intended to be cleaned or otherwise reused as a recovery or absorbent article after a single use. Examples of such disposable absorbent articles include, but are not limited to, personal care absorbent articles, health / medical absorbent articles, and household / industrial absorbent articles.

  As used herein, the term "dried superabsorbent polymer composition" generally refers to a superabsorbent polymer composition that contains less than 10% moisture.

  The term "gel permeable" is a property of the material of the particle as a whole, and relates to particle size distribution, particle shape, and connectivity of the pores between particles, shear modulus, and surface deformation of the expanded gel. In practical terms, the gel permeability of the superabsorbent polymer composition measures how fast the liquid flows through the material of the expanded particles. Low gel permeability does not allow the fluid to easily flow through the superabsorbent polymer composition, commonly referred to as gel blocking, and any forced fluid flow (eg, during the use of a diaper, a second Application of urine indicates that an alternative route (e.g. diaper leak) must be taken.

  The term "mass median particle size" of a given sample of particles of superabsorbent polymer composition means that the sample is divided in half on the basis of mass, ie half the mass sample is greater than the mass median particle size Defined as a particle size with a large particle size, with half the mass sample having a particle size smaller than the mass median particle size. Thus, for example, if the 1⁄2 sample by mass is measured as 2 micrometers or more, then the mass median particle size of the sample of superabsorbent polymer composition particles is 2 micrometers.

  The terms "particles", "particulates" and the like mean the form of discrete units when used with the term "superabsorbent polymer". Units include flakes, fibers, agglomerates, granules, powders, spheres, particulate materials, etc., and combinations thereof. The particles can have any desired shape, such as, for example, cubes, rod-shaped polyhedrons, spheres or hemispheres, curved or semi-curved, angular or random.

  The term "permeability" as used herein means the measurement of the effective connectivity of the porous structure, here a crosslinked polymer, and the porosity and connectivity of the particulate superabsorbent polymer composition It can be specified by the degree of

  The term "polymer" includes, but is not limited to, homopolymers, copolymers such as blocks, grafts, random and alternating copolymers, terpolymers, etc., as well as blends and variations thereof. Furthermore, unless specifically limited, the term "polymer" encompasses all possible configuration isomers of the material. These configurations include, but are not limited to isotactic, zinciotactic, and atactic symmetry.

  As used herein, the term "polyolefin" is generally, but not limited to, materials such as polyethylene, polypropylene, polyisobutylene, polystyrene, materials such as ethylene vinyl acetate copolymer, homopolymers, copolymers, terpolymers etc. of these, as well as Blends and variations are included. The term "polyolefin" is intended to encompass all its possible structures and includes but is not limited to isotactic, zinciotactic and random symmetries. Copolymers include atactic copolymers and block copolymers.

  As used herein, the term "superabsorbent polymer" refers to at least 10 times its weight, or at least 15 times its weight, in an aqueous solution comprising 0.9 weight percent sodium chloride under most preferred conditions. Or a water-swellable, water-insoluble organic or inorganic material comprising a superabsorbent polymer and a superabsorbent polymer composition capable of absorbing at least 25 times its mass.

  The term "superabsorbent polymer composition" as used herein means a superabsorbent polymer comprising a surface additive according to the present invention.

  As used herein, the term "surface cross-linking" means a degree of functional crosslinking that is generally higher than the degree of functional crosslinking inside the superabsorbent polymer particles near the surface of the superabsorbent polymer particles. As used herein, the term "surface" refers to the boundary of the outer surface of the particle.

  As used herein, the term "thermoplastic resin" refers to a material that softens when exposed to heat and substantially returns to the unsoftened state when cooled to room temperature.

  The terms "% by weight" or "% wt" as used herein refer to a component of the superabsorbent polymer composition and, unless otherwise specified herein, the weight of the dried superabsorbent polymer composition It is interpreted as being based on

  These terms may be defined by the further description of the following part of the specification.

  While typical aspects of the embodiments and / or embodiments have been set forth for the purpose of explanation, the detailed description and the accompanying drawings are not to be considered as limiting the scope of the present invention. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present invention. As a hypothetical example, the disclosure of ranges 1 to 5 herein refers to the following range of claims: 1 to 5; 1 to 4; 1 to 3; 1 to 2; 2 to 5; 4; 2-3; 3-5; 3-4; and 4-5 are all considered to be supported.

  The object of the present invention is to provide a superabsorbent polymer or particulate superabsorbent polymer composition crosslinked by at least one internal crosslinker composition, as well as a method for producing a particulate superabsorbent polymer composition, which particulates Superabsorbent polymer compositions are suitable for use in absorbent articles, such as diaper constructions, or other technical applications.

The particulate superabsorbent polymer composition of the present invention is
a) A polymerizable unsaturated acidic group-containing monomer, wherein the monomer is selected from unsaturated acid group-containing monomers, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof Group-containing monomers;
b) an internal crosslinking agent composition,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl Compound and / or saturated polyglycidyl compound, or (iii) reaction of one selected from ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound An internal crosslinker composition which is a product;
Here, components a) and b) are polymerized and granulated to form a particulate superabsorbent polymer having a particle surface, wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm. And
c) 0.01 to 5% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface crosslinker applied to the particle surface;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
It is a particulate superabsorbent polymer composition.

Another embodiment of the present invention is a method of making a particulate superabsorbent polymer composition, comprising:
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
An internal crosslinking agent composition of 0.001% by mass to 1% by mass based on the monomers,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Preparing a superabsorbent polymer by polymerizing with an internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
c) polymerizing the superabsorbent polymer;
d) granulating the superabsorbent polymer to form a particulate superabsorbent polymer wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm;
e) Surface crosslinking the particulate superabsorbent polymer with a surface crosslinker applied to the surface of the particles of 0.001 to 5.0% by weight based on the weight of the dried superabsorbent polymer composition powder; and f C.) Heat treating the surface-crosslinked particulate superabsorbent polymer of step e) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form a surface cross-linked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
It is a method of making a particulate superabsorbent polymer composition.

Another embodiment of the present invention is a method of making a particulate superabsorbent polymer composition, comprising:
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
An internal crosslinking agent composition of 0.001% by mass to 1% by mass based on the monomers,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Preparing a superabsorbent polymer by polymerizing with an internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm;
d) 0.01-5% by weight of the surface-crosslinked particulate superabsorbent polymer of step c), based on the weight of the dried superabsorbent polymer composition, insoluble inorganic powder, and / or dried superabsorbent polymer Surface treating with 0.01 to 5% by weight of polyvalent metal salt based on the weight of the composition powder;
e) surface crosslinking the particulate superabsorbent polymer with a surface crosslinking agent applied to the surface of the particles of 0.001 to 5.0% by weight based on the weight of the dried superabsorbent polymer composition; and f) Heat treating the surface-crosslinked particulate superabsorbent polymer of step e) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form a surface cross-linked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
It is a method of making a particulate superabsorbent polymer composition.

Another embodiment of the present invention is an absorbent article comprising: (a) a liquid-permeable top sheet; (b) a liquid-impermeable back sheet; and (c) between (a) and (b) A core disposed in the core, the core comprising 10% to 100% by weight of the particulate superabsorbent polymer composition, and 0% to 90% by weight of the hydrophilic fiber material; (d) above Including any tissue layer disposed directly above and below the core (c); and an optional acquisition layer disposed between (e) (a) and (c),
The particulate superabsorbent polymer composition is
i) a monomer selected from an ethylenically unsaturated carboxylic acid, an anhydride of an ethylenically unsaturated carboxylic acid, a salt, or a derivative thereof;
ii) an internal crosslinking agent composition,
(Α) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Β) Ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and saturated glycidyl compounds and / or saturated polyglycidyl compounds, or (γ) ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and ethylenicity An internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
iii) 0.001 to 5% by weight, based on the weight of the dried superabsorbent polymer composition, of a surface crosslinker applied to the particle surface;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
It is an absorbent article.

  The particulate superabsorbent polymer composition according to embodiments of the present invention is obtained by prepolymerization of 55% to 99.9% by weight of the polymerizable unsaturated acidic group-containing monomer based on the superabsorbent polymer. Suitable polymerizable monomers include any containing a carboxyl group, such as acrylic acid, methacrylic acid, or 2-acrylamido-2-methylpropane sulfonic acid, or mixtures thereof. Desirably, at least 50 wt%, more desirably at least 75 wt% of the acidic groups are carboxyl groups.

  For acrylic acid, use is made of acrylic acid whose content is pure, ie known as acrylic acid having a concentration of at least 99.5% by weight, or at least 99.7% by weight, or at least 99.8%. is important. The main components of this monomer may be acrylic acid or acrylic acid and acrylic acid salt. Impurities of acrylic acid include water, propionic acid, acetic acid, and diacrylic acid, commonly referred to as acrylic acid dimer. When acrylic acid is used in the method, the content of diacrylic acid should be 1000 ppm or less, or 500 ppm or less, or 300 ppm or less. Furthermore, it is important to minimize the formation of β-hydroxypropionic acid to less than 1000 ppm, or less than 500 ppm, of β-hydroxypropionic acid during the neutralization process.

  Furthermore, in the case of acrylic acid, the content of protoanemonin and / or furfural is 0 to 20 ppm by weight according to the conversion value based on acrylic acid. In view of the improvement of the physical properties and characteristics of the water-absorbing resin, the content of protoanemonin and / or furfural in the monomer is less than 10 ppm by weight by conversion value based on acrylic acid, or 0. 01-5 ppm, or 0.05-2 ppm by mass, or 0.1-1 ppm by mass.

  Furthermore, for the same reason, the amount of aldehyde component other than furfural and / or maleic acid in the monomer is preferably as low as possible. Specifically, the content of the aldehyde component other than furfural and / or maleic acid is 0-5 ppm by mass at conversion value based on acrylic acid, or 0-3 ppm by mass, or 0-1 ppm by mass, or mass May be 0 ppm (below detection limit). Examples of aldehyde components other than furfural include benzaldehyde, acrolein, acetaldehyde and the like.

  Furthermore, the content of saturated carboxylic acid composed of acetic acid and / or propionic acid in the monomer or particulate water-absorbing agent of the present invention is less than 1000 ppm by mass at conversion value based on acrylic acid, or 10-800 ppm by mass Or 100 to 500 ppm by mass is preferable.

  In some aspects, suitable monomers that can be copolymerized with ethylenically unsaturated monomers include, but are not limited to, acrylamide, methacrylamide, hydroxyethyl acrylate, dimethylaminoalkyl (meth) -acrylate, ethoxyl (meth) -Acrylate, dimethylaminopropyl acrylamide, or acrylamidopropyl trimethyl ammonium chloride. Such monomers may be present in the range of 0% to 40% by weight of the copolymerized monomers.

  The acidic group may be neutralized to an extent of at least 25 mol%, ie, desirably, the acidic group may be present as a sodium salt, potassium salt, or ammonium salt. Neutralization may be achieved either by adding the caustic solution to the monomer solution or by adding the monomer solution to the caustic solution. In some aspects, the degree of neutralization may be at least 50 mol%, or 50 mol% to 80 mol%. It is desirable to use a polymer obtained by polymerizing acrylic acid or methacrylic acid in which carboxyl groups are neutralized to about 50 mol% to 80 mol% in the presence of an internal crosslinking agent.

  When partially neutralized or completely neutralized acrylate salt is used as a polymer, partially neutralized or completely neutralized polyacrylate salt is completely equimolar unneutralized polyacrylic acid The conversion value based on acrylic acid may be determined by converting it as being

The superabsorbent polymer comprises crosslinking points at which the superabsorbent polymer can crosslink with the internal crosslinker composition. In this embodiment, suitable internal crosslinking agent compositions include, but are not limited to:
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Mention may be made of internal crosslinker compositions which are reaction products of those selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds.

  Saturated amines, ethylenically unsaturated amines, saturated polyamines and / or ethylenically unsaturated polyamines include aliphatic and aromatic, heterocyclic and cyclic compounds as amine components suitable for reaction with glycidyl compounds For example, (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine and ethyl Allylamine; methyl-, ethyl-, propyl- and butylamine, diallylamine (DAA), dimethallylamine, aniline, ethylenediamine (EDA), diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1, -Propylenediamine, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methylaminopropane, bis (3 -Aminopropyl) methylamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4 ', 4'-diaminodiphenylmethane, There may be mentioned 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof.

The ethylenically unsaturated glycidyl compound, the ethylenically unsaturated polyglycidyl compound, the saturated glycidyl compound, and / or the saturated polyglycidyl compound used in the present invention may be monofunctional, difunctional or multifunctional. Examples of monofunctional compounds used alone or in mixtures are: ethylene glycol monoglycidyl ether, and related C ₁ -C ₆ -alkyl ethers or esters; glycidol, ethylene oxide (EO), propylene oxide (PO), (meth) Allyl glycidyl ether (AGE), (meth) allyl glycidyl ether, polyethylene glycol monoglycidyl ether, and related C ₁ -C ₆ -alkyl ethers or esters; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether Or 1-halogen-2,3-epoxypropane. Ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylolpropane or pentaerythritol triglycidyl ether; polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or mixtures thereof are used as polyfunctional glycidyl ethers. The polyethylene glycol chains of the glycidyl compounds described above may comprise up to 45, or up to 20, or up to 12 ethylene glycol units.

 The structures shown in Table 1 below are examples of suitable glycidyl compounds.

  In another embodiment of the present invention, the internal crosslinking agent may be alkoxylated at the free hydroxyl group or part of the NH group. For this purpose, according to the invention, the alcohol is reacted, for example, with ethylene or propylene oxide or mixtures thereof. Reaction with ethylene oxide (EO) can also improve the water solubility of the crosslinker. Up to 45 moles of EO, or up to 20 moles of EO, or up to 12 moles of EO may be added per hydroxyl group. Propylene oxide may be used instead of EO.

  Some examples of internal crosslinking agents according to the present invention include, but are not limited to, diallylaminoethanol, diallylamino polyglycol ether, 1,3-bis (diallylamino) -2-propanol, N, N-diallylamino-1 -Amino-3-allyloxy-2-propanol, polyethylene glycol di (N, N-diallyl-3-amino-2-hydroxy-prop-1-yl) ether, ethylene glycol di (N, N-diallyl-3-amino) -2-Hydroxy-prop-1-yl) ether, alkoxylated 1,3-bis (diallylamino) -2-propanol, alkoxylated 1-allyloxy-3- (diallylamino) -2-propanol, alkoxylated polyethylene glycol Di (N-diallyl-3-amino-2-hydroxy-p P-1-yl) ether, alkoxylated ethylene glycol di (N, N-diallyl-3-amino-2-hydroxy-prop-1-yl) ether, N, N-di (allyloxy-2-hydroxy-prop-) 3-yl) aniline, alkoxylated N, N-di (allyloxy-2-hydroxy-prop-3-yl) aniline, 1,2-bis [N, N-di (allyloxy-2-hydroxy-prop-3-) )] Ethane, and bis [N, N-di (allyloxy-2-hydroxy-prop-3-yl) aminoethyl- (allyloxy-2-hydroxy-prop-3-yl) amine, and alkoxylation thereof The product is mentioned. The polyethylene glycol ether units described above may comprise up to 45 moles of ethylene oxide and / or propylene oxide, or up to 20, or up to 15 moles of ethylene oxide and / or propylene oxide. According to another embodiment of the invention, the N-atoms of the crosslinker are partially or completely quaternized.

  The internal crosslinking agent or the mixture thereof used in the present invention is 0.01% by mass to 3.0% by mass, or 0.02% by mass to 1.5% by mass, or the content of the polymerizable unsaturated acidic group-containing monomer It is used in an amount of 0.03% by mass to 1.0% by mass.

  In another embodiment, the superabsorbent polymer is a composition comprising 0.001 to 0.5% by weight, based on the polymerizable unsaturated acidic group-containing monomer, of at least two ethylenically unsaturated double bonds, for example Methylene bis acrylamide or-methacrylamide, or ethylene bis acrylamide; esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylates or triacrylates, such as butanediol or ethylene glycol diacrylate or methacrylates; tri Methylolpropane triacrylate and alkoxylated derivatives thereof; further allyl compounds such as allyl (meth) acrylate, triallyl cyanurate, diallyl ester of maleic acid, polyallyl ester, tetraallyloxyethane, - and triallylamine, tetraallylethylenediamine, may include a second, different internal cross-linking agent selected from allyl esters of phosphoric acid or phosphorous acid. Furthermore, a compound having at least one functional group reactive to an acidic group may be used. Examples thereof include tetrakis-N, N, N ', N', [3-allyloxy-2-hydroxypropyl] diethylenediamine, N-methylol compounds of amides such as methacrylamide or acrylamide, ethers derived therefrom, And di- and polyglycidyl compounds.

  In some aspects, an initiator can be added to the monomer solution to initiate free radical polymerization. Suitable initiators include, but are not limited to, azo or peroxo compounds, redox systems, or UV initiators, sensitizers, and / or radiation.

  After polymerization, the superabsorbent polymer present in the form of a gel is generally formed or granulated into superabsorbent polymer particles or particulate superabsorbent polymers. The particle size of the particulate superabsorbent polymer of the present invention is generally in the range of 50 to 1000 μm, or 150 to 850 μm. The present invention is measured by screening through a U.S. standard 30 mesh screen, and remains on the U.S. standard 50 mesh screen, particles of at least 40% by weight particles with a particle size of 300 .mu.m to It may comprise at least 50% by weight of particles having a diameter, or at least 60% by weight of particles having a particle diameter of 300 μm to 600 μm. Furthermore, the superabsorbent polymer particle size distribution of the present invention is described, for example, in W. S. Particles less than 30% by weight with a diameter greater than 600 μm and diameters less than 300 μm, as measured using the RO-TAP® Mechanical Sieve Shaker Model B available from Tyler, Mentor, Ohio And may contain less than 30% by weight of particles.

  Particulate superabsorbent polymers may be surface treated with additional compounds and treatments as described herein. Specifically, the surface of the particulate superabsorbent polymer may be crosslinked by the addition of a surface crosslinking agent, generally surface crosslinking, and heat treatment. In general, surface crosslinking is a process that is believed to increase the crosslink density of the polymer matrix near the surface of the particulate superabsorbent polymer relative to the crosslink density inside the particles. It should be noted that the treatment of the particulate superabsorbent polymer with inorganic particles and / or water or an aqueous solution can be carried out either before or after surface crosslinking.

  Desirable surface crosslinkers include compounds having one or more functional groups reactive with the pendent groups of the polymer chain, typically acidic groups. Surface crosslinking agents include compounds containing at least two functional groups that can react with the functional groups of the polymer structure in condensation reactions (condensation crosslinking agents), in addition reactions, or in ring opening reactions. As these compounds, condensation crosslinking agents such as diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyethanolamine, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester Polyoxyethylene sorbitan fatty acid ester, trimethylolpropane, pentaerythritol, polyvinyl alcohol, sorbitol, 1,3-dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolane-2-one (propylene carbonate) ), 4,5-Dimethyl-1,3-dioxolane-2-one, 4,4-Dimethyl-1,3-dioxolane-2-one, 4-Ethy -1,3-dioxolane-2-one, 4-hydroxymethyl-1,3-dioxolane-2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2-one, Examples include 4,6-dimethyl-1,3-dioxan-2-one, and 1,3-dioxolane-2-one. The amount of surface crosslinker is, for example, 0.1% to 3% by weight based on the weight of the dried superabsorbent polymer composition of 0.01% to 5% by weight and the dried particulate superabsorbent polymer, and For example, it may be present in an amount of 0.1% by weight to 1% by weight.

  After contacting the particulate superabsorbent polymer with the surface crosslinker composition or the fluid comprising the surface crosslinker composition, the treated particulate superabsorbent polymer is made more so that the outer region of the polymer structure is compared to the inner region Heat treatment to strongly crosslink (i.e., surface crosslink), e.g., heat the treated particulate superabsorbent polymer to a temperature of 50C to 300C, 75C to 275C, or 150C to 250C. The duration of the heat treatment is limited by the risk that the desired property profile of the polymer structure is destroyed as a result of the influence of heat.

  In other embodiments, the fluid comprising the surface crosslinker, separately or together, may contain other components, such as polyvalent metal cations such as aluminum sulfate or aluminum lactate, and / or insoluble inorganic powders such as silica, such as It may further comprise SIPERNAT® 22S fumed silica available from Evonik Industries, Inc. and the ingredients are described in more detail below.

  In one aspect of surface crosslinking, the particulate superabsorbent polymer can be coated or surface treated with an alkylene carbonate such as ethylene carbonate and heated to improve surface crosslink density and gel strength properties of the superabsorbent polymer particles Allow surface crosslinking. More specifically, the surface crosslinker is coated onto the superabsorbent polymer microparticles by mixing the particulate superabsorbent polymer with an aqueous alcohol solution of an alkylene carbonate surface crosslinker. The amount of alcohol in the aqueous alcohol solution may be determined by the solubility of the alkylene carbonate and is kept as low as possible for various reasons, for example to protect against explosions. Suitable alcohols include methanol, isopropanol, ethanol, butanol or butyl glycol and mixtures of these alcohols.

In some aspects, the solvent is desirably water, typically used in an amount of 0.3% to 5.0% by weight based on the weight of the dried superabsorbent polymer composition. In another embodiment, the alkylene carbonate surface crosslinker is dissolved in water without any alcohol. In yet another aspect, the alkylene carbonate surface crosslinker may be applied, for example, from a powder mixture comprising an inorganic support material, such as silicon dioxide (SiO ₂ ), or in vapor form by sublimation of the alkylene carbonate.

  In order to achieve the desired surface crosslinking properties, the alkylene carbonate should be uniformly distributed in the particulate superabsorbent polymer. For this purpose, the mixing is carried out with suitable mixers known in the art, such as fluidized bed mixers, paddle mixers, rotary drum mixers or twin worm mixers. It is also possible to carry out the coating of the particulate superabsorbent polymer during one of the process steps of producing the particulate superabsorbent polymer.

  Heat treatment following coating of the particulate superabsorbent polymer with a solution of surface crosslinker may be performed as follows. Generally, the heat treatment is performed at a temperature of 100 ° C to 300 ° C. Lower temperatures are possible when using highly reactive epoxide crosslinkers. However, when using an alkylene carbonate, the heat treatment is suitably at a temperature of 150 ° C to 250 ° C. In this particular aspect, the treatment temperature depends on the residence time and the type of alkylene carbonate. For example, the heat treatment is performed at a temperature of 150 ° C. for one hour or more. In contrast, several minutes (e.g., 0.5 minutes to 5 minutes) at a temperature of 250 <0> C are sufficient to achieve the desired surface crosslinking properties. The heat treatment may be carried out in a conventional dryer or oven known in the art.

  In addition to the surface cross-linking including the heat treatment step, the particulate super-absorbent polymer composition of the present invention may be used to improve its properties such as strength, permeability, processability, odor control, color etc. Further surface treatment may be performed using a chemical composition. These additives may be applied to the particulate superabsorbent polymer composition before, during or after surface crosslinking, wherein the additive is prior to the surface crosslinking agent or Or after the surface crosslinker and before or after the heat treatment.

  The particulate superabsorbent polymer composition of the present invention may also comprise from 0 to 5% by weight, based on the weight of the dried superabsorbent polymer composition, of the penetration modifier added immediately before, during or after surface crosslinking. Good. Examples of penetration modifiers include superabsorbent polymer particles, fibers, films of surface modifiers by altering the viscosity, surface tension, ionic or adhesive properties of the above agents, or the medium to which these agents are applied. , Compounds which alter the depth of penetration into the foam or bead. Penetration regulators include polyethylene glycol, tetraethylene glycol dimethyl ether, monovalent metal salts, surfactants, and water soluble polymers.

  The particulate superabsorbent polymer composition according to the present invention may be 0.01 wt% to 5 wt%, or 0.01 wt% to 1 wt%, or 0.01 wt% based on the weight of the dried superabsorbent polymer composition. % To 0.5% by weight of polyvalent metal salt may be included on the surface of the particulate superabsorbent polymer based on the weight of the mixture. The polyvalent metal salt is preferably water soluble. Examples of metal cations include cations of Al, Fe, Zr, Mg, Ce and Zn. Preferably, the polyvalent metal salt has a valence of at least +3, with Al being most preferred. Examples of anions of polyvalent metal salts include halides, sulfates, nitrates, lactates and acetates, preferably chlorides, sulfates and acetates, more preferably sulfates and lactates. Aluminum sulfate and aluminum lactate are examples of polyvalent metal salts and are readily commercially available. The preferred form of aluminum sulfate is hydrated aluminum sulfate, preferably aluminum sulfate having 12 to 14 water of hydration. Mixtures of polyvalent metal salts may be used.

  Suitable superabsorbent polymers and polyvalent metal salts are mixtures by dry blending, or solutions, using means known to the person skilled in the art. For dry blending, a sufficient amount of binder may be used to ensure that a substantially uniform mixture of salt and superabsorbent polymer is maintained. The binder may be water or a low volatility organic compound having a boiling point of at least 150 ° C. Examples of binders include water, polyols such as propylene glycol, glycerin and poly (ethylene glycol).

  The particulate superabsorbent polymer composition of the present invention is 0.01% by mass to 5% by mass, or 0.01% by mass to 1% by mass, or 0.1% by mass, based on the mass of the dried superabsorbent polymer composition powder. The water-insoluble inorganic powder can be contained in an amount of 01% to 0.5% by mass. Examples of insoluble inorganic powders include silicon dioxide, silicic acid, silicate, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, talc, calcium phosphate, clay, diatomite soil, zeolite, bentonite, kaolin, hydrotalcite, activated clay, etc. Can be mentioned. The insoluble inorganic powder additive may be a single compound or a mixture of compounds selected from the above list. Among all these examples is amorphous silicon dioxide or aluminum oxide. An example of silica is SIPERNAT® 22S fumed silica, commercially available from Evonik Industries. Furthermore, the particle diameter of the inorganic powder may be 1000 μm or less, or 100 μm or less.

  In some aspects, the particulate superabsorbent polymer composition of the present invention is 0 wt% to 5 wt%, or 0.001 wt% to 1 wt%, of the weight of the dried superabsorbent polymer composition powder, or It may be surface-treated with 0.01% by mass to 0.5% by mass of a polymer coating, such as a thermoplastic resin coating, or a cationic coating, or a combination of a thermoplastic resin coating and a cationic coating. In some particular aspects, the polymer coating is desirably a polymer in solid, emulsion, suspension, colloid, or solubilized state, or combinations thereof. Polymer coatings suitable for the present invention include, but are not limited to, thermoplastic resin coatings having a melting temperature of the thermoplastic resin, the polymer coating being at the temperature of the thermoplastic resin melting temperature of the superabsorbent polymer particles to be treated Apply to particle surfaces that match or are less than.

  Examples of thermoplastic polymers include polyolefin, polyethylene, polyester, polyamide, polyurethane, styrene polybutadiene, linear low density polyethylene (LLDPE), ethylene acrylic acid copolymer (EAA), ethylene alkyl methacrylate copolymer (EMA), polypropylene (PP) Maleated polypropylene, ethylene vinyl acetate copolymer (EVA), polyesters, polyamides and blends of all polyolefin families, such as PP, EVA, EMA, EEA, EBA, HDPE, MDPE, LDPE, LLDPE, and / or Alternatively, blends of VLDPE may be used advantageously. The term polyolefin as used herein is as defined above. In a particular aspect, maleated polypropylene is a preferred thermoplastic polymer for use in the present invention. The thermoplastic polymer may be functionalized to have further advantages, such as water solubility or dispersibility.

  As used herein, cationic polymer means a polymer or mixture of polymers containing functional groups or groups that have the potential to ionize in aqueous solution to positively charged ions. Suitable functional groups of the cationic polymer include, but are not limited to, primary, secondary or tertiary amino groups, imino groups, imide groups, amido groups, and quaternary ammonium groups. Examples of synthetic cationic polymers include poly (vinylamine), poly (allylamine), poly (ethyleneimine), poly (aminopropanol vinyl ether), poly (acrylamidopropyltrimethylammonium chloride), and poly (diallyldimethylammonium chloride) Salt or partial salt is mentioned. Examples of naturally occurring cationic polymers include partially deacetylated chitin, chitosan and chitosan salts. Synthetic polypeptides such as polyasparagine, polylysine, polyglutamine and polyarginine are also suitable cationic polymers.

  In some aspects, additional surface additives that may optionally be used with the particulate superabsorbent polymer composition include odor-binding substances such as cyclodextrin, zeolites, inorganic or organic salts, and the like. Materials: Anti-caking additives, flow control agents, surfactants, viscosity control agents, etc. may be mentioned. In addition, surface additives may be used which perform several roles during surface deformation. For example, a single additive may be a surfactant, may be a viscosity modifier, and may react to crosslink the polymer chains.

  In some aspects, the particulate superabsorbent polymer of the present invention, such that the superabsorbent polymer composition has a water content of up to 10% by weight, or 1 to 6% by weight of the weight of the superabsorbent polymer composition The composition may be treated with water after the heat treatment step. This water may be added to the superabsorbent polymer along with one or more of the surface additives described above.

  The superabsorbent polymers of the present invention may desirably be prepared by two methods. The composition can be prepared continuously or discontinuously in a large scale industrial manner to carry out post-crosslinking according to the invention.

  According to one method, a partially neutralized monomer, such as acrylic acid, is converted to a gel by free radical polymerization in an aqueous solution in the presence of a crosslinker and any further components to break up the gel Dry, grind and sieve to desired particle size. The polymerization can be carried out continuously or discontinuously. In the present invention, the diameter of the high volume particulate superabsorbent polymer composition depends on the manufacturing process including milling and sieving. It is known to the person skilled in the art that the particle size distribution of superabsorbent polymer particles is similar to a normal distribution or bell curve. For various reasons, it is also known that the normal distribution of particle size distribution may bend in any direction.

  According to another method, inverse suspension polymerization and emulsion polymerization can also be used to prepare the products according to the invention. According to these methods, a partially neutralized aqueous solution of a monomer, such as acrylic acid, is dispersed in a hydrophobic organic solvent with the aid of a protective colloid and / or an emulsifier, and a free radical initiator The polymerization starts by The internal crosslinking agent may be dissolved in the monomer solution and metered with it, or may be added separately, optionally during the polymerization. The addition of the water-soluble polymer as graft substrate is optionally carried out by means of a monomer solution or by direct introduction into the oil phase. Water is removed azeotropically from the mixture and the polymer is filtered off and optionally dried. Internal crosslinking can be carried out by polymerization in a multifunctional crosslinking agent dissolved in the monomer solution and / or by reacting the appropriate crosslinking agent with the functional groups of the polymer during the polymerization process.

  The result of these methods is a superabsorbent polymer, or a superabsorbent polymer semi-finished product. The superabsorbent polymer semi-finished products used herein make the superabsorbent, including drying the material and rough grinding in a crusher to remove particles larger than 850 micrometers and particles smaller than 150 micrometers. Manufactured by repeating all of the steps.

  The particulate superabsorbent polymer composition of the present invention has a centrifugal retention capacity, 0.9 psi (6.2 kPa) load absorbency (AUL (0.9 psi (6.2 kPa))), gel bed permeability (GBP), Specific features or characteristics, as measured by 0.7 psi (4.8 kPa) pressure absorbency (AAP (0.7 psi (4.8 kPa))), and saline flow induction (SFC) Indicates

  The resulting CRC is stated as grams of liquid (g / g) retained per gram mass of sample, 20 g / g to 40 g / g, 22 g / g to 35 g / g, or 24 g / g to 30 g / g It may be.

  The load absorption of 0.9 psi (6.2 kPa) (AUL (0.9 psi (6.2 kPa))) may be 12 g / g to 30 g / g, or 15 g / g to 25 g / g.

  The gel bed permeability (GBP) may be at least 5 Darcy or more, or 10 Darcy to 200 Darcy, or 20 Darcy to 150 Darcy.

  The pressure absorbency of 0.7 psi (4.8 kPa) (AAP (0.7 psi (4.8 kPa))) may be from 20 g / g to 30 g / g.

The permeability measured in the saline flow induction value (SFC) test is 20 × 10 ⁻⁷ cm ³ · s · g ⁻¹ to 200 × 10 ⁻⁷ cm ³ · s · g ⁻¹ Good.

  The superabsorbent polymer composition according to the invention can be used in many absorbent articles, including sanitary napkins, diapers, or wound dressings, which rapidly produce large amounts of menstrual blood, urine or other bodily fluids. It has the property of absorbing. The agent according to the invention can hold the absorbed liquid even under pressure and allow further liquid to be distributed into the structure in the expanded state, as compared to the conventional current superabsorbent compositions. Thus, they are more desirably used at higher concentrations as compared to hydrophilic fiber materials, such as fluff. They are also suitable for use as a fluff-free uniform superabsorbent layer in diaper constructions, so that particularly thin articles are possible. Furthermore, the polymers are suitable for use in adult hygiene articles (incontinence products).

  An absorbent article, such as a diaper, is disposed between (a) a liquid-permeable top sheet; (b) a liquid-impermeable back sheet; and (c) between (a) and (b) A core comprising 100% by weight, or 50% to 100% by weight of particles of polyamine-coated SAP present, and 0% to 90% by weight of a hydrophilic fiber material; (d) above the core (c) And any tissue layer disposed directly underneath; and (e) an optional acquisition layer disposed between (a) and (c).

"Test procedure"
Centrifuge retention capacity test (CRC)
The CRC test measures the ability of a superabsorbent polymer to saturate and retain liquid after centrifugation at controlled conditions. The retention capacity obtained is stated as grams of liquid retained per gram mass of sample (g / g).

  Retention capacity is determined by placing 0.16 grams of the prescreened superabsorbent polymer sample in a water permeable bag containing the sample and using the test solution (0.9 weight percent sodium chloride in distilled water) as the sample. Measured by free absorption. Heat sealable tea bag materials, such as those available from Dexter Corporation (with offices in Windsor Rocks, Conn., USA) as Model No. 1234T heat sealable filter papers, work well for most applications. The bag was formed by folding the 5 inch by 3 inch sample bag material in half and heat sealing the two open ends to form a 2.5 inch by 3 inch rectangular pouch. The heat seal was 0.25 inch inward from the end of the material. After placing the sample in the pouch, the remaining open edge of the pouch was also heat sealed. An empty bag was made to serve as a control. Three samples were prepared to test each superabsorbent polymer composition.

  The sealed bag was immersed in a pan containing the test solution at the predetermined test temperature to ensure that the bag was held down until it was completely wet. After wetting, the samples were left in solution, removed from solution, and laid temporarily on a non-absorptive plane for a predetermined time of testing.

The wet bags were placed on the outer periphery of the basket and the wet bags were placed in the basket away from each other, and the basket was a suitable centrifuge capable of giving the sample a gravitational acceleration 350. One suitable centrifuge is a CLAY ADAMS DYNAC II, model # 0103, with a water collection basket, a digital rpm gauge, and a machined drainage basket suitable for holding and draining flat bag samples. When centrifuging multiple samples, the samples were placed at opposite positions in the centrifuge to balance the basket as it was rotated. The bags (including wet empty bags) were centrifuged for 3 minutes at 1,600 rpm (e.g. achieving a target gravity acceleration of 350 g with a variation of 240-360 g). Gravitational acceleration is defined as a unit of inertial force on an object subject to rapid acceleration or gravity equal to 32 ft / sec ² at sea level. The bags were removed and weighed, first weighing the empty bag (for control) and then the bag containing the superabsorbent polymer composition sample. The amount of solution retained by the superabsorbent polymer sample taking into account the solution retained by the bag itself is the centrifuge retention capacity (CRC) of the superabsorbent polymer, of fluid per gram of superabsorbent polymer Expressed as grams. More specifically, the holding capacity is expressed by the following formula. CRC = [sample bag after centrifugation-empty bag after centrifugation-dried sample mass] / dried sample mass.

  Three samples were tested and the results averaged to determine the CRC of the superabsorbent polymer composition.

Free-Expansion Gel Bed Permeability Test (FSGBP)
As used herein, a Free Expanded Gel Bed Permeability Test, also referred to as the Gel Bed Permeability (GBP) Test under 0 psi inflation pressure, generally refers to gel particles (eg, surface treated) under conditions referred to as "free swell" conditions Determine the permeability of the expanded bed of absorbent material or superabsorbent material (before surface treatment). The term "free expansion" means that the gel particles can absorb and expand the test solution without restraining load, as described below. A suitable device to conduct gel bed permeability testing is shown in FIGS. 1, 2 and 3 and is generally designated 500. Test device assembly 528 includes a sample container generally indicated at 530 and a plunger generally indicated at 536. The plunger includes an axis 538 with a cylinder bore open below the long axis, and a head 550 located at the bottom of the axis. The axial hole 562 has a diameter of 16 mm. The plunger head is attached to the shaft, for example by gluing. There are 12 holes 544 in the radial direction of the shaft axis, and every 90 degrees, 3 holes with a diameter of 6.4 mm are located. The shaft 538 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.

  Plunger head 550 has a concentric, inner ring of seven holes 560 and an outer ring of fourteen holes 554, all holes having a diameter of 8.8 millimeters and axially aligned 16 mm It is a hole of Plunger head 550 is machined from a LEXAN rod, or equivalent material, and has a height of about 16 mm and a diameter designed to fit but freely slide in cylinder 534 with minimal wall clearance . The total length of plunger head 550 and shaft 538 is 8.25 cm, and the top of the shaft can be machined to obtain plunger 536 of the desired mass. Plunger 536 includes a screen 564 of 100 mesh stainless steel cloth stretched and tensioned by two axes and attached to the lower end of plunger 536. The screen is attached to the plunger head 550 using an appropriate solvent that securely adheres to the plunger head 550. Care must be taken to avoid excess transfer of solvent to the open parts of the screen and to reduce the area open to the liquid flow. The acrylic solvent Weld-on 4 from IPS (Gardena, California, with offices in the United States) is a suitable solvent.

  The sample container 530 has a cylinder 534 and a screen 566 of 400 mesh stainless steel cloth stretched and biaxially stretched and attached to the lower end of the cylinder 534. The screen is attached to the cylinder using an appropriate solvent to ensure that the screen adheres to the cylinder. Care must be taken to avoid excess transfer of solvent to the open parts of the screen and to reduce the area open to the liquid flow. The acrylic solvent Weld-on 4 from IPS (Gardena, California, with offices in the United States) is a suitable solvent. The gel particle sample, shown as 568 in FIG. 2, is supported on screen 566 in cylinder 534 during the test.

The cylinder 534 may be drilled in a transparent LEXAN rod or equivalent material, or may be cut from a LEXAN tube or equivalent material, with an inner diameter of 6 cm (e.g. 28.27 cm ² cross section) 0.5 cm Wall thickness, and a height of about 7.95 cm. The steps are machined on the outside diameter of the cylinder 534 such that at the bottom 31 mm of the cylinder 534 there is a region 534a with an outside diameter of 66 mm. An O-ring 540, which conforms to the diameter of the area 534a, may be placed at the top of the step.

The annular weight 548 has a 2.2 cm diameter and 1.3 cm deep counter-bored hole so as to slide down freely onto the shaft 538. The annular weight has a 16 mm thru-bore 548a. Annular weight 548 can be made of stainless steel or any other suitable material that is resistant to corrosion in the presence of a test solution that is a 0.9 weight percent sodium chloride solution in distilled water. The combined mass of plunger 536 and annular weight 548 equals approximately 596 grams (g), 0.3 pounds per square inch (2.07 kPa), or 20 per inch on a 28.27 cm sample surface. Corresponding to the pressure applied to sample 568 of 7 dynes / cm ² (2.07 kPa).

  As described below, the sample container 530 generally rests on the crucible 600 as the test solution flows through the test apparatus during the test. The purpose of the weir is to divert the liquid that has overflowed from the top of the sample container 530 and to direct the overflow liquid to another collection device 601. The crucible can be placed above the balance 602 on which the beaker 603 collecting the saline that has passed through the expanded sample 568 rests.

  Place the plunger 536 with the weight 548 on top in the empty sample container 530 to perform the gel bed permeability test in the "free-swell" condition, the height from the top of the weight 548 to the bottom of the sample container 530 Was measured using a suitable gauge with an accuracy of 0.01 mm. The force applied to the thickness gauge should be as small as possible during the measurement, preferably less than 0.74 newtons. Measuring the combined height of each of the empty sample container 530, plunger 536 and weight 548, and tracking which plunger 536 and weight 548 were used when using multiple test devices This is very important. If the sample 568 saturates and expands, the same plunger 536 and weight 548 should be used for the measurement. It may be desirable for the bottom on which the sample cup 530 is placed to be standard and for the top surface of the weight 548 to be parallel to the bottom surface of the sample cup 530.

  The samples to be tested were prepared from superabsorbent polymer composition particles which were pre-sieved with a U.S. standard 30 mesh screen and left on the U.S. standard 50 mesh screen. As a result, the test sample contained a particle size of 300 to 600 micrometers. Superabsorbent polymer particles, for example, as described in W. S. It can be pre-sieved with RO-TAP Mechanical Sieve Shaker Model B, available from Tyler (Mentor Ohio). Sieve for 10 minutes. About 2.0 grams of sample was placed in the sample container 530 and allowed to diffuse evenly to the bottom of the sample container. Submerge a container with 2.0 grams of sample in it and no plunger 536 and weight 548 in 0.9% saline for 60 minutes to saturate the sample without any restraining load And let the sample expand freely. The sample cup 530 was placed on the mesh located in the liquid reservoir so that the sample cup 530 was lifted slightly above the bottom of the liquid reservoir during saturation. The mesh did not inhibit the flow of saline into the sample cup 530. A suitable mesh can be obtained from Eagle Supply and Plastic, Inc., which has offices in Appleton, Wisconsin, USA, as part number 7308. The saline did not completely cover the superabsorbent polymer composition particles as evidenced by the perfectly flat saline surface in the test cell. Also, the saline depth was not reduced as low as the surface in the cell was defined only by the swollen superabsorbent and not the saline.

  At the end of this period, the plunger 536 and weight 548 assembly was placed on the saturated sample 568 in the sample container 530 and the sample container 530, plunger 536, weight 548 and sample 568 were removed from solution. After removal and prior to measurement, leave sample container 530, plunger 536, weight 548, and sample 568 on a suitable flat, large grid non-deformable uniform thickness plate for 30 seconds did. Using the same thickness gauge previously used, saturated sample 568 by re-weighing the height from the top of weight 548 to the bottom of sample container 530, without changing the zero point from the initial height measurement. The thickness of was determined. The sample container 530, plunger 536, weight 548, and sample 568 may be placed on a flat large grid non-deformable uniform thickness plate that provides drainage. The plates have a total size of 7.6 cm x 7.6 cm, and each grid has a cell size of 1.59 cm long x 1.59 cm wide x 1.12 cm deep. A suitable flat, large grid non-deformable plate material can be cut to size, available from McMaster Carr Supply Company, Inc. with offices in Chicago, Illinois, USA, Parabolic Diffuser Panel, Catalog No. 1624K27 It is. This flat large mesh non-deformable plate must also be present when weighing the height of the first empty assembly. After engaging the thickness gauge, height measurements should be made as soon as possible. The height measurement obtained from the measurement of the empty sample container 530, the plunger 536 and the weight 548 is subtracted from the height measurement obtained after saturating the sample 568. The resulting value is the thickness or height "H" of the expanded sample.

  Permeability measurements were initiated by supplying a 0.9% saline flow to a sample container 530 having a saturated sample 568, a plunger 536, and a weight 548 therein. The flow rate of the test solution into the container was adjusted to cause the saline to overflow from the top of the cylinder 534, resulting in a consistent head pressure equal to the height of the sample container 530. The test solution may be added by any suitable means sufficient to hold a small but consistent amount of overflow from the top of the cylinder, for example using a metering pump 604. Overflow liquid is directed to a separate collection device 601. The amount of solution passing through sample 568 versus time was weighed gravimetrically using balance 602 and beaker 603. As the overflow began, data points from balance 602 were collected every second for at least 60 seconds. Data collection may be done manually or with data collection software. The flow rate (Q) through the expanded sample 568 was determined in grams per second (g / s) by a linear least squares fit to the fluid (grams) passing time (seconds) passing through the sample 568.

Permeable cm ² was obtained by the following formula:
K = [Q * H * μ] / [A * ρ * P].
Where: K = permeability (cm ² ), Q = flow rate (g / s), H = height of expanded sample (cm), μ = viscosity of liquid (poises) (about the test solution used in this test Approximately 1 centipoise), A = cross-sectional area of liquid flow (28.27 cm ² for the sample container used in this test), == liquid density (g / cm ³ ) (approximately 1 g / g for the test solution used in this test) cm ³ ), and P = hydrostatic pressure (dynes / cm ² ) (usually about 7,797 dynes / cm ² ). The hydrostatic pressure is calculated from P = ** g * h, where ρ = liquid density (g / cm ³ ), g = gravity acceleration, nominal 981 cm / sec ² , and h = liquid height, eg, this specification 7.95 cm for the gel bed permeability test described in

  At least two samples were tested and the results averaged to determine the gel bed permeability of the samples.

<Load absorption test (AUL (0.9 psi (6.2 kPa))))>
The load absorption (AUL) test showed that the superabsorbent polymer composition particles had a 0.9 weight percent sodium chloride solution in distilled water at room temperature (test solution) with the material loaded at 0.9 psi (6.2 kPa). Measure the ability to absorb). The AUL test apparatus consisted of:
AUL assembly including cylinder, 4.4 g piston and a standard 317 gm weight.
The parts of this assembly are described in further detail below.
Flat bottom square plastic trays wide enough so that the glass frit can lie on the bottom without contacting the tray wall. A plastic tray having a depth of 9 "x 9" (22.9 cm x 22.9 cm), 0.5 "to 1" (1.3 cm to 2.5 cm) was generally used for this test method.
Sintered glass frit, having a diameter of 9 cm, porosity "C" (25 to 50 micrometers). The frit was previously prepared through equilibration in saline (0.9 wt% sodium chloride in distilled water). The frit, in addition to washing with fresh saline at least twice, must be immersed in saline for at least 12 hours prior to AUL measurement.
· Whatman grade 1, round filter paper with a diameter of 9 cm.
Supply of saline solution (0.9% by mass sodium chloride in distilled water).

  Referring to FIG. 4, the cylinder 412 of the AUL assembly 400 used to contain the superabsorbent polymer composition particles 410 is machined-out to ensure substantially concentric inner diameter 1 inch (2.54 cm) ) Made of thermoplastic resin tube. After machining, a 400 mesh stainless steel wide cross 414 was attached to the bottom of the cylinder 412 by heating the steel wide cross 414 to a red heat in a flame, and the cylinder 412 was kept cold on the steel wide cross. In case of failure or breakage, a soldering iron can be used to finish the seal. Care must be taken to maintain a flat, smooth bottom and not distort within the cylinder 412.

  A 4.4 g piston (416) is made from a 1 inch (2.54 cm) diameter solid material (e.g. PLEXIGLAS (R)) and machined to fit closely without being constrained in cylinder 412 did.

A standard 317 gm weight 418 was used to provide a 62. 053 dynes / cm ² (0.9 psi (6.2 kPa)) suppression load. The weight was a 1-inch (2.5 cm) diameter cylindrical, stainless steel weight that was machined to fit closely without being constrained in the cylinder.

  Unless otherwise stated, a sample 410 corresponding to a layer of at least 300 gsm (0.16 g) of superabsorbent polymer composition powder particles was utilized for testing of the AUL. Sample 410 was taken from superabsorbent polymer composition particles pre-sieved with U.S. Standard # 30 mesh and remaining on U.S. Standard # 50 mesh. Superabsorbent polymer composition particles, for example, as described in W. S. It can be pre-sieved with RO-TAP.TM. Mechanical Sieve Shaker Model B, available from Tyler, Mentor Ohio. Sieve for 10 minutes.

  Before placing the superabsorbent polymer composition particles 410 in the cylinder 412, the interior of the cylinder 412 was wiped with an antistatic cloth.

  The desired amount of the screened sample of superabsorbent polymer composition particles 410 (0.16 g) was weighed onto a weighing paper and uniformly distributed over the wide cloth 414 at the bottom of the cylinder 412. The mass of superabsorbent polymer composition particles at the bottom of the cylinder was recorded as "SA" for the calculation of AUL described below. Care was taken that the superabsorbent polymer particles did not stick to the wall of the cylinder. AUL assembly comprising cylinder, piston, weight and superabsorbent polymer composition particles after carefully placing 4.4 g of piston 412 and 317 g of weight 418 on the superabsorbent polymer composition particles 410 of cylinder 412 Weighed 400 and recorded the mass as mass "A".

Sintered glass frit 424 (described above) was placed in plastic tray 420 with saline 422 added to an equal level to the upper surface of glass frit 424.
One round filter paper 426 was gently placed on the glass frit 424 and the AUL assembly 400 with superabsorbent polymer composition particles 410 was placed on the filter paper 426. The AUL assembly 400 was left on the filter paper 426 for a test time of 1 hour, taking care to keep the saline level in the tray constant. At the end of the one hour test time, the AUL apparatus was weighed and this value was recorded as mass "B".

AUL (0.9 psi (6.2 kPa)) was calculated as follows:
AUL (0.9 psi (6.2 kPa)) = (B-A) / SA.
Where A = mass of AUL device with dried SAP,
B = mass of AUL device with SAP after absorption for 60 minutes,
SA = actual SAP mass.

  At least two tests were performed and the results averaged to determine the AUL value under a 0.9 psi (6.2 kPa) load. The samples were tested at 23 ° C. and 50% relative humidity.

<0.7 psi (4.8 kPa) pressure absorption (AAP (0.7 psi (4.8 kPa))) test>
The absorbency at a pressure of 0.7 psi (4.8 kPa) (pressure load 50 g / cm ² ) was determined by the method described in EP-A-0 033 461, page 7. About 0.9 g of the particulate superabsorbent polymer composition was weighed into a cylinder with a sieve plate. The uniformly dispersed particulate superabsorbent polymer composition layer was placed under load in the form of a plunger exerting a pressure of 0.7 psi (4.8 kPa) or 50 g / cm ² . A pre-weighed cylinder was placed on a glass filter disc set up in a bowl containing 0.9% NaCl solution, the liquid level corresponding exactly to the height of the filter disc. After letting the cylinder apparatus suck up a 0.9% NaCl solution for 1 hour, it was weighed again, and AAP was calculated as follows: AAP = amount weighed out when out (cylinder apparatus + Particulate superabsorbent polymer composition)-containing weighed in (cylinder apparatus + granular superabsorbent polymer composition immersed to volume) / particulate superabsorbent polymer composition When weighed in (weighed in).

<Saline flow induction value (SFC) test>
Permeability to a common salt solution of 0.9% in the expanded state (SFC). Permeability in the expanded state (SFC test according to WO 95/22356). About 0.9 g of the particulate superabsorbent polymer composition was weighed into a cylinder with a sieve plate and carefully distributed on the surface of the sieve. Composition: Super granular superabsorbent polymer composition JAYCO synthetic [Composition: 2.0 g of potassium chloride as an anhydrous salt dissolved in 1 liter of distilled water; 2.0 g of sodium sulfate; 0.85 g of phosphoric anhydride Ammonium; 0.15 g of ammonium hydrogen phosphate; 0.19 g of calcium chloride; 0.23 g of magnesium chloride] and expanded at an opposing pressure of 20 g / cm ² for 1 hour. After determining the expanded height of the superabsorbent, 0.118 M NaCl solution was passed through the expanded gel layer from a level of supply vessel under constant hydrostatic pressure. During the measurement, the 0.118 M NaCl solution is uniformly distributed on the gel, and expanded with a special sieve cylinder that guarantees constant conditions (measurement temperature 20-25 ° C.) between measurements with respect to the state of the gel bed Covered the gel layer. The pressure acting on the expanded particulate superabsorbent polymer composition continued at 20 g / cm ² . Using a computer and a balance, the amount of fluid passing through the gel layer was determined at intervals of 10 seconds for 10 minutes as a function of time. Using regression analysis, the flow rate (g / s) through the expanded gel layer at t = 0 was determined at the midpoint of the flow between 2 and 10 minutes by extrapolating the gradient.

The SFC value (K) was calculated as follows:
K = F _s (t = 0) · L ₀ / (r · A · ΔP) = F _s (t = 0) · L ₀ / (139506)
Here, F _s (t = 0) is the flow velocity g / s,
L ₀ is the thickness cm of the gel layer,
r is the density of the NaCl solution (1.003 g / cm ³ ),
A is the area of the upper surface of the gel layer in the measuring cylinder (28.27 cm ² ),
ΔP is the hydrostatic pressure (4920 dynes / cm ² ) that squeezes the gel layer, and K is the SFC value [10 ⁻⁷ · cm ³ · s · g ⁻¹ ].

  The following comparative examples and examples, as well as semi-finished products are provided to illustrate the invention, but not to limit the scope of the claims. Unless stated otherwise, all parts and percentages are by weight.

Cross-linking agent 1: (EDA + 4 AGE) ethylene diamine-AGE
Ethylenediamine (60.1 g) and water (10.0 g) were reacted at 80 ° C. with allyl glycidyl ether (456.2 g). The clear, slightly yellowish product was an adduct of ethylenediamine with 4.0 mol of allyl glycidyl ether.

Crosslinking agent 2: (EDA + 4AGE + 0.035% SR454) ethylenediamine-AGE adduct
Ethylenediamine (60.1 g) and water (10.0 g) were reacted at 80 ° C. with allyl glycidyl ether (456.2 g). The clear, slightly yellowish product was an adduct of ethylenediamine with 4.0 mol of allyl glycidyl ether. Ethylene diamine-AGE adduct was added to the monomer mixture and 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA was added just prior to polymerization.

<< Crosslinking agent 3: (EDA + 4AGE + 0.5PO) ethylenediamine-AGE-PO >>
Ethylenediamine (60.1 g) and water (10.0 g) were reacted at 80 ° C. with allyl glycidyl ether (456.2 g). After reacting for 4 hours, propylene oxide (27.4 g) was put into a tube within 2 minutes. The mixture was stirred at 80 ° C. for 75 minutes and heated to 110 ° C. Water and unreacted propylene oxide were distilled under reduced pressure (20 mbar) and the final product was cooled to room temperature. The clear, slightly yellowish product was an adduct of ethylenediamine with 4.0 mol of allyl glycidyl ether.

Cross-linking agent 4: (EDA + 4 AGE + 0.5 PO + 0.035% SR 454) ethylene diamine-AGE-PO adducts
The procedure described in Crosslinker 3 was repeated and added to the monomer, and 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA, was added just prior to polymerization. .

Crosslinking agent 5: (diallylamine-AGE)
Diallylamine (97.1 g) and water (3.0 g) were reacted with allyl glycidyl ether (102.6 g) at 100 ° C. for 4.5 hours. Water and residual diallylamine were distilled at 115 ° C. under reduced pressure. The clear, slightly yellowish product was an adduct of diallylamine and 0.9 mol of allyl glycidyl ether.

Crosslinking agent 6: (diallylamine-AGE + 0.035% SR 454)
The procedure described in Crosslinker 5 was repeated to add 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA, just prior to polymerization.

<< Crosslinking agent 7: (Diallylamine-AGE-PO) >>
Diallylamine (97.1 g) and water (3.0 g) were reacted with allyl glycidyl ether (102.6 g) at 100 ° C. for 4.5 hours. Propylene oxide (17.4 g) was placed in a tube. After a further reaction at 100 ° C. for 70 minutes, water and residual propylene oxide were distilled at 115 ° C. under reduced pressure. The clear, slightly yellowish product was a composition of an adduct of diallylamine, allyl glycidyl ether and propylene oxide.

Crosslinker 8: (Diallylamine-AGE-PO + 0.035% SR454)
The procedure described in Crosslinker 7 was repeated and added to the monomer, and 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA, was added just prior to polymerization. .

<< Crosslinking agent 9: (HMDA-AGE) >>
Hexamethylenediamine (116.1 g) and water (10.0 g) were reacted at 80 ° C. with allyl glycidyl ether (456.2 g). The clear, slightly yellowish product was an adduct of hexamethylenediamine with 4.0 mol of allyl glycidyl ether, which is the crosslinker composition in the present invention.

Crosslinking agent 10: (diallylamine-AGE + 0.035% SR 454)
The procedure described in Crosslinker 9 was repeated and added to the monomer, and 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA, was added just prior to polymerization. .

<< Crosslinking agent 11: (HMDA-AGE-PO) >>
Hexamethylenediamine (116.1 g) and water (10.0 g) were reacted at 80 ° C. with allyl glycidyl ether (456.2 g). After reacting for 4 hours, propylene oxide (23.2 g) was put into a tube. After further reaction at 80 ° C. for 60 minutes, water and residual propylene oxide were removed by vacuum distillation at 115 ° C. The clear, slightly yellowish product was the crosslinker composition of the present invention, an adduct of hexamethylene diamine, 3.8 mol of allyl glycidyl ether, and 0.2 mol of propylene oxide.

Cross-linking agent 12: (Diallylamine-AGE-PO + 0.035% SR454)
Repeating the procedure described in Crosslinker 11, 0.035 wt% SR 454 which is an ethoxylated (3) trimethylolpropane triacrylate available from Sartomer Company of Easton PA, was added just prior to polymerization.

Granular Superabsorbent Polymer Composition
A particulate superabsorbent polymer composition was made as follows. In a polyethylene container equipped with an agitator and a cooling coil, 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 added to the caustic solution and the solution was again cooled to 20 ° C. The degree of neutralization of the acid group was 75 mol%. According to Tables 1-12 below, the internal crosslinking agent composition, and the predetermined amount of internal crosslinking agent composition, and 413 grams of glacial acrylic acid were added to the first solution and cooled to 4 to 6 ° C. Nitrogen was bubbled through the monomer solution for 10 minutes. The cooling coil was removed from the vessel. 20 g of a 1 wt% aqueous H ₂ O ₂ solution, 30 g of a 2 wt% aqueous sodium persulfate solution, and 18 g of a 0.5 wt% aqueous sodium erythorbate solution were added to the monomer solution to initiate the polymerization reaction. The agitator was turned off and the initiated monomer was allowed to polymerize for 20 minutes. The solids content of the material was 30%. The resulting hydrogel is chopped and extruded with a commercial extruder Hobart 4M6, 150 ° C. with an upward air flow on a 20 ′ ′ × 40 ′ ′ perforated metal tray using a Procter & Schwartz 062 hot air dryer. For 120 minutes, and downward with a stream of air for 6 minutes to make the final product water concentration less than 5% by weight. The dry particulate superabsorbent polymer composition is coarsely ground on a Prodeva Model 315-S crusher, milled on an MPI 666-F 3-stage roller mill, and sieved using a Minox MTS 600 DS3V, particles larger than 850 μm And particles less than 150 μm.

Examples 1 to 240 and Comparative Examples 1 to 36
According to Tables 1-12, including Examples 1-240, and Comparative Examples C1-C36, the internal crosslinker compositions 1-12 are added to the monomer solution of the superabsorbent polymer composition of Examples 1-240 to obtain particulate superabsorbent The polymer was further treated by surface crosslinking and optional surface treatment as shown in the table below.

In the table below, the following terms for particulate superabsorbent polymer composition are used: SX means surface cross-linking; pretreatment before SX applies the components on the surface of the superabsorbent polymer particles Post treatment after SX means surface treatment of surface cross-linked superabsorbent polymer particles; and EC means ethylene carbonate. The units of properties of the particulate superabsorbent polymer composition are: CRC (g / g); AUL (0.9 psi (6.2 kPa)) (g / g); GBP (Darcy); AAP (0.7 psi (4. 8kPa)) (g / g) , and a ^{SFC (10 -7 · cm 3 ·} s · g -1). In the table, all% means mass% as defined herein.

  Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Unless otherwise indicated, all numbers referring to the amounts of components, reaction conditions, etc. used in the specification and claims are understood to be modified by the term "about" in all instances unless otherwise indicated. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

  Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Unless otherwise indicated, all numbers referring to the amounts of components, reaction conditions, etc. used in the specification and claims are understood to be modified by the term "about" in all instances unless otherwise indicated. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.Hereinafter, examples of embodiments of the present invention will be listed.
[1]
A particulate superabsorbent polymer composition having increased permeability, said particulate superabsorbent polymer comprising
a) a polymerizable monomer, wherein the monomer is selected from unsaturated acid group-containing monomers, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof;
b) an internal crosslinking agent composition,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound, or
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or
(Iii) Internal crosslinker composition which is the reaction product of an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and one selected from an ethylenically unsaturated glycidyl compound and / or an ethylenically unsaturated polyglycidyl compound When;
Here, components a) and b) are polymerized and granulated to form a particulate superabsorbent polymer having particle surfaces, wherein at least 40% by weight of said particulate superabsorbent polymer has a particle size of 300 μm to 600 μm. Have
c) 0.01 to 5% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface crosslinker applied to the surface of said particles;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Particulate superabsorbent polymer composition.
[2]
A particulate superabsorbent polymer composition according to item 1, wherein
d) 0.01% by weight to 5% by weight based on the weight of the dried particulate superabsorbent polymer composition powder, and / or 0.01 to 5% by weight based on the weight of the dried polymer powder Multivalent metal salts;
Further include,
The particulate superabsorbent polymer composition has a gel bed permeability of 10 Darcy to 200 Darcy as determined by the gel bed permeability test described herein,
Particulate superabsorbent polymer composition.
[3]
e) The particulate superabsorbent polymer composition according to item 1, further comprising 0.01% by weight to 5% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a polyvalent metal salt.
[4]
f) The particulate superabsorbent polymer composition according to any one of the preceding items, further comprising 0.01 to 0.5% by weight of thermoplastic polymer based on the weight of the dried superabsorbent polymer composition object.
[5]
g) The particulate superabsorbent polymer composition according to any one of items 1 to 4, further comprising 0.01 to 1% by weight of a cationic polymer based on the weight of the dried particulate superabsorbent polymer composition .
[6]
0.01 to 1% by mass of the internal crosslinking agent composition based on the polymerizable monomer, and 0.001 to 1.0% by mass of the second internal crosslinking agent composition based on the polymerizable monomer A particulate superabsorbent polymer composition according to any one of the preceding items.
[7]
The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is ethylene glycol monoglycidyl ether, and related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide, (meth) allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3-epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol 7. The particulate superabsorbent polymer composition according to any one of items 1 to 6, selected from propane or pentaerythritol triglycidyl ether; polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or mixtures thereof.
[8]
Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units 8. A particulate superabsorbent polymer composition according to any one of the preceding items comprising a glycidyl compound comprising
[9]
9. The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate according to any one of items 1 to 8, Particulate superabsorbent polymer composition.
[10]
The saturated amine and / or the saturated polyamine may be (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methyl allylamine, methyl methallyamine Ethylmethallylamine and ethylallylamine; methyl-, ethyl-, propyl- and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino- -Methylaminopropane, bis (3-aminopropyl) methylamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4 Any of items 1 to 9, selected from 4,4'-diaminodiphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof A particulate superabsorbent polymer composition according to any one of the preceding claims.
[11]
11. Any one of items 1 to 10, wherein said saturated amine and / or said saturated polyamine is selected from ethylene diamine, hexamethylene diamine, diethylene triamine, or 2,2 '-[1,2-ethanediyl bis (oxy)] bis-ethanamine A particulate superabsorbent polymer composition according to one of the claims.
[12]
An unsaturated mono-ol of polyol, wherein the second internal crosslinking agent composition comprises methylene bis acrylamide or-methacrylamide, or ethylene bis acrylamide; diacrylate, or triacrylate, butanediol-or ethylene glycol diacrylate or-methacrylate -Or esters of polycarboxylic acids; trimethylolpropane triacrylate and alkoxylates thereof; allyl (meth) acrylate, triallyl cyanurate, diallyl ester of maleic acid, polyallyl ester, tetraallyloxyethane, di- and triallylamine, The particulate super-absorbent polymer according to any one of items 6 to 11, selected from allyl compounds, including allyl ester of tetraallyl ethylenediamine, phosphoric acid or phosphorous acid Composition.
[13]
12. Any of the items 1 to 12, wherein the unsaturated acidic group-containing monomer is selected from acrylic acid, methacrylic acid, vinyl acetic acid, vinyl sulfonic acid, methallyl sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid A particulate superabsorbent polymer composition according to one of the claims.
[14]
Item 1 to 13, further comprising 0 to 40% by mass, relative to the polymerizable monomer, of a comonomer selected from the group consisting of (meth) acrylamide, (meth) acrylonitrile, vinylpyrrolidone, hydroxyethyl acrylate, and vinylacetamide. Particulate superabsorbent polymer composition according to any one of the preceding claims.
[15]
A particulate superabsorbent polymer composition according to any of the preceding claims, wherein the surface crosslinker comprises ethylene carbonate.
[16]
The particulate superabsorbent polymer composition according to any one of claims 1 to 15, wherein the polymerizable monomer has a degree of neutralization of 50 mol% to 85 mol%.
[17]
19. A particulate superabsorbent polymer composition according to any one of the preceding items, having a gel bed permeability of 50 Darcy to 150 Darcy as determined by the gel bed permeability test described herein.
[18]
0.9 psi (6.2 kPa) load absorbency (AUL (0. 1 kPa), 12 g / g to 30 g / g, determined by the load absorption (0.9 psi (6.2 kPa)) test described herein. 9 psi (6.2 kPa))); or 15 g / g to 40 g / g, as determined by the pressure absorbency (0.7 psi (4.8 kPa)) test described herein. 7 psi (4.8 kPa) pressure absorbency (AAP (0.7 psi (4.8 kPa))); or 20 as determined by the Saline Flow Induced Value (SFC) test described herein × 10 ^-7 ・ Cm ³ ・ S ・ g ^-1 ~ 200 × 10 ^-7 ・ Cm ³ ・ S ・ g ^-1 20. A particulate superabsorbent polymer composition according to any of the preceding items, having a saline flow derivative of
[19]
A method of making a particulate superabsorbent polymer composition, comprising
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or
(Iii) 0.001 mass%, which is the reaction product of an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and one selected from an ethylenically unsaturated glycidyl compound and / or an ethylenically unsaturated polyglycidyl compound Preparing a superabsorbent polymer by polymerizing 1% by weight of the internal crosslinker composition;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer having a particle size of at least 40% of the particulate superabsorbent polymer of from 300 μm to 600 μm;
d) surface crosslink the particulate superabsorbent polymer with 0.001% to 5.0% by weight of surface crosslinker applied to the particle surface based on the weight of the dried superabsorbent polymer composition powder And
e) heat treating the surface crosslinked particulate superabsorbent polymer of step d) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form said surface crosslinked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Process for the production of particulate superabsorbent polymer compositions.
[20]
A method according to item 19;
f) 0.01 to 5% by weight of insoluble inorganic powder and / or dried based on the weight of the dry superabsorbent polymer composition powder, wherein the surface cross-linked granular superabsorbent polymer composition of step e) is dried Further comprising surface treating with 0.01% to 5% by weight of polyvalent metal salt based on the weight of the superabsorbent polymer composition,
The method wherein the superabsorbent polymer has a gel bed permeability of 20 Darcy to 200 Darcy as determined by the gel bed permeability test described herein.
[21]
A method according to item 19;
g) to 0.01% by mass to 5% by mass of the dry particulate superabsorbent polymer composition, based on the weight of the dry particulate superabsorbent polymer composition powder, Further comprising surface treating with 0.01% by mass to 5% by mass of polyvalent metal salt based on
The superabsorbent polymer has a gel bed permeability of 20 Darcy to 200 Darcy as determined by the gel bed permeability test described herein,
Method.
[22]
The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is ethylene glycol monoglycidyl ether, and related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide, (meth) allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3-epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol The method according to item 19, which is selected from propane or pentaerythritol triglycidyl ether; polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or a mixture thereof.
[23]
Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units 20. A method according to item 19, comprising a glycidyl compound comprising
[24]
The method according to item 19, wherein the ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.
[25]
The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl-, and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino A method according to items 19-24, selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof.
[26]
26. The method according to items 19-25, wherein the amine compound is selected from ethylenediamine, diallylamine, hexamethylenediamine, diethylenetriamine or 2,2 '-[1,2-ethanediylbis (oxy)] bis-ethanamine.
[27]
A method of making a particulate superabsorbent polymer composition, comprising
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
An internal crosslinking agent composition of 0.001% by mass to 1% by mass based on the monomers,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or
(Iii) Internal crosslinker composition which is the reaction product of an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and one selected from an ethylenically unsaturated glycidyl compound and / or an ethylenically unsaturated polyglycidyl compound When
Preparing a superabsorbent polymer by polymerizing
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer, wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm;
d) 0.01 to 5% by weight of insoluble inorganic powder of the surface-crosslinked particulate superabsorbent polymer of step c) based on the weight of the dried superabsorbent polymer composition, and / or dried superabsorbent Surface treating with 0.01 to 5% by weight of polyvalent metal salt based on the weight of the polymer composition;
e) surface cross-linking the particulate superabsorbent polymer with 0.001% to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface cross-linking agent applied to the particle surface And
f) heat treating the surface cross-linked particulate superabsorbent polymer of step e) at a temperature of 150 ° C to 250 ° C for 20 to 120 minutes to form a surface cross-linked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Process for the production of particulate superabsorbent polymer compositions.
[28]
27. A method according to item 27, wherein
g) the surface-crosslinked particulate superabsorbent polymer of step f) is 0.01-5% by weight insoluble inorganic powder and / or dried superabsorbent based on the weight of the dried superabsorbent polymer composition powder, and / or Surface treating with 0.01 to 5% by weight of a polyvalent metal salt based on the weight of the basic polymer composition powder,
The particulate superabsorbent polymer composition has a gel bed permeability of 20 to 200 Darcy, as determined by the gel bed permeability test described herein,
Method.
[29]
Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units 29. A method according to item 28, comprising a glycidyl compound comprising
[30]
30. The method according to item 27, wherein the ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.
[31]
The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl-, and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino 31. The method according to items 27 to 30, which is selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and a mixture thereof.
[32]
32. A method according to items 27-31, wherein the amine compound is selected from ethylenediamine, diallylamine, hexamethylenediamine, diethylenetriamine or 2,2 '-[1,2-ethanediylbis (oxy)] bis-ethanamine.
[33]
An absorbent article comprising: (a) a liquid-permeable top sheet; (b) a liquid-impermeable back sheet; and (c) a core disposed between (a) and (b), Said core comprising a core comprising 10% by weight to 100% by weight particulate superabsorbent polymer composition, and 0% by weight to 90% hydrophilic fiber material; (d) above and below said core (c) And (e) an optional acquisition layer disposed between (a) and (c);
The particulate superabsorbent polymer composition is
i) a monomer selected from an ethylenically unsaturated carboxylic acid, an anhydride of an ethylenically unsaturated carboxylic acid, a salt, or a derivative thereof;
ii) an internal crosslinking agent composition,
(Α) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Β) Ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and saturated glycidyl compound and / or saturated polyglycidyl compound, or
(Γ) an internal crosslinker composition which is the reaction product of an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and one selected from an ethylenically unsaturated glycidyl compound and / or an ethylenically unsaturated polyglycidyl compound When;
iii) 0.001% to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface cross-linking agent applied to the particle surface
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Absorbent article.
[34]
34. An absorbent article according to item 33, wherein the particulate superabsorbent polymer composition is
iv) further comprising 0.01 to 5% by weight of insoluble inorganic powder based on the weight of the dried superabsorbent polymer composition,
The particulate superabsorbent polymer composition has a gel bed permeability of 20 to 200 Darcy as determined by the gel bed permeability test described herein,
Absorbent article.
[35]
The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is ethylene glycol monoglycidyl ether, and related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide, (meth) allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ ~ C ₆ -Alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3-epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol 34. Absorbent article according to item 33, selected from propane or pentaerythritol triglycidyl ether; polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or mixtures thereof.
[36]
The ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound may comprise polyethylene glycol chains having up to 45 ethylene glycol units, or up to 20 ethylene glycol units, or up to 12 ethylene glycol units. 34. An absorbent article according to item 33, comprising.
[37]
Item 34. The absorbent article according to item 33, wherein the ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.
[38]
The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl-, and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino An absorbent article according to items 33 to 37, selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof.
[39]
An absorbent article according to items 33 to 38, wherein the amine compound is selected from ethylene diamine, hexamethylene diamine, diethylene triamine or 2,2 '-[1,2-ethanediyl bis (oxy)] bis-ethanamine.
[40]
The absorbent article according to items 33 to 39, wherein the absorbent article is a diaper.

Claims (40)

A particulate superabsorbent polymer composition having increased permeability, said particulate superabsorbent polymer comprising
a) a polymerizable monomer, wherein the monomer is selected from unsaturated acid group-containing monomers, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof;
b) an internal crosslinking agent composition,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound, or (ii) ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and saturated glycidyl Compound and / or saturated polyglycidyl compound, or (iii) reaction of one selected from ethylenically unsaturated amine and / or ethylenically unsaturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound An internal crosslinker composition which is a product;
Here, components a) and b) are polymerized and granulated to form a particulate superabsorbent polymer having particle surfaces, wherein at least 40% by weight of said particulate superabsorbent polymer has a particle size of 300 μm to 600 μm. Have
c) 0.01 to 5% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface crosslinker applied to the surface of said particles;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Particulate superabsorbent polymer composition. A particulate superabsorbent polymer composition according to claim 1, wherein
d) 0.01% by weight to 5% by weight based on the weight of the dried particulate superabsorbent polymer composition powder, and / or 0.01 to 5% by weight based on the weight of the dried polymer powder Multivalent metal salts;
Further include,
The particulate superabsorbent polymer composition has a gel bed permeability of 10 Darcy to 200 Darcy as determined by the gel bed permeability test described herein,
Particulate superabsorbent polymer composition.   The particulate superabsorbent polymer composition of claim 1, further comprising e) 0.01 wt% to 5 wt% of a polyvalent metal salt based on the weight of e) dried superabsorbent polymer composition powder.   f) The particulate superabsorbent polymer according to any one of claims 1 to 3, further comprising 0.01 to 0.5 wt% of a thermoplastic polymer based on the weight of the dried superabsorbent polymer composition. Composition.   g) The particulate superabsorbent polymer composition according to any one of claims 1 to 4, further comprising 0.01 to 1 wt% of a cationic polymer based on the weight of the dried particulate superabsorbent polymer composition. object.   0.01 to 1% by mass of the internal crosslinking agent composition based on the polymerizable monomer, and 0.001 to 1.0% by mass of the second internal crosslinking agent composition based on the polymerizable monomer A particulate superabsorbent polymer composition according to any one of the preceding claims. The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound may be ethylene glycol monoglycidyl ether and related C ₁ -C ₆ -alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide ( ) Allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ -C ₆ -alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3 -Epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol propane or pentaerythritol triglycidyl ace Le; polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, or mixtures thereof, the particulate superabsorbent polymer composition according to any one of claims 1 to 6.   Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units A particulate superabsorbent polymer composition according to any one of the preceding claims comprising a glycidyl compound comprising   9. The method according to any one of the preceding claims, wherein the ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate. Granular superabsorbent polymer composition.   The saturated amine and / or the saturated polyamine may be (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methyl allylamine, methyl methallyamine Ethylmethallylamine and ethylallylamine; methyl-, ethyl-, propyl- and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino- -Methylaminopropane, bis (3-aminopropyl) methylamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4 10. 4'-Diaminodiphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof according to claim 1 A particulate superabsorbent polymer composition according to any one of the preceding claims.   The saturated amine and / or the saturated polyamine are selected from ethylene diamine, hexamethylene diamine, diethylene triamine, or 2,2 '-[1,2-ethanediyl bis (oxy)] bis-ethanamine. A particulate superabsorbent polymer composition according to any one of the preceding claims.   An unsaturated mono-ol of polyol, wherein the second internal crosslinking agent composition comprises methylene bis acrylamide or-methacrylamide, or ethylene bis acrylamide; diacrylate, or triacrylate, butanediol-or ethylene glycol diacrylate or-methacrylate -Or esters of polycarboxylic acids; trimethylolpropane triacrylate and alkoxylates thereof; allyl (meth) acrylate, triallyl cyanurate, diallyl ester of maleic acid, polyallyl ester, tetraallyloxyethane, di- and triallylamine, 12. The particulate superabsorbent poly according to any one of claims 6 to 11, selected from allyl compounds, including allyl esters of tetraallyl ethylenediamine, phosphoric acid or phosphorous acid. Over the composition.   The monomer according to any of the preceding claims, wherein said unsaturated acidic group-containing monomer is selected from acrylic acid, methacrylic acid, vinylacetic acid, vinylsulfonic acid, methallylsulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid. A particulate superabsorbent polymer composition according to any one of the preceding claims.   The composition according to claim 1, further comprising 0 to 40% by weight of a comonomer selected from the group consisting of (meth) acrylamide, (meth) acrylonitrile, vinyl pyrrolidone, hydroxyethyl acrylate, and vinyl acetamide, based on the polymerizable monomer. A particulate superabsorbent polymer composition according to any one of 13.   A particulate superabsorbent polymer composition according to any one of the preceding claims, wherein the surface crosslinker comprises ethylene carbonate.   The particulate superabsorbent polymer composition according to any one of claims 1 to 15, wherein the polymerizable monomer has a degree of neutralization of 50 mol% to 85 mol%.   17. A particulate superabsorbent polymer composition according to any one of the preceding claims, having a gel bed permeability of 50 Darcy to 150 Darcy as determined by the gel bed permeability test described herein. 0.9 psi (6.2 kPa) load absorbency (AUL (0. 1 kPa), 12 g / g to 30 g / g, determined by the load absorption (0.9 psi (6.2 kPa)) test described herein. 9 psi (6.2 kPa))); or 15 g / g to 40 g / g, as determined by the pressure absorbency (0.7 psi (4.8 kPa)) test described herein. 7 psi (4.8 kPa) pressure absorbency (AAP (0.7 psi (4.8 kPa))); or 20 as determined by the Saline Flow Induced Value (SFC) test described herein × having ^{10 -7 · cm 3 · s ·} g -1 ~200 × 10 -7 · cm 3 · saline flow value of s · ^{g -1,} according to any one of claims 1 to 17 Granular superabsorbent polymer composition. A method of making a particulate superabsorbent polymer composition, comprising
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Superabsorbent polymer by polymerizing from 0.001% by weight to 1% by weight of an internal crosslinker composition which is the reaction product of an unsaturated glycidyl compound and / or a product selected from ethylenically unsaturated polyglycidyl compounds To prepare;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer having a particle size of at least 40% of the particulate superabsorbent polymer of from 300 μm to 600 μm;
d) surface crosslink the particulate superabsorbent polymer with 0.001% to 5.0% by weight of surface crosslinker applied to the particle surface based on the weight of the dried superabsorbent polymer composition powder And e) heat treating the surface crosslinked particulate superabsorbent polymer of step d) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form said surface crosslinked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Process for the production of particulate superabsorbent polymer compositions. 21. The method of claim 19, wherein
f) 0.01 to 5% by weight of insoluble inorganic powder and / or dried based on the weight of the dry superabsorbent polymer composition powder, wherein the surface cross-linked granular superabsorbent polymer composition of step e) is dried Further comprising surface treating with 0.01% to 5% by weight of polyvalent metal salt based on the weight of the superabsorbent polymer composition,
The method wherein the superabsorbent polymer has a gel bed permeability of 20 Darcy to 200 Darcy as determined by the gel bed permeability test described herein. 21. The method of claim 19, wherein
g) to 0.01% by mass to 5% by mass of the dry particulate superabsorbent polymer composition, based on the weight of the dry particulate superabsorbent polymer composition powder, Further comprising surface treating with 0.01% by mass to 5% by mass of polyvalent metal salt based on
The superabsorbent polymer has a gel bed permeability of 20 Darcy to 200 Darcy as determined by the gel bed permeability test described herein,
Method. The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound may be ethylene glycol monoglycidyl ether and related C ₁ -C ₆ -alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide ( ) Allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ -C ₆ -alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3 -Epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol propane or pentaerythritol triglycidyl ace Le; polyglycerol polyglycidyl ether is selected from sorbitol polyglycidyl ether, or mixtures thereof, The method of claim 19.   Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units 20. The method of claim 19, comprising a glycidyl compound comprising   The method according to claim 19, wherein the ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.   The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl- and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino The method according to claims 19-24, selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof.   26. The method according to claims 19-25, wherein the amine compound is selected from ethylenediamine, diallylamine, hexamethylenediamine, diethylenetriamine or 2,2 '-[1,2-ethanediylbis (oxy)] bis-ethanamine. A method of making a particulate superabsorbent polymer composition, comprising
a) at least one monomer selected from ethylenically unsaturated carboxylic acids, anhydrides of ethylenically unsaturated carboxylic acids, salts, or derivatives thereof, based on the superabsorbent polymer,
An internal crosslinking agent composition of 0.001% by mass to 1% by mass based on the monomers,
(I) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Ii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and a saturated glycidyl compound and / or a saturated polyglycidyl compound, or (iii) an ethylenically unsaturated amine and / or an ethylenically unsaturated polyamine, and an ethylenic Preparing a superabsorbent polymer by polymerizing with an internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
b) polymerizing the superabsorbent polymer;
c) granulating the superabsorbent polymer to form a particulate superabsorbent polymer, wherein at least 40% by weight of the particulate superabsorbent polymer has a particle size of 300 μm to 600 μm;
d) 0.01 to 5% by weight of insoluble inorganic powder of the surface-crosslinked particulate superabsorbent polymer of step c) based on the weight of the dried superabsorbent polymer composition, and / or dried superabsorbent Surface treating with 0.01 to 5% by weight of polyvalent metal salt based on the weight of the polymer composition;
e) surface cross-linking the particulate superabsorbent polymer with 0.001% to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition powder, of a surface cross-linking agent applied to the particle surface And f) heat treating the surface-crosslinked particulate superabsorbent polymer of step e) at a temperature of 150 ° C. to 250 ° C. for 20 to 120 minutes to form a surface cross-linked particulate superabsorbent polymer;
Contains and
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Process for the production of particulate superabsorbent polymer compositions. 28. The method of claim 27, wherein
g) the surface-crosslinked particulate superabsorbent polymer of step f) is 0.01-5% by weight insoluble inorganic powder and / or dried superabsorbent based on the weight of the dried superabsorbent polymer composition powder Surface treating with 0.01 to 5% by weight of a polyvalent metal salt based on the weight of the basic polymer composition powder,
The particulate superabsorbent polymer composition has a gel bed permeability of 20 to 200 Darcy, as determined by the gel bed permeability test described herein,
Method.   Polyethylene glycol chain wherein said ethylenically unsaturated glycidyl compound and / or said ethylenically unsaturated polyglycidyl compound has at most 45 ethylene glycol units, or at most 20 ethylene glycol units, or at most 12 ethylene glycol units 29. A method according to claim 28, comprising a glycidyl compound comprising   28. The method according to claim 27, wherein the ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.   The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl- and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino 31. The method according to claims 27-30, wherein the method is selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine, and mixtures thereof.   32. The method according to claims 27-31, wherein the amine compound is selected from ethylenediamine, diallylamine, hexamethylenediamine, diethylenetriamine or 2,2 '-[l, 2-ethanediyl bis (oxy)] bis-ethanamine. An absorbent article comprising: (a) a liquid-permeable top sheet; (b) a liquid-impermeable back sheet; and (c) a core disposed between (a) and (b), Said core comprising a core comprising 10% by weight to 100% by weight particulate superabsorbent polymer composition, and 0% by weight to 90% hydrophilic fiber material; (d) above and below said core (c) And (e) an optional acquisition layer disposed between (a) and (c);
The particulate superabsorbent polymer composition is
i) a monomer selected from an ethylenically unsaturated carboxylic acid, an anhydride of an ethylenically unsaturated carboxylic acid, a salt, or a derivative thereof;
ii) an internal crosslinking agent composition,
(Α) saturated amine and / or saturated polyamine, and ethylenically unsaturated glycidyl compound and / or ethylenically unsaturated polyglycidyl compound,
(Β) Ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and saturated glycidyl compounds and / or saturated polyglycidyl compounds, or (γ) ethylenically unsaturated amines and / or ethylenically unsaturated polyamines, and ethylenicity An internal crosslinker composition which is the reaction product of one selected from unsaturated glycidyl compounds and / or ethylenically unsaturated polyglycidyl compounds;
iii) 0.001 to 5.0% by weight, based on the weight of the dried superabsorbent polymer composition powder, comprising a surface cross-linking agent applied to the particle surface,
The particulate superabsorbent polymer composition is determined by a centrifugal retention volume of 20 g / g to 40 g / g as determined by the centrifugal retention volume test as described herein and a gel bed permeability test as described herein Have a gel bed permeability of at least 5 Darcy or more,
Absorbent article. An absorbent article according to claim 33, wherein the particulate superabsorbent polymer composition is
iv) further comprising 0.01 to 5% by weight of insoluble inorganic powder based on the weight of the dried superabsorbent polymer composition,
The particulate superabsorbent polymer composition has a gel bed permeability of 20 to 200 Darcy as determined by the gel bed permeability test described herein,
Absorbent article. The ethylenically unsaturated glycidyl compound and / or the ethylenically unsaturated polyglycidyl compound may be ethylene glycol monoglycidyl ether and related C ₁ -C ₆ -alkyl ethers or esters thereof; glycidol, ethylene oxide, propylene oxide ( ) Allyl glycidyl ether, polyethylene glycol monoglycidyl ether, related C ₁ -C ₆ -alkyl ethers or esters thereof; vinyl glycidyl ether, glycidyl (meth) acrylate, glycidyl (meth) allyl ether, or 1-halogen-2,3 -Epoxypropane; ethylene glycol or polyglycol diglycidyl ether; glycerol, trimethylol propane or pentaerythritol triglycidyl ace Le; polyglycerol polyglycidyl ether is selected from sorbitol polyglycidyl ether, or mixtures thereof The absorbent article of claim 33.   The ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound may comprise polyethylene glycol chains having up to 45 ethylene glycol units, or up to 20 ethylene glycol units, or up to 12 ethylene glycol units. 34. An absorbent article according to claim 33 comprising.   34. Absorbent article according to claim 33, wherein the ethylenically unsaturated glycidyl and / or the ethylenically unsaturated polyglycidyl compound is selected from (meth) allyl glycidyl ether or glycidyl (meth) acrylate.   The above amine compounds are (mono, di and poly) aminoalkanes, (mono, di and poly) amino polyethers, allylamine, alkyl (meth) allylamines such as methylallylamine, methylmethallylamine, ethylmethallylamine, and Ethyl allylamine; methyl-, ethyl-, propyl-, and butylamine, diallylamine, dimethallylamine, aniline, ethylenediamine, diethylenetriamine, hexamethylenediamine, trimethylhexamethylenediamine, neopentanediamine, 1,2-propylenediamine, 4,7-dioxadecane -1,10-diamine, 4,9-dioxadodecane-1,12-diamine, polyether diamine, polyalkylene glycol diamine, 3-amino-1-methyl amino propane, (3-aminopropyl) methylamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 1- (2-aminoethyl) piperazine, o-, m- or p-phenylenediamine, 4,4'-diamino 38. Absorbent article according to claims 33 to 37, selected from diphenylmethane, 1,4-diaminoanthraquinone, 2,4,6-triamino-1,3,5-triazine, aminopyridine, glucosamine and mixtures thereof .   39. Absorbent article according to claims 33 to 38, wherein the amine compound is selected from ethylene diamine, hexamethylene diamine, diethylene triamine or 2,2 '-[l, 2-ethanediyl bis (oxy)] bis-ethanamine.   The absorbent article according to claim 33, wherein the absorbent article is a diaper.

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